KR101809989B1 - Liquid crystal display device - Google Patents

Abstract

An object of the present invention is to provide a vertically aligned liquid crystal device using a positive-type liquid crystal which satisfies generally required characteristics such as voltage holding ratio and light resistance, and which has a short electro-optical response time.
A pair of liquid crystal alignment layers disposed on both sides of the liquid crystal layer; and a pair of liquid crystal alignment layers disposed on both sides of the liquid crystal layer, (A) a liquid crystal alignment layer containing a polymer having a group represented by the following formula (A1), wherein the liquid crystal alignment layer contains a positive-type liquid crystal and at least one electrode for generating a transverse electric field is provided on at least one side of the substrate, Liquid crystal display element.

Description

[0001] LIQUID CRYSTAL DISPLAY DEVICE [0002]

The present invention relates to a liquid crystal display element and an alignment agent. To a liquid crystal display element (LCD) using a positive type liquid crystal and a suitable alignment agent as a material for forming a liquid crystal alignment film of the liquid crystal display element.

As a liquid crystal display element capable of responding to a high viewing angle, a vertically aligned liquid crystal display element using a positive liquid crystal is known (see Patent Documents 1 to 3). Since such a liquid crystal display element is expected to be a moving image display device such as a cellular phone or a liquid crystal television, it is required to further increase the response time of the electro-optical effect in order to suppress the afterimage as much as possible while smoothly displaying the moving image . However, there is a problem that the liquid crystal response speed at the time of voltage application is slow in a vertically aligned liquid crystal display element using a positive liquid crystal (see Non-Patent Document 1).

With respect to this problem, there has been reported a technique for improving the quality of a liquid crystal alignment film by imparting a structure that imparts dielectric anisotropy to polymer side chains used in a liquid crystal alignment film (see Patent Documents 4 and 5). However, this patent document relates to a conventional vertical alignment device using a positive liquid crystal or a negative alignment liquid crystal using a positive liquid crystal, and has not been studied with respect to a vertical alignment device using the positive liquid crystal of the present invention.

From such a situation, development of a vertically aligned liquid crystal display device using a positive-type liquid crystal having a short electro-optic response time while satisfying characteristics such as a voltage holding ratio and light resistance generally required for a liquid crystal display element is desired.

Japanese Patent Application Laid-Open No. 10-333171 Japanese Patent Application Laid-Open No. 10-161145 Japanese Laid-Open Patent Publication No. 2009-25834 Japanese Patent Publication No. 2007-521361 Japanese Patent Publication No. 2007-521506

 T.Sakurai et al., SID 2010 DIGEST p.721-724

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a vertically aligned liquid crystal display element using a positive-type liquid crystal which satisfies generally required characteristics such as voltage holding ratio and light resistance, and has a short electro-optical response time.

In order to solve the above problems,

A pair of substrates disposed opposite to each other,

A liquid crystal layer disposed between the two substrates;

A pair of liquid crystal alignment layers disposed on both sides of the liquid crystal layer,

And electrodes for generating a transverse electric field which are arranged on at least one of the pair of substrates,

Wherein the liquid crystal layer contains a positive type liquid crystal, and

Wherein the liquid crystal alignment layer comprises,

[A] A liquid crystal aligning agent containing a polymer having a group represented by the following formula (A1) (hereinafter sometimes referred to as "[A] polymer") (hereinafter sometimes referred to as "liquid crystal aligning agent (A) ). ≪ / RTI >

(Wherein R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group, some or all of the hydrogen atoms of these groups may be substituted, R ² is a double 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 0 or 1.

The liquid crystal display element of the present invention is characterized in that the liquid crystal display element is provided with a liquid crystal alignment layer containing a positive type liquid crystal and a liquid crystal alignment layer formed of a liquid crystal aligning agent containing a polymer having the specific structure group Satisfactory electro-optic response time can be achieved.

The liquid crystal alignment layer is preferably a vertical liquid crystal alignment layer.

By using the vertical liquid crystal alignment film as the liquid crystal alignment film to be used, the liquid crystal display device can easily and reliably form the liquid crystal layer of the transverse electric field system and can effectively exhibit the above-mentioned characteristics.

R ³ in the formula (A1) is preferably represented by the following formula (A2).

(In the formula (A2), R ⁴ is a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a divalent heterocyclic group; R ⁵ is a linking group containing at least one of a methylene group which may have a substituent and an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic group, all or part of which may be substituted; R ⁶ is a (c + 1) -valent group other than (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or a heterocyclic compound; R ⁷ represents a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group Or an alkylcarbonyloxy group, b is 0 or 1, c is an integer of 1 to 9, d is 1 or 2, and R ⁴ , R ^5, and R ⁷ are each a plurality of R ⁴ , R ⁵ and R < ⁷ > may be the same or different.

According to the liquid crystal display device, the above-mentioned effect can be further improved by having R ³ in the polymer [A] contained in the liquid crystal aligning agent used has the specific structure described above.

The polymer [A] preferably has a polyorganosiloxane structure.

In the liquid crystal display element of the present invention, the polymer [A] has a polyorganosiloxane structure, so that the light resistance can be improved.

The liquid crystal aligning agent preferably further comprises at least one polymer selected from the group consisting of [B] polyamic acid and polyimide (hereinafter sometimes referred to as " [B] polymer ").

This liquid crystal display element can improve the solution characteristics of the liquid crystal aligning agent obtained by further containing the liquid crystal aligning agent [B] polymer to be used and the electrical characteristics of the obtained liquid crystal display element.

The polymer [B] is preferably obtained by using a diamine containing a cholestanyl group, a diamine containing a cholesteryl group, or a diamine represented by the following formula (A-1).

( ^I ) wherein X ¹ and X ² are each independently a single bond, -O-, -COO- or -OCO-, R ¹ is a methylene group or an alkylene group having 2 or 3 carbon atoms ;? is 0 or 1;? is an integer of 0 to 2, provided that? and? are not 0 at the same time; and? is an integer of 1 to 20).

The liquid crystal display element can improve the vertical alignment property by using a polymer obtained by using the specific diamine as the [B] polymer.

In the alignment agent of the present invention,

As a positive type liquid crystal alignment agent for a transverse electric field type liquid crystal display element,

[A] is characterized by containing a polymer having a group represented by the following formula (A1).

(Wherein R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group, some or all of the hydrogen atoms of these groups may be substituted, R ² is a double 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 0 or 1.

Since such an aligning agent contains a polymer having the above specific structure, it can be suitably used as a positive type liquid crystal aligning agent of a transverse electric field type liquid crystal display element.

The liquid crystal display element of the present invention can satisfy the general required characteristics such as the voltage holding ratio and the light resistance, and can improve the liquid crystal response speed. Further, the aligning agent of the present invention can be suitably used as a positive type liquid crystal aligning agent of a transverse electric field type liquid crystal display element.

(Mode for carrying out the invention)

<Liquid crystal display element>

In the liquid crystal display element of the present invention,

A pair of substrates disposed opposite to each other,

A liquid crystal layer disposed between the two substrates,

A pair of liquid crystal alignment layers disposed on both sides of the liquid crystal layer,

And electrodes for generating a transverse electric field which are arranged on at least one of the pair of substrates,

Wherein the liquid crystal layer contains a positive type liquid crystal, and

Wherein the liquid crystal alignment layer comprises,

[A] A liquid crystal display element formed of a liquid crystal aligning agent containing a polymer having a group represented by the following formula (A1).

The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) and (2).

[(1) Process]

First, the liquid crystal aligning agent (A) is applied onto the substrate, and then the coated surface is heated to form a coating film on the substrate. The liquid crystal aligning agent (A) will be described later. A liquid crystal aligning agent (A) is preferably provided on an electrode formation surface in the case of having a pair of substrates provided with electrodes for generating a transverse electric field on at least one of the substrates and having electrodes on the substrate, A coating method, a printing method, a spin coating method, or an ink-jet printing method, and then each coated surface is heated to form a coated film. Here, since the liquid crystal display element of the present invention is excellent in printing property, it is preferable to use the offset printing method or the inkjet printing method as a coating method from the viewpoint of maximizing the excellent effects of the present invention.

Examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film to be formed on one surface of the substrate, an ITO film made of NESA film (a registered trademark of PPG Corporation of the US) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) . In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photoetching after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern in forming a transparent conductive film, have. When applying the liquid crystal aligning agent, a functional silane compound, a functional titanium compound or the like is preferably added to the surface of the substrate on which the coating film is to be formed in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film The pre-treatment for pre-coating may be carried out.

As the electrode for generating a transverse electric field, a transparent conductive film patterned in a comb shape is suitably used.

Preheating (prebaking) is preferably performed for the purpose of preventing the liquid flow of the applied aligning agent after application of the liquid crystal aligning agent (A). The prebaking temperature is preferably 30 ° C to 200 ° C, more preferably 40 ° C to 150 ° C, and particularly preferably 40 ° C to 100 ° C. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the acid units contained in the polymer. The firing (post-baking) temperature is preferably 80 to 300 캜, more preferably 120 to 250 캜. The post baking time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

The coating film formed as described above can be used as it is as a liquid crystal alignment film, but may be provided for use after rubbing treatment as desired.

[(2) Process]

Two substrates each having the liquid crystal alignment film formed thereon as described above are prepared, and the liquid crystal is arranged between the two substrates arranged opposite to each other to manufacture a liquid crystal cell. Here, when the coating film is subjected to the rubbing treatment, the two substrates are opposed to each other such that the rubbing directions of the coating films are at a predetermined angle, for example, orthogonal or anti-parallel to each other.

To place the liquid crystal between the substrates, for example, the following two methods can be used.

The first method is a conventionally known method. First, two substrates are opposed to each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other. The peripheral portions of the two substrates are bonded together using a sealant, The liquid crystal is injected and filled in the cell gap, and then the injection port is sealed, whereby the liquid crystal cell can be manufactured.

The second method is a method called ODF (One Drop FIll) method in which a sealing agent of, for example, an ultraviolet light hardening property is applied to a predetermined place on one of the two substrates on which a liquid crystal alignment film is formed, The liquid crystal cell can be manufactured by dropping the liquid crystal on the liquid crystal alignment film surface, bonding the other substrate to the liquid crystal alignment film so as to face each other, and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealant.

Regardless of the method, the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used has an isotropic phase, and then slowly cooled to room temperature, It is preferable to remove the orientation.

The liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell.

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

Examples of the positive-type liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable. For example, a cypher base liquid crystal, an agglutinative liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane liquid crystal, Based liquid crystal, a fluorine-based liquid crystal having a positive dielectric anisotropy, and a cyanide-based liquid crystal material having a positive dielectric anisotropy, such as an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, A liquid crystal including at least one of liquid crystal and the like can be used.

As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate having a cellulose acetate protective film sandwiched between a polarizing film called &quot; H film &quot; in which iodine is absorbed while stretching polyvinyl alcohol in a stretched orientation, .

&Lt; Liquid crystal aligning agent (A) &gt;

The liquid crystal aligning agent (A) used in the formation of the liquid crystal alignment layer of the liquid crystal display element of the present invention,

[A] contains a polymer having a group represented by the formula (A1).

Further, the liquid crystal aligning agent (A) may contain "other polymer" such as a [B] polymer described later. Further, the liquid crystal aligning agent (A) may contain other components within the range not impairing the effect of the present invention. This liquid crystal aligning agent (A) develops vertical orientation. Each component will be described in detail below.

<[A] Polymer>

The polymer [A] has a group represented by the formula (A1).

[The group represented by the formula (A1)

R ¹ in the formula (A1) is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group. Some or all of the hydrogen atoms of these groups may be substituted.

Examples of the alkylene group having 2 to 30 carbon atoms represented by R ¹ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, , A tetradecylene group, a hexadecylene group, an octadecylene group, a nonadecylene group, an eicosylene group, a hemexocylene group, a docosylene group, a tricoxylene group, a tetracosylene group, a pentacosylene group, A silylene group, a heptacosylene group, an octacosylene group, a nonacosylene group, and a triacontylene group. Of these, in order to stably exhibit the liquid crystal alignment, it is preferable to use an aromatic hydrocarbon group such as an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, An alkylene group having 8 to 20 carbon atoms such as a silylene group is preferable.

R ² is a linking group including a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom. Examples of R ² include an etendiyl group, an ethynediyl group, an ester group, a methanediyloxy group, a fluoromethanediyloxy group, and a difluoromethanediyloxy group. R ² may contain any of the above bonds, but may contain a combination of these bonds. When R &lt; ¹ &gt; is a phenylene group or a cyclohexylene group, it is preferable that R &lt; ² &gt; 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 solvents. Also, a is 0 or 1.

R ³ is a group having at least two monocyclic structures, and is preferably a group exhibiting positive or negative dielectric anisotropy. The monocyclic structure is a structure which does not have a so-called condensed ring structure in which one cyclic structure is present independently from other cyclic structures, and the bond of one cyclic structure is shared with other cyclic structures. As the monocyclic structure, any of an alicyclic structure, an aromatic cyclic structure and a heterocyclic structure may be used, or a combination thereof may be used.

R ³ is not particularly limited as long as it is a group having at least two monocyclic structures, and R ³ is preferably a group represented by the following formula (A2).

In the formula (A2), R ⁴ is a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a divalent heterocyclic group. Some or all of the hydrogen atoms of these groups may be substituted. R ⁵ is a linking group comprising at least one of a methylene group which may have a substituent and an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic group. R ⁶ is a (c + 1) -valent group excluding (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or a heterocyclic compound. Some or all of the hydrogen atoms of these groups may be substituted. R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group. b is 0 or 1; and c is an integer of 1 to 9. d is 1 or 2; When there are a plurality of R ⁴ , R ⁵ and R ⁷ each, a plurality of R ⁴ , R ⁵ and R ⁷ may be the same or different.

By introducing the group represented by the formula (A2) into the side chain of the polymer [A] contained in the liquid crystal aligning agent, the electrooptical responsiveness of the obtained liquid crystal display element can be further increased. In the formula (A2), R ⁴ is a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a divalent heterocyclic group. Examples of the divalent heterocyclic group include a pyridinylene group, a pyridazinylene group, and a pyrimidinylene group.

In the formula (A2), R ⁵ represents a group selected from the group consisting of a methylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, ⁴ and R ⁶ , and can be appropriately selected in accordance with the orientation and induction anisotropy required for the [A] polymer. Examples of R ⁵ include a methanediyl group, an ethanediyl group, a propanediyl group, an ethanediyl group, an ethynylthio group, an ether group, an ester group, a methanediyloxy group, an ethanedioxy group, a fluoromethanedioxy group, a difluoro Methanedioxy group and the like. Among them, an ethanediyl group, an ethynediyl group, an ester group, a methanediyloxy group, and a difluoromethanediyloxy group are preferable. Since b is 0 or 1, R ⁵ may or may not be contained in the design of the side chain structure.

In the formula (A2), R ⁶ is a (c + 1) -valent group excluding (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or a heterocyclic compound. and c is an integer of 1 to 9. As R ⁶ , for example, when c is 1, there can be mentioned the same groups as the divalent groups exemplified as R ⁴ above.

In the formula (A2), R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group and a propoxycarbonyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group and the like , And the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

In the above formula (A2), when R ⁶ has a plurality of substituents (R ⁷ ), different ones may be used in combination. As a combination when R ⁶ has a plurality of substituents, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, and a combination of a cyano group and an alkyl group are preferable in order to stably express the desired dielectric anisotropy. Also, c is an integer of 1 to 9.

If the polymer [A] has a group having a structure represented by the above formula (A1), a known polymer main chain can be appropriately selected, but a polyorganosiloxane, a polyimide, a polyamic acid, a polyacrylate, , A poly (styrene-phenylmaleimide) derivative, a cellulose derivative, a polyester, a polyamide, a polystyrene derivative and a polyamic acid ester in the main chain structure is preferable in terms of electrical characteristics and the polyorganosiloxane Hereinafter sometimes referred to as &quot; [a] polyorganosiloxane compound &quot;).

When the polymer [A] contained in the liquid crystal aligning agent has a polyorganosiloxane structure,

[a] containing a polyorganosiloxane compound,

The polyorganosiloxane compound [a]

A part derived from a polyorganosiloxane having an epoxy group,

It is preferable to have a moiety derived from a compound having a carboxyl group represented by the following formula (A1-C) (hereinafter occasionally referred to as "specific carbonic acid").

In the formula (A1-C), R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group. Some or all of the hydrogen atoms of these groups may be substituted. R ² is a linking group including a double 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. a is 0 or 1;

Since the polyorganosiloxane compound contained in the liquid crystal aligning agent has a structure derived from the specific compound, a structure having dielectric anisotropy is introduced into the side chain, and a liquid crystal alignment film formed using the liquid crystal aligning agent The electric characteristics and the afterimage characteristics are further improved and the response time is further shortened. Further, by using the reactivity between the epoxy group and the carboxyl group, it is possible to easily introduce a structure having a dielectric anisotropy represented by the formula (A1-C) as a side chain in the polyorganosiloxane as a main chain.

<[A] polyorganosiloxane compound>

The [a] polyorganosiloxane compound has a part derived from a polyorganosiloxane having an epoxy group and a part derived from a specific carbonic acid represented by the formula (A1-C). The polymer [A] contained in the liquid crystal aligning agent (A) has such a specific structural unit that a structure having dielectric anisotropy is introduced into the side chain, and a liquid crystal display having a liquid crystal alignment film formed using the liquid crystal aligning agent The device further improves the electrical characteristic and the afterimage characteristic, and the response time is further shortened. Further, by utilizing the reactivity between the epoxy group and the carboxyl group, a structure having the dielectric anisotropy represented by the above formula (1) as a side chain can be easily introduced into the polyorganosiloxane as a main chain.

It is considered that the polyorganosiloxane compound [a] is mainly obtained as a reaction product of the epoxy group of the polyorganosiloxane and the carboxyl group of the specific carbonic acid. However, in order to facilitate the following description, A] polyorganosiloxane compound contained in the liquid crystal aligning agent (A) divided into a part derived from the organosiloxane (and a derivative thereof) and a part derived from the specific carbon acid will be described.

[Parts derived from a polyorganosiloxane having an 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 main chain of the polyorganosiloxane in the structure of the [a] polyorganosiloxane compound. As described above, in the [a] polyorganosiloxane compound, it is considered that most epoxy groups do not have an initial structure due to reaction with a specific carbonic acid, but there may be a case where a specific carbonic acid is bonded to a part other than an epoxy group . Therefore, in the present invention, it is referred to as &quot; a part derived from a polyorganosiloxane having an epoxy group &quot;

Since the polyorganosiloxane compound [a] includes a moiety derived from a polyorganosiloxane having an epoxy group such as a glycidyl group, a glycidyloxy group, or an epoxycyclohexyl group, the liquid crystal aligning agent (A) Electric characteristics such as orientation and voltage holding ratio are further improved.

The epoxy group is preferably a group represented by the following formula (X ¹ -1-1) or (X ¹ -2-1). By including in the polyorganosiloxane having the structural unit represented by the above formula (1) a group represented by the formula (X ¹ -1-1) or (X ¹ -2-1), the polyorganosiloxane of the liquid crystal aligning agent (A) It becomes easy to introduce a side chain group derived from a compound having a specific structure represented by the formula (1) into the organosiloxane compound.

In the above formulas (X ¹ -1 -1) and (X ¹ -2 -1), * indicates a binding hand.

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

[Method of synthesizing polyorganosiloxane having epoxy group]

The polyorganosiloxane having an epoxy group is preferably obtained by subjecting a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound to hydrolysis in the presence of a suitable organic solvent, Or by hydrolysis and condensation.

Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidylsilane, 3-glycidyloxypropyldimethylethoxysilane, 2- 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyl Glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldi 4-glycidyloxybutyldimethylmethoxysilane, 4-glycidyloxybutyldimethylethoxy (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) Ethoxy silane, 3- (3,4-epoxycyclohexyl) propyl triethoxy silane and the like. These may be used alone or in combination of two or more.

As other silane compounds, for example,

As a compound having one silicon atom,

Having four hydrolysable groups,

Tetrachlorosilane; Tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,

As having three hydrolyzable groups,

Trihalosilanes such as trichlorosilane; Trialkoxysilanes such as trimethoxysilane and triethoxysilane; Fluorotrichlorosilane; Fluorotrialkoxysilanes such as fluorotrimethoxysilane and fluorotriethoxysilane; Alkyl trichlorosilanes such as methyltrichlorosilane; Alkyltrialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane; Fluorinated alkyl trichlorosilanes such as 2- (trifluoromethyl) ethyl trichlorosilane; Fluorinated alkyltrialkoxysilanes such as 2- (trifluoromethyl) ethyltrimethoxysilane and 2- (trifluoromethyl) ethyltriethoxysilane; Hydroxyalkyl trichlorosilane such as hydroxymethyl trichlorosilane; Hydroxyalkyltrialkoxysilane such as hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane and the like; (Meth) acryloxyalkyltrichlorosilane such as 3- (meth) acryloxypropyltrichlorosilane; (Meth) acryloxyalkyltrialkoxysilane such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane; Mercaptoalkyl trichlorosilanes such as mercaptomethyl trichlorosilane and 3-mercaptopropyl trichlorosilane; Mercaptoalkyltrialkoxysilanes such as mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane; Alkenyl trichlorosilane such as vinyl trichlorosilane and allyl trichlorosilane; Alkenyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and allyltriethoxysilane; Aryl trichlorosilane such as phenyl trichlorosilane; Aryl trialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane, and the like,

As having two hydrolyzable groups,

Alkyldichlorosilane such as methyldichlorosilane; Alkyldialkoxysilanes such as methyldimethoxysilane and methyldiethoxysilane; Dialkyldichlorosilanes such as dimethyldichlorosilane; Dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; (Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane; (Methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane; (Methyl) (3-mercaptopropyl) dichlorosilane, and other mercaptoalkyldichlorosilanes; (Methyl) (3-mercaptopropyl) dimethoxysilane, and other alkyl mercaptoalkyl dialkoxysilanes; (Methyl) (vinyl) dichlorosilane, and other alkylalkenyldichlorosilanes; Dialkenyldichlorosilane such as divinyldichlorosilane; Dialkenyldialkoxysilanes such as divinyldimethoxysilane; Diaryldichlorosilane such as diphenyldichlorosilane; Diaryldialkoxysilanes such as diphenyldimethoxysilane;

Having one hydrolyzable group,

Dialkyl chlorosilanes such as chlorodimethylsilane; Dialkylalkoxysilanes such as methoxydimethylsilane; Trialkylhalosilanes such as chlorotrimethylsilane, bromotrimethylsilane and iodotrimethylsilane; Trialkylalkoxysilanes such as methoxytrimethylsilane; Dialkyl alkenyl chlorosilanes such as (chloro) (vinyl) dimethylsilane; (Methoxy) (vinyl) dimethylsilane, and other dialkylalkenylalkoxysilanes; Diarylalkylchlorosilanes such as (chloro) (methyl) diphenylsilane; And diarylalkylalkoxysilanes such as (methoxy) (methyl) diphenylsilane.

As a commercially available product, for example,

KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X- X-22-170B, X-22-170D, X-22-170DX, X-22-176B, X-22-170B, X- 22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X- X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, KR-212, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, K56002, KF6003, KR- KR5230, KR5235, KR9218 and KR9706 (all manufactured by Shin-Etsu Chemical Co., Ltd.);

Glass Resin (manufactured by Showa Denko K.K.);

SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (manufactured by Toray Dow Corning);

FZ3711 and FZ3722 (manufactured by Nippon Unicar Co., Ltd.);

DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS- 227, PSD-0332, PDS-1615, PDS-9931 and XMS-5025 (all manufactured by Chisso Corporation);

Methyl silicate MS51, methyl silicate MS56 (all manufactured by Mitsubishi Chemical Corporation);

Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.);

GR100, GR650, GR908 and GR950 (all manufactured by Showa Denko K.K.).

Of these other silane compounds, tetraethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltri (meth) acrylate, (Meth) acrylates such as methoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane are preferable Do.

The polyorganosiloxane having an epoxy group preferably used in the present invention preferably has an epoxy equivalent of 100 to 10,000 g / mol, more preferably 150 to 1,000 g / mol, for introducing a side chain having dielectric anisotropy in a sufficient amount And particularly preferably 150 to 300 g / mol. Therefore, when synthesizing a precursor of a polyorganosiloxane having an epoxy group, the ratio of the silane compound to the other silane compound is adjusted so that the epoxy equivalent of the polyorganosiloxane having the epoxy group is within the above range . In synthesizing the polyorganosiloxane having an epoxy group used in the present invention, it is more preferable to use only the silane compound and not use any other silane compound.

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

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

The amount of the organic solvent to be used is preferably 10 parts by mass to 10,000 parts by mass, more preferably 50 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the total silane compound. The amount of water used when preparing the polyorganosiloxane having an epoxy group is preferably 0.5 to 1 mol, and more preferably 1 to 30 mol per mol of the total silane compound.

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

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

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene; And quaternary organic amines such as tetramethylammonium hydroxide. In view of the fact that the reaction proceeds mildly among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

As the catalyst for producing the polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, a target polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing a side reaction such as ring opening of an epoxy group, Do. The liquid crystal aligning agent (A) containing a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a specific carboxylic acid is suitable because of its excellent storage stability. This is because, as indicated in Chemical Reviews, vol. 95, p1409 (1995), when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis and condensation reaction, a random structure, a ladder- Structure is formed, and a polyorganosiloxane having a small content of silanol groups is obtained. In the case where the condensation reaction between the silanol groups is suppressed because the content of the silanol groups is small and the liquid crystal aligning agent (A) contains the other polymer described later, the condensation reaction between the silanol group and the other polymer It is inferred that the storage stability is excellent.

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used differs depending on the kind of the organic base and the reaction conditions such as the temperature and the like and should be set appropriately. For example, it is preferably 0.01 to 3 moles per mole of the total silane compound, more preferably 0.05 One to one.

The hydrolysis or hydrolytic condensation reaction in the production of a polyorganosiloxane having an epoxy group can be carried out by dissolving an epoxy group-containing silane compound and, if necessary, other silane compounds in an organic solvent, mixing the solution with an organic base and water For example, by heating with an oil bath or the like.

In the hydrolysis / condensation reaction, the heating temperature of the oil bath is preferably 130 ° C or lower, more preferably 40 ° C to 100 ° C, preferably 0.5 hours to 12 hours, more preferably 1 hour to 8 hours It is preferable to heat it. During the heating, the mixed solution may be stirred or refluxed.

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of this cleaning, it is preferable that the cleaning is performed by washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 mass% or the like. The washing is carried out until the water layer after the washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain a polyorganosiloxane having a desired epoxy group Siloxane can be obtained.

In the present invention, a commercially available polyorganosiloxane having an epoxy group may be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21 and EMS-32 (manufactured by Chisso Corporation).

The [a] polyorganosiloxane compound may be a part derived from a hydrolyzate produced by hydrolysis of the polyorganosiloxane itself having an epoxy group or a hydrolyzed condensate obtained by hydrolysis and condensation of polyorganosiloxanes having an epoxy group And the like. These hydrolyzates and hydrolyzed condensates which are the constituent materials of this part can also be synthesized in the same manner as the hydrolysis and condensation conditions of the polyorganosiloxane having an epoxy group.

[Part derived from a specific carbon acid]

This part represented by the formula (A1) is a structure derived from an epoxy group mainly extending from the main chain of the polyorganosiloxane among the structure of the polyorganosiloxane compound of the polymer [A] contained in the liquid crystal aligning agent (A) And corresponds to a side chain structure having a structure derived from a carboxyl group bonded as a starting point. However, in the present invention, it is also referred to as &quot; a part derived from a specific carbon acid &quot; including a case where a specific carbon acid bonds to a part other than an epoxy group.

The formula (A1) of R ¹ ~R ^3, and a description of R ⁴ ~R ⁷ of the group represented by the formula is preferred as R ³ (A2), it is as described above.

Examples of the compound having a carboxyl group represented by the formula (A1-C) include compounds represented by the following formulas (D-1) to (D-25).

In the formulas (D-1) to (D-25), R ³ is the same as in the formula (A1). m is an integer of 1 to 30;

Examples of the group represented by the formula (A2) include groups represented by the following formulas (E-1) to (E-123).

In the formulas (E-1) to (E-123), R represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Each X independently represents a hydrogen atom or a fluorine atom.

Examples of the alkyl group represented by R include a methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, n-pentyl group and n-hexyl group. Examples of the alkoxy group represented by R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

[Method for synthesizing a specific carbon acid]

The order of synthesis of the specific carbonic acid is not particularly limited, and it can be carried out by combining conventionally known methods. As a typical synthetic procedure, for example, (1) a method of reacting a compound having a phenol skeleton with a compound in which an alkyl chain portion of a higher fatty acid ester is substituted with a halogen under basic conditions to obtain a (2) reacting a compound having a phenol skeleton with ethylene carbonate to produce a terminal alcohol compound, reacting the hydroxyl group with a halogenated benzene sulfonyl chloride to form a terminal alcohol compound, and And then reacting the activated portion with methyl benzoate containing a hydroxyl group to produce a bond with a hydroxyl group of a methyl benzoate containing a hydroxyl group as a substituent and a hydroxyl group of a terminal alcohol compound with elimination of a sulfonyl moiety, Is reduced to give a specific carbonic acid. However, the synthesis order of the specific carbonic acid is not limited to these.

&Lt; Synthesis method of [a] polyorganosiloxane compound &gt;

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

The specific carbonic acid is used in an amount of preferably 0.001 to 10 moles, more preferably 0.01 to 5 moles, and still more preferably 0.05 to 2 moles, based on 1 mole of the epoxy group of the polyorganosiloxane.

In the present invention, a part of the specific carbonic acid may be substituted by a compound represented by the following formula (4) within the range not to impair the effect of the present invention. In this case, the synthesis of the [a] polyorganosiloxane compound is carried out by reacting a mixture of a polyorganosiloxane having an epoxy group with a specific carbonic acid and a compound represented by the following formula (4).

In the above formula (4)

A ¹ is 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 alkoxy group, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton. Provided that some or all of the hydrogen atoms of the alkyl group and the alkoxy group may be substituted with substituents such as a cyano group, a fluorine atom, and a trifluoromethyl group.

L ⁰ is a single bond, -O-, -COO- or -OCO-.

L ¹ represents a single bond, methylene group, alkylene group of 2 to 20 carbon atoms, phenylene group, biphenylene group, cyclohexylene group, a cyclohexylene group or by the formula (L ¹ -1) or (L ¹ -2) .

Z is a monovalent organic group capable of reacting with an epoxy group in the [a] polyorganosiloxane compound to form a bonding group.

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

In the above expressions (L ¹ -1) and (L ¹ -2), the combined hands marked with "*" are combined with Z, respectively.

Z is preferably a carboxyl group.

Examples of the linear or branched alkyl group having 1 to 30 carbon atoms represented by A ¹ in the formula (4) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, , n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2- Dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1, 3-dimethylbutyl group, Dimethylbutyl group, 1,1-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group , 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl, 2,4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl, 2,3 Dimethylpentyl, 1,3-dimethylpentyl, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3 , 3-trimethylbutyl group, 1,2,3-tri Methylheptyl group, a 2-methylheptyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 3-methylheptyl group, a 2-methylheptyl group, n-heptadecyl, n-hexadecyl, n-heptadecyl, n-hexadecyl, n-hexadecyl, , n-octadecyl group, and n-nonadecyl group.

Examples of the cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group or alkoxy group having 1 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, Dodecyl group and the like.

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

As A ¹ in the formula (4), an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and a group selected from the group represented by the formula (H-1) or (H-3) are preferable.

As the compound represented by the formula (4), compounds represented by the following formulas (4-1) to (4-6) are preferable.

In the formulas (4-1) to (4-6), u is an integer of 1 to 5. v is an integer of 1 to 18; w is an integer of 1 to 20; k is an integer of 1 to 5; p is 0 or 1; q is an integer of 0 to 18; r is an integer of 0 to 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 (5-8) are more preferable.

The compound represented by the formula (4) is a compound that reacts with a polyorganosiloxane having an epoxy group together with a specific carbonic acid, and becomes a site that gives pretilt angularity to the resulting liquid crystal alignment film. In the present specification, the compound represented by the formula (4) is hereinafter sometimes referred to as "other pretilt angle-expressing compound".

In the present invention, when other pretilt angle-expressing compounds are used together with the specific carbonic acid, the total usage ratio of the specific carbonic acid and other pretilt angle-expressing compounds is preferably in the range of 1 mole to 1 mole of the epoxy group of the polyorganosiloxane Preferably from 0.001 mol to 1.5 mol, more preferably from 0.01 mol to 1 mol, and still more preferably from 0.05 mol to 0.9 mol. In this case, the other pretilt angle-expressing compound is used in an amount of preferably not more than 75 mol%, more preferably not more than 50 mol% with respect to the total amount with the specific carbonic acid. When the proportion of the other pretilt angle-expressing compound is more than 75 mol%, there is a case where the high-speed responsiveness of the liquid crystal is adversely affected.

Examples of the catalyst used in the reaction of the epoxy group in the polyorganosiloxane with the carboxylic acid group-containing compound represented by the formula (4) and other pretilt angle-expressing compounds include organic bases or organic acids which accelerate the reaction between the epoxy compound and the acid anhydride, Known compounds can be used as so-called curing accelerators.

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene; And 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 preferred.

As the curing accelerator, for example,

Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine and triethanolamine;

2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) 1- (2-cyanoethyl) -2-n-octylimidazole, 1- (2-cyanoethyl) 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- (2-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate (2- cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- Ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s- Triazine, 2 , Isocyanuric acid adducts of 4-diamino-6- [2'-ethyl-4'-methylimidazolyl (1 ')] ethyl-s-triazine, 2-methylimidazole, Imidazole derivatives such as isocyanuric acid adduct of imidazole and isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl (1 ')] ethyl-s- compound;

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenphosphate; Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphor Ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetra Quaternary phosphonium salts such as fluoroborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;

Organometallic compounds such as zinc octylate, tin octylate and aluminum acetyl acetone complex;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride;

Boron compounds such as boron trichloride and triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

A high melting point dispersed latent curing accelerator such as an amine addition type accelerator such as dicyandiamide or an adduct of an amine with an epoxy resin;

A microcapsulated 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;

Amine salt type latent curing accelerator;

And 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 parts by mass to 100 parts by mass, and still more preferably 0.1 parts by mass to 20 parts by mass, based on 100 parts by mass of the polyorganosiloxane having an epoxy group .

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

The synthesis reaction of the [a] polyorganosiloxane compound can be carried out in the presence of an organic solvent if necessary. Examples of such an organic solvent include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, and an alcohol compound. Of these, ether compounds, ester compounds, and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of products. The solvent preferably 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) of preferably 0.1% by mass or more and 70% by mass or less, more preferably 5% As shown in FIG.

The weight average molecular weight of the [a] polyorganosiloxane compound thus obtained by gel permeation chromatography as converted to styrene is not particularly limited, but is preferably 1,000 to 200,000, and more preferably 2,000 to 20,000. Within this molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

The polyorganosiloxane compound [a] of the present invention introduces a structure derived from a specific carbonic acid by ring-opening addition to the epoxy group of the carboxylate moiety of the specific carbonic acid in the polyorganosiloxane having an epoxy group. This production method is very convenient in that it is simple, and further, the introduction rate of a structure derived from a specific carbon acid can be increased.

<Other ingredients>

The liquid crystal aligning agent may be, for example, a polymer other than the [A] polymer (hereinafter, referred to as &quot; other polymer &quot;) as long as it does not impair the effect of the present invention, ), A curing catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule (hereinafter sometimes referred to as "epoxy compound"), a functional silane compound, a surfactant, and the like Component.

[Other Polymers]

Other polymers can be used to further improve the solution characteristics of the liquid crystal aligning agent (A) and the electric characteristics of the resulting liquid crystal display element. As the other polymer, for example,

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 (a1), a condensate of the hydrolyzate thereof and a hydrolyzate thereof (hereinafter sometimes referred to as "other polyorganosiloxane");

Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like can be given as examples of the polyamide acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative,

In the formula (a1), X ^A 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 ^A is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

<[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]

The polyamic acid is obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound.

&Lt; Tetracarboxylic acid dianhydride >

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid in the present invention include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic dianhydride, and the like.

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2,4,6,8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3 , 5,8,10-tetraon, and the like,

As the aromatic tetracarboxylic acid dianhydride, for example, pyromellitic dianhydride and the like can be given.

As the tetracarboxylic acid dianhydride, tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used.

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid preferably includes an alicyclic tetracarboxylic acid dianhydride, more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1, , 2,3,4-cyclobutanetetracarboxylic acid dianhydride, and particularly preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid include 2,3,5-tricarboxycyclopentylacetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride, Is preferably contained in an amount of 10 mol% or more, more preferably 20 mol% or more, and more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclo Butane tetracarboxylic acid dianhydride is most preferable.

<Diamine>

Examples of the diamine used for synthesizing the polyamic acid in the present invention include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes and the like. Specific examples thereof include aliphatic diamines such as 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) cyclohexane.

Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7'- Bis (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2, 4-diaminodiphenyl ether, (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- (p- phenylenediisopropylidene ) Bisaniline, 4,4'- (m-phenylene diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'- , 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl-3, 6-diaminocarbazole, N- N, N'-bis (4-aminophenyl) benzene, N, N'-bis ) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy- 2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy- 5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy- Diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy- 4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4 -Aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4 '- (trifluoromethylbenzoyloxy) cyclohexyl-3, 5-diaminobenzoate, 1,1-bis 4-heptylcyclohexane, 1,1-bis (4 - ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1- Bis (4 - ((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 2,4- diamino-N, N-diallylaniline, Benzylamine, 1- (2,4-diaminophenyl) piperazine-4-carboxylic acid, 4- (morpholin- -Aminophenyl) piperidinyl) propane,? -Amino-? - aminophenylalkylene and diamine compounds represented by the following formula (A-1).

In the formula (A-1), X ^I and X ^Ⅱ is, each independently, a single bond, -O-, -COO- or -OCO-. R ^I is a methylene group or an alkylene group having 2 or 3 carbon atoms. ? is 0 or 1. beta is an integer of 0 to 2. There is no case where? And? Become 0 at the same time. ? is an integer of 1 to 20.

Examples of the divalent group represented by X ^I -R ^I -X ^II - in the formula (A-1) include a methylene group, an alkylene group having 2 or 3 carbon atoms, -O-, * -COO- or * -O-CH ₂ CH ₂ -O- (provided that the bonding hands attached with * are bonded to a diaminophenyl group). Specific examples of the C _粒 H _{2 γ + 1} - group include a methyl group, an ethyl group, a n-propyl group, an n-butyl group, a n-pentyl group, N-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-octadecyl group, n-hexadecyl group, - nonadecyl group, and n-eicosyl group. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or the 3,5-position with respect to the other groups.

Examples of the compound represented by the above formula (A-1) include compounds represented by the following formulas (A-1-1) to (A-1-6).

In the above formula (A-1), it is preferable that? And? Do not become 0 at the same time.

As the diaminoorganosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, diamines described in JP-A-2010-97188 can be used.

The diamine used for synthesizing the polyamic acid in the present invention is preferably a diamine containing a cholestanyl group, a diamine containing a cholesteryl group, or a diamine represented by the formula (A-1) in order to exhibit sufficient vertical orientation . The amount of these diamines to be used is preferably 5 mol% or more, more preferably 10 mol% to 90 mol%, particularly preferably 21 mol% to 80 mol%, based on the total diamine .

The ratio of the tetracarboxylic dianhydride and the diamine compound to be used in the synthesis reaction of the polyamic acid is such that the ratio of the acid anhydride group of the tetracarboxylic acid dianhydride to the equivalent of the amino group contained in the diamine compound ranges from 0.2 to 2 equivalents , More preferably 0.3 equivalents to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under a temperature condition of preferably -20 ° C to 150 ° C, more preferably 0 ° C to 100 ° C, preferably 0.5 hours to 24 hours Preferably 2 hours to 10 hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, , Aprotic polar solvents such as N, N-dimethylimidazolidinone, dimethylsulfoxide,? -Butyrolactone, tetramethylurea and hexamethylphosphotriamide; phenol-based solvents such as m-cresol, xylenol, phenol, and halogenated phenol. The amount (a) of the organic solvent used is preferably 0.1% by mass to 50% by mass, more preferably 5% by mass, based on the total amount (a + b) of the reaction solution and the total amount (b) of the tetracarboxylic acid dianhydride and the diamine compound By mass to 30% by mass.

The organic solvent may be used in combination with alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like, which are poor solvents of polyamic acid, in a range in which the resulting polyamic acid is not precipitated. Examples of such poor solvents include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, ethylene glycol monomethyl ether, , Butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, propylene carbonate, diethyl oxalate, Diethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether (ethylene glycol monoethyl ether), ethylene glycol diethyl ether, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, , Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Diethylene glycol monomethyl 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 and xylene. 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. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or after the isolated polyamic acid is purified, . The polyamic acid may be isolated by pouring the reaction solution into a large amount of a poor solvent to obtain a precipitate, drying the precipitate under reduced pressure, or a method of distilling off the reaction solution under reduced pressure using a separator. The polyamic acid can be purified by a method in which the polyamic acid is dissolved again in an organic solvent, followed by precipitation with a poor solvent, or a step of distillation under reduced pressure using a diverter, once or several times.

[Polyimide]

The polyimide can be produced by subjecting the acid structure of the polyamic acid obtained as described above to dehydration ring closure. At this time, the whole of the arboric acid structure may be completely imidized by dehydration ring closure, or only a part of the arboric acid structure may be dehydrated and ring-closed to form a partial imide cargo having an acid structure and an imide structure.

The dehydration ring-closure of the polyamic acid can be carried out by a method of (i) heating the polyamic acid, or (ii) a method of dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring- Lt; / RTI &gt;

The reaction temperature in the method of heating the polyamic acid of (i) is preferably 50 ° C to 200 ° C, and more preferably 60 ° C to 170 ° C. When the reaction temperature is 50 ° C or higher, the dehydration ring-closure reaction can be sufficiently promoted. By setting the reaction temperature to 200 ° C or lower, it is possible to suppress the 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 hours to 48 hours, more preferably 2 hours to 20 hours.

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

In the method (ii), a reaction solution containing polyimide is obtained as described above. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent or may be provided in the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated, Or may be provided to the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent substitution can be applied. Isolation and purification of polyimide can be carried out by carrying out the same operation as described above as a method for isolating and purifying polyamic acid.

[Other polyorganosiloxane]

The liquid crystal aligning agent (A) may contain other polyorganosiloxane than the [a] polyorganosiloxane compound. The other polyorganosiloxane is preferably at least one selected from the group consisting of the polyorganosiloxane represented by the formula (a1), a hydrolyzate thereof and a condensate of the hydrolyzate thereof. When the liquid crystal aligning agent (A) contains other polyorganosiloxane, most of the other polyorganosiloxanes are present independently of the [a] polyorganosiloxane compound, and some of them are [a ] May be present as a condensate with the polyorganosiloxane compound.

In X ^A and Y ^A in the formula (a1)

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a n-hexyl group, n-heptadecyl group, n-heptadecyl group, n-octadecyl group, n-hexadecyl group, n-hexadecyl group, An n-nonadecyl group, and an n-eicosyl group.

Examples of the alkoxy group having 1 to 16 carbon atoms include methoxy group and ethoxy group,

As the aryl group having 6 to 20 carbon atoms, for example, a phenyl group and the like can be given.

The other polyorganosiloxane is preferably at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter sometimes referred to as &quot; raw silane compound &quot;), 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 compounds usable herein include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra- -Butoxysilane, tetra-tert-butoxysilane, tetrachlorosilane; Butoxysilane, methyltri-sec-butoxysilane, methyltri-sec-butoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri- propyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopropoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri- butoxy silane, ethyl tri-sec-butoxy silane, ethyl tri-tert-butoxy silane, ethyl trichlorosilane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl trichlorosilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane; Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and the like. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane, and trimethylethoxysilane are preferable.

Examples of the organic solvent that can optionally be used in the synthesis of other polyorganosiloxane include an alcohol compound, a ketone compound, an amide compound or an ester compound or other aprotic compound. These compounds may be used singly or in combination of two or more.

As the alcohol compound, for example,

Propanol, n-butanol, i-butanol, sec-butanol, t-butanol, Butanol, 2-ethylhexanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol sec-octadecyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, n-octanol, n-nonyl alcohol, 2,6- , Monoalcohol compounds such as cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4- Polyhydric alcohol compounds such as 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;

Ethylene glycol monoethyl 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 mono Methyl ethyl 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 And partial ethers of polyhydric alcohol compounds such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether. These alcohol compounds may be used alone or in combination of two or more.

As the ketone compound, for example,

But are not limited to, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, Monoketone compounds such as ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone and fenchone;

Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, Dione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4 -Diketone compounds such as heptanedione and the like. These ketone compounds may be used singly or in combination of two or more kinds.

Examples of the amide compound include N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N -Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. These amide compounds may be used singly 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,? -Butyrolactone,? -Valerolactone, n-propyl acetate, sec-butyl acetate, sec-butyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, Acetic acid ethyl ester, acetic acid ethylene glycol monomethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ester, acetic acid ethyleneglycol monomethyl ether, Ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monoacetate T-butyl ether, acetic acid propylene glycol monoethyl ether, acetic acid propylene glycol monopropyl ether, acetic acid propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, Ethyl lactate, n-butyl lactate, diethyl malonate, dimethyl phthalate, di-n-butyl lactate, di-n-butyl lactate, di-n-propyl lactate, Ethyl and the like. These ester compounds may be used alone or in combination of two or more.

Examples of other aprotic compounds include acetonitrile, dimethylsulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholine, Methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4- Pyridone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro- And the like. Of these solvents, polyhydric alcohol compounds, partial ethers of polyhydric alcohol compounds, and ester compounds are particularly preferable.

The amount of water used in the synthesis of the other polyorganosiloxane is preferably 0.01 to 100 moles, more preferably 0.1 moles per mole of the total amount of the alkoxy group and the halogen atom contained in the raw material silane compound To 30 moles, more preferably 1 mole to 1.5 moles.

Examples of the catalyst 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 trialkoxy mono (acetylacetonate) titanium such as triethoxy mono (acetylacetonate) titanium; Dialkoxy bis (acetylacetonate) titanium such as diethoxy bis (acetylacetonate) titanium; Monoalkoxy tris (acetylacetonate) titanium such as monoethoxy tris (acetylacetonate) titanium; Tetrakis (acetylacetonate) titanium; Trialkoxy mono (ethylacetate) titanium such as triethoxy mono (ethylacetate) titanium; Dialkoxy bis (ethylacetate) titanium such as diethoxy bis (ethylacetate) titanium; Monoalkoxy tris (ethylacetate) titanium such as monoethoxy tris (ethylacetate) titanium; Tetrakis (ethylacetate) titanium; And two or more chelate ligands such as mono (acetylacetonate) tris (ethylacetate) titanium, bis (acetylacetonate) bis (ethylacetate) titanium and tris (acetylacetonate) A titanium chelate compound such as a titanium compound;

Trialkoxy mono (acetylacetonate) zirconium such as triethoxy mono (acetylacetonate) zirconium; Dialkoxy bis (acetylacetonate) zirconium such as diethoxy bis (acetylacetonate) zirconium; Monoalkoxy tolyl (acetylacetonate) zirconium such as monoethoxy tris (acetylacetonate) zirconium; Tetrakis (acetylacetonate) zirconium; Trialkoxy mono (ethylacetate) zirconium such as triethoxy mono (ethylacetate) zirconium; Dialkoxy bis (ethylacetate) zirconium such as diethoxy bis (ethylacetate) zirconium; Monoalkoxy tris (ethylacetate) zirconium such as monoethoxy tris (ethylacetate) zirconium; Tetrakis (ethylacetate) zirconium; And at least two chelate ligands such as mono (acetylacetonate) tris (ethylacetate) zirconium, bis (acetylacetonate) bis (ethylacetate) zirconium and tris (acetylacetonate) mono A zirconium chelate compound such as a zirconium compound;

Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetate) aluminum, and the like.

Examples of the organic acid include aliphatic saturated carboxylic acids such as formic acid, acetic acid and propionic acid; Aliphatic unsaturated carboxylic acids such as malonic acid and fumaric acid; Aromatic carboxylic acids such as salicylic acid, benzoic acid and phthalic acid; aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; Halogen-containing carbonic acids such as monochloroacetic acid, trichloroacetic acid, and trifluoroacetic 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, monomethyldiethanol Amine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicyclo-undecene, tetramethylammonium hydroxide and the like.

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 preferable. 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 based on 100 parts by mass of the raw material silane compound.

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

The water to be added in the synthesis of the other polyorganosiloxane may be added intermittently or continuously in a silane compound as a raw material or in a solution in which a silane compound is dissolved in an organic solvent.

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

When the liquid crystal aligning agent (A) contains other polymer together with the [A] polymer, the content of the other polymer is preferably 10,000 parts by mass or less based on 100 parts by mass of the [A] polymer. The more preferable content of the other polymer differs depending on the kind of the other polymer.

In the case where the liquid crystal aligning agent (A) contains both the [A] polymer and the [B] polymer, a preferable ratio of both of them is 100 parts by mass as the total amount of the polymer [B] relative to 100 parts by mass of the [A] To 5,000 parts by mass, and more preferably 200 parts by mass to 3,000 parts by mass.

On the other hand, in the case where the liquid crystal aligning agent (A) contains the [a] polyorganosiloxane compound and the other polyorganosiloxane, the preferable ratio of both of them is [a] 100 parts by mass of the polyorganosiloxane compound Is 100 parts by mass to 2,000 parts by mass as the amount of other polyorganosiloxane.

When the liquid crystal aligning agent (A) contains other polymer together with the [A] polymer, the [B] polymer or other polyorganosiloxane is preferable as the other polymer.

[Curing agent, curing catalyst and curing accelerator]

The curing agent and the curing catalyst may be included in the liquid crystal aligning agent for the purpose of making the crosslinking reaction of the [a] polyorganosiloxane compound stronger. The curing accelerator may be included in the liquid crystal aligning agent (A) for the purpose of accelerating the curing reaction which is carried out by the curing agent.

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

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

Examples of the cyclohexanetricarboxylic acid anhydrides include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic-3,5- Hexane-1,2,3-tricarboxylic acid-2,3-acid anhydride and the like. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, The resulting compound, a tetracarboxylic acid dianhydride generally used for the synthesis of polyamic acid, a di-alder reaction product of an alicyclic compound having a conjugated double bond such as? -Terpinene, alloocimene and the like and maleic anhydride And hydrogenated products thereof.

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

As the curing catalyst, for example, antimony hexafluoride compound, hexafluorophosphate compound, aluminum trisacetylacetonate and the like can be used. These catalysts can catalyze the cationic polymerization of an epoxy group by heating.

As the curing accelerator, for example, an imidazole compound; A quaternary compound; Quaternary amine compounds; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate and aluminum acetyl acetone complex; Boron compounds such as boron trichloride and triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride; A high melting point dispersing latent curing accelerator such as dicyandiamide, an amine addition type accelerator such as an adduct of an amine and an epoxy resin; A microcapsulated latent curing accelerator in which a surface of a quaternary phosphonium salt or the like is coated with a polymer; Amine salt type latent curing accelerator; High-temperature dissociation type thermal cationic polymerization latent curing accelerators such as Lewis acid salts and Bronsted acid salts, and the like.

[Epoxy Compound]

The epoxy compound can be included in the liquid crystal aligning agent (A) from the viewpoint of improving the adhesion to the substrate surface of the liquid crystal alignment film to be 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 di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglyl N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane , N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- Cyclohexane is preferred.

When the liquid crystal aligning agent (A) contains an epoxy compound, the content thereof is preferably 0.01 to 40 parts by mass per 100 parts by mass of the total amount of the polymer More preferably 0.1 part by mass to 30 parts by mass.

Further, when the liquid crystal aligning agent (A) contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of efficiently causing the crosslinking reaction.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the adhesion of the obtained liquid crystal alignment film to the substrate. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silane triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N- 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. And reaction products of a tetracarboxylic acid dianhydride and a silane compound having an amino group described in JP-A-63-291922.

When the liquid crystal aligning agent (A) contains a functional silane compound, the content of the liquid crystal aligning agent (A) is preferably 50 parts by mass per 100 parts by mass of the total of 100 parts by mass of the polyorganosiloxane compound [a] Or less, more preferably 20 parts by mass or less.

[Surfactants]

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 (A) contains a surfactant, the content thereof is preferably 10 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the liquid crystal aligning agent (A) to be.

&Lt; Process for preparing liquid crystal aligning agent (A)

As described above, the liquid crystal aligning agent (A) may contain other components as necessary and contain the polymer [A] as an essential component. Preferably, the liquid crystal aligning agent (A) is a solution composition in which each component is dissolved in an organic solvent It is prepared.

As the organic solvent that can be used for preparing the liquid crystal aligning agent (A), it is preferable that the [A] polymer and other optional components used are dissolved and not reacted with them. The organic solvent which can be preferably used for the liquid crystal aligning agent (A) differs depending on the kind of the other polymer optionally added.

Examples of the preferable organic solvent when the liquid crystal aligning agent (A) contains the [A] polymer and the [B] polymer include the organic solvents exemplified above, which are used for the synthesis of polyamic acid. At this time, the poor solvent exemplified for use in the synthesis of the polyamic acid of the present invention may be used in combination. These organic solvents may be used alone or in combination of two or more.

On the other hand, when the liquid crystal aligning agent (A) contains only the [a] polyorganosiloxane compound as the polymer, or when the [a] polyorganosiloxane compound and other polyorganosiloxane are contained, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, di Propylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, Hexyl 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, sec-butyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, Octyl acetate, amyl acetate, isoamyl acetate, 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-

A preferable solvent used for the preparation of the liquid crystal aligning agent (A) can be obtained by combining one or more of the above-mentioned organic solvents depending on whether or not other polymers are used and the kind thereof. These solvents are such that the components contained in the liquid crystal aligning agent (A) are not precipitated at the following preferable solid concentration and the surface tension of the liquid crystal aligning agent (A) is in the range of 25 to 40 mN / m.

The solid concentration of the liquid crystal aligning agent (A), that is, the ratio of the mass of all the components other than the solvent in the liquid crystal aligning agent (A) to the total mass of the liquid crystal aligning agent (A) is selected in consideration of viscosity, volatility, And preferably 1% by mass to 10% by mass. The liquid crystal aligning agent (A) is applied to the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. When the solid concentration is 1% by mass or more, the film thickness of this coating film is less likely to become excessively small and a good liquid crystal alignment film can be obtained have. On the other hand, when the solid concentration is 10% by mass or less, it is possible to prevent an excessive film thickness of the coating film from being obtained, to obtain a good liquid crystal alignment film, and to prevent the viscosity of the liquid crystal aligning agent (A) Can be made good. A particularly preferable range of the solid concentration is different depending on the method employed when the liquid crystal aligning agent (A) is applied to the substrate. For example, in the case of the spinner method, the range of 1.5% by mass to 4.5% by mass is particularly preferable. In the case of the printing method, it is particularly preferable that the solid concentration is set in the range of 3 mass% to 9 mass%, and the solution viscosity is accordingly set in the range of 12 mPa · s to 50 mPa · s. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1% by mass to 5% by mass, and the solution viscosity is accordingly in the range of 3 mPa · s to 15 mPa · s. The temperature for preparing the liquid crystal aligning agent (A) is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 40 ° C.

(Example)

Hereinafter, the present invention will be described concretely by way of examples, but the present invention is not limited to these examples.

The weight average molecular weight (Mw) of the obtained polyorganosiloxane and [a] polyorganosiloxane compound obtained in the following Examples is the polystyrene conversion value measured by GPC in the following specification.

Column: TSKgelGRCXLII, manufactured by Toso K.K.

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

The necessary amounts of the starting compounds and polymers used in the following examples were ensured by repeating the synthesis of the starting compounds and the polymers in the synthesis scale shown in the following synthesis examples as necessary.

The liquid crystal display device manufactured was evaluated as follows. The evaluation results are summarized in Table 1.

&Lt; Synthesis of polyorganosiloxane having epoxy group &gt;

[Synthesis Example 1]

100 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube And the mixture was mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group As a transparent liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane having the epoxy group, it was found that the peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm in accordance with the theoretical strength, and no side reaction of the epoxy group occurred during the reaction . The weight average molecular weight (Mw) of the polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 was 2,200 and the epoxy equivalent was 186 g / mol.

&Lt; Synthesis of Specific Carbonic Acid &gt;

[Synthesis of Specific Carboxylic Acid 1]

A specific carbonic acid 1 was synthesized according to the following reaction formula.

[Synthesis Example 2]

6.3 g of 4-cyano-4'-hydroxybiphenyl, 10 g of methyl 11-bromododecanoate, 14.2 g of potassium carbonate and 200 mL of N, N-dimethylformamide were added to a 500 mL three-necked flask equipped with a cooling tube , And the mixture was heated and stirred at 160 DEG C for 5 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, followed by mixing and stirring. The precipitated white solid was filtered off and further washed with water. The resulting solid was vacuum-dried at 80 占 폚 to obtain 11 g of Compound 1.

[Synthesis Example 3]

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 cooling tube, and the mixture was heated and stirred at 80 캜 for 4 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, diluted hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered, washed with water and then with ethanol in this order. The resulting solid was vacuum-dried at 80 占 폚 to obtain 8 g of a specific carboxylic acid 1.

[Synthesis of Specific Carboxylic Acid 2]

A specific carbonic acid 2 was synthesized according to the following reaction formula.

[Synthesis Example 4]

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 were added to a 500 mL three-necked flask equipped with a cooling tube , And the mixture was heated and stirred at 150 占 폚 for 9 hours. After completion of the reaction was confirmed 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-aqueous sodium hydroxide solution. The organic layer was extracted, and then 100 mL of 1N aqueous sodium hydroxide solution and 100 mL of water were sequentially washed. 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 from 100 mL of ethanol / 250 mL of hexane to obtain 13.1 g of Compound 2. [

[Synthesis Example 5]

A cooling tube 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 cooling the reaction solution with an ice bath, a solution of 6.6 g of triethylamine in 10 mL of dehydrated methylene chloride was added dropwise over 10 minutes. The mixture was stirred for 30 minutes with ice bath, returned to room temperature and stirred for additional 6 hours. 150 mL of chloroform was added to the reaction solution, and the solution was washed 4 times with 100 mL of water. The extracted organic layer was dried with magnesium sulfate, and the organic solvent was distilled off. The resulting solid was washed with ethanol to obtain 16.1 g of Compound 3.

[Synthesis Example 6]

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 cooling tube, and the mixture was heated and stirred at 80 占 폚 for 9 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The applied 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 resulting solid was vacuum-dried at 80 占 폚 to obtain 10 g of Compound 4. [

[Synthesis Example 7]

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 to a 100 mL three-necked flask equipped with a cooling tube and the mixture was heated and stirred at 80 占 폚 for 4 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, diluted hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered, washed with water and then with ethanol in this order. The resulting solid was vacuum-dried at 80 占 폚 to obtain 9 g of a specific carboxylic acid 2.

[Synthesis of Specific Carboxylic Acid 3]

A specific carbonic acid 3 was synthesized according to the following reaction formula.

[Synthesis Example 8]

In Synthesis Example 2, compound No. 5 was obtained in the same manner as in Synthesis Example 2, except that 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- g.

[Synthesis Example 9]

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

[Synthesis of Specific Carboxylic Acid 4]

A specific carbonic acid 4 was synthesized according to the following reaction formula.

[Synthesis Example 10]

In Synthesis Example 4, by using 25.5 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol instead of 4-cyano-4'- 23.1 g.

[Synthesis Example 11]

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

[Synthesis Example 12]

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

[Synthesis Example 13]

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

[Synthesis of Specific Carboxylic Acid 5]

A specific carbonic acid 5 was synthesized according to the following reaction formula.

[Synthesis Example 14]

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 carbonic acid 1.

[Synthesis of Specific Carboxylic Acid 6]

According to the following reaction formula, a specific carbonic acid 6 was synthesized.

[Synthesis Example 15]

In a 500 ml three-necked flask equipped with a condenser tube, 10.1 g of 2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl, 10 g of methyl 11-bromododecanoate, And 200 mL of N, N-dimethylformamide were added and the mixture was heated and stirred at 160 占 폚 for 5 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, followed by mixing and stirring. The precipitated white solid was filtered off and further washed with water. The resulting solid was vacuum-dried at 80 占 폚, thereby obtaining 10.8 g of Compound 9.

[Synthesis Example 16]

Next, 10 g of Compound 9, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 캜 for 4 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, diluted hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered, washed with water and then with ethanol in this order. The obtained solid was vacuum-dried at 80 占 폚 to obtain 6 g of a specific carboxylic acid 6.

[Synthesis of Specific Carboxylic Acid 7]

According to the following reaction formula, a specific carbonic acid 7 was synthesized.

[Synthesis Example 17]

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,3-difluoro-4- -Propyl-cyclohexyl) phenol), 9.1 g of the specific carbonic acid 7 was obtained in the same manner as the synthesis of the specific carbonic acid 6.

[Synthesis of Specific Carboxylic Acid 8]

According to the following reaction formula, a specific carbonic acid 8 was synthesized.

[Synthesis Example 18]

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,2', 3,3'-tetrafluoro (4-propyl-4 "-hydroxyterphenyl) was changed to 12.9 g, in the same manner as in the synthesis of the specific carboxylic acid 6, 7.1 g of the specific carboxylic acid 8 was obtained.

[Synthesis of Specific Carboxylic Acid 9]

According to the following reaction formula, a specific carbonic acid 9 was synthesized.

[Synthesis Example 19]

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,3-difluoro-4- -Propylcyclohexylmethoxy) phenol), the specific carbonic acid 9 was obtained in the same manner as in the synthesis of the above specific carbonic acid 6.

[Synthesis of Specific Carboxylic Acid 10]

According to the following reaction formula, a specific carbonic acid 10 was synthesized.

[Synthesis Example 20]

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,3-difluoro-4' 4-propylphenylethyl) biphenyl) was replaced by 12.6 g, the specific carbonic acid 10 (7.2 g) was obtained in the same manner as the synthesis of the specific carbonic acid 6.

[Synthesis of Specific Carboxylic Acid 11]

According to the following reaction formula, a specific carbonic acid 11 was synthesized.

[Synthesis Example 21]

Except that 10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was replaced with 14.2 g of the compound described in the above reaction formula, 7.6 g of the specific carboxylic acid 11 was obtained in the same manner as in the synthesis.

[Synthesis of Specific Carboxylic Acid 12]

According to the following reaction formula, a specific carbonic acid 12 was synthesized.

[Synthesis Example 22]

In a 500 ml three-necked flask equipped with a condenser tube, 12.5 g of 4- [difluoro (4-pentylcyclohexyl) methoxy] -2,3-difluorophenol, 10 g of methyl 11-bromododecanoate, 14.2 g of potassium and 200 mL of N, N-dimethylformamide were added and the mixture was heated and stirred at 160 DEG C for 5 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, followed by mixing and stirring. The precipitated white solid was filtered off and further washed with water. The resulting solid was vacuum-dried at 80 占 폚 to obtain 14.8 g of Compound 10.

[Synthesis Example 23]

Next, 10 g of Compound 10, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 캜 for 4 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, diluted hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered, washed with water and then with ethanol in this order. The resulting solid was vacuum-dried at 80 占 폚 to obtain 6 g of a specific carboxylic acid 12.

<Synthesis of [a] polyorganosiloxane compound>

[Synthesis Example 24]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 5.0 g of the specific carbonic acid 1 obtained in Synthesis Example 3, 5.0 g of the specific carbonic acid 1 obtained in the above Synthesis Example 1, 3.3 g of 4-octyloxybenzoic acid represented by the formula (5-5) shown as the compound and 0.20 g of UCAT 18X (quaternary amine salt manufactured by San A Pro Co.) were added, and the mixture was stirred at 80 캜 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. This solution was washed three times with water and then the solvent was distilled off to obtain [a] polyorganosiloxane compound A- 14.5 g of a white powder was obtained. The Mw of the [a] polyorganosiloxane compound A-1 was 6,500.

[Synthesis Example 25]

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

[Synthesis Example 26]

The procedure of Synthetic Example 24 was repeated except that 6.8 g of the specific carboxylic acid 3 obtained in Synthesis Example 9 was used instead of the specific carbonic acid 1 to obtain 14.7 g of a white powder of the [a] polyorganosiloxane compound A-3. The Mw of A-3 was 8,100.

[Synthesis Example 27]

The procedure of Synthetic Example 24 was repeated except that 5.6 g of the specific carbonic acid 4 obtained in Synthesis Example 13 was used instead of the specific carbonic acid 1 to obtain 15.0 g of a white powder of the [a] polyorganosiloxane compound A-4. The Mw of A-4 was 7,500.

[Synthesis Example 28]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 10 g of the specific carboxylic acid 1 obtained in the above Synthesis Example 3 and 10 g of UCAT 18X (manufactured by San- , And the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water, and the solvent was distilled off to obtain [a] polyorganosiloxane compound A-5 as a white powder 16.0 g. The Mw of A-5 was 8,500.

[Synthesis Example 29]

4.1 g of the specific carboxylic acid 5 obtained in Synthesis Example 14 instead of the specific carbonic acid 1, 4 g of 4'-pentyl-1,1'-bi (cyclohexyl) benzene represented by the above formula (5-8) instead of 4-octyloxybenzoic acid, -4-carboxylic acid was used in an amount of 3.7 g in the same manner as in Synthesis Example 24, 12.4 g of a white powder of the [a] polyorganosiloxane compound A-6 was obtained. The Mw of A-6 was 6,200.

[Synthesis Example 30]

A] polyorganosiloxane compound A (a) was obtained in the same manner as in Synthesis Example 24, except that 3.6 g of 4- (4-pentylcyclohexyl) benzoic acid represented by the formula (5-7) -7 white powder. The Mw of A-7 was 7,900.

[Synthesis Example 31]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 8.0 g of the specific carbonic acid 1 obtained in Synthesis Example 3, 8.0 g of the compound represented by the formula (5-7) (4-pentylcyclohexyl) benzoic acid and 0.20 g of UCAT 18X (quaternary amine salt, manufactured by San A Pro Co.) were added thereto, and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed with water three times, and then the solvent was distilled off to obtain [a] polyorganosiloxane compound A-8 as a white powder 13.9 g. The Mw of A-8 was 8,900.

[Synthesis Example 32]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 2.0 g of the specific carbonic acid 1 obtained in the above Synthesis Example 3, 5.8 g of 4- (4-pentylcyclohexyl) benzoic acid represented by the following formula, and 0.20 g of UCAT 18X (quaternary amine salt manufactured by San A Pro Co.) were added and stirred at 80 ° C for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. This solution was washed three times with water and then the solvent was distilled off to obtain [a] polyorganosiloxane compound A-9 13.4 g was obtained as a white powder. The Mw of A-9 was 7,600.

[Synthesis Example 33]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 8.0 g of the specific carbonic acid 1 obtained in Synthesis Example 3, 8.0 g of the compound represented by the formula (5-6) , And 0.20 g of UCAT 18X (quaternary amine salt manufactured by SANA PROVANCE CO., LTD.), And the mixture was stirred at 80 캜 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water and then the solvent was distilled off to obtain [a] polyorganosiloxane compound A-10 as a white powder 15.5 g. The Mw of A-10 was 9,200.

[Synthesis Example 34]

18.4 g of a white powder of the [a] polyorganosiloxane compound A-11 was obtained in the same manner as in Synthesis Example 24 except that 6.1 g of the specific carbonic acid 6 obtained in Synthesis Example 16 was used instead of the specific carbonic acid 1. The Mw of A-11 was 7,300.

[Synthesis Example 35]

17.5 g of a white powder of the [a] polyorganosiloxane compound A-12 was obtained in the same manner as in Synthesis Example 24 except that 5.7 g of the specific carbonic acid 7 obtained in Synthesis Example 17 was used instead of the specific carbonic acid 1. The Mw of A-12 was 7,600.

[Synthesis Example 36]

19.1 g of a white powder of the [a] polyorganosiloxane compound A-13 was obtained in the same manner as in Synthesis Example 24 except that 7.2 g of the specific carbonic acid 8 obtained in Synthesis Example 18 was used instead of the specific carbonic acid 1. The Mw of A-13 was 7,000.

[Synthesis Example 37]

18.1 g of a white powder of the [a] polyorganosiloxane compound A-14 was obtained in the same manner as in Synthesis Example 24 except that 6.2 g of the specific carbonic acid 9 obtained in Synthesis Example 19 was used instead of the specific carbonic acid 1. The Mw of A-14 was 6,900.

[Synthesis Example 38]

19.4 g of a white powder of the [a] polyorganosiloxane compound A-15 was obtained in the same manner as in Synthesis Example 24 except that 7.0 g of the specific carbonic acid 10 obtained in Synthesis Example 20 was used instead of the specific carbonic acid 1. The Mw of A-15 was 7,500.

[Synthesis Example 39]

20.1 g of a white powder of the [a] polyorganosiloxane compound A-16 was obtained in the same manner as in Synthesis Example 24 except that 8.4 g of the specific carbonic acid 11 obtained in Synthesis Example 21 was used instead of the specific carbonic acid 1. The Mw of A-16 was 7,300.

[Synthesis Example 40]

19.5 g of a white powder of the [a] polyorganosiloxane compound A-17 was obtained in the same manner as in Synthesis Example 24 except that 7.2 g of the specific carbonic acid 12 obtained in Synthesis Example 23 was used instead of the specific carbonic acid 1. The Mw of A-17 was 7,300.

[Comparative Synthesis Example 1]

In a 100 mL three-necked flask, 9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 3.3 g of 4-octyloxybenzoic acid and 4 g of UCAT 18X (manufactured by San A Pro Co., Salt) were added, and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water and then the solvent was distilled off to obtain [a] polyorganosiloxane compound CA-1 as a white powder 9.6 g. The Mw of CA-1 was 6,000.

<Synthesis of [B] polymer>

[Synthesis Example 41]

38.32 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 12.43 g of pyromellitic dianhydride, 18.86 g of p-phenylenediamine as a diamine compound, and 18.86 g of p- 30.40 g of the resulting diamine was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours. The viscosity of this polymer solution was measured and found to be 4,100 mPa · s. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried under reduced pressure at 40 占 폚 for 24 hours to obtain 75.1 g of polyamic acid PA-1.

[Synthesis Example 42]

23.06 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 11.01 g of 3,5-diaminobenzoic acid as a diamine compound, 10.81 g of a diamine represented by the formula (G-4) 5.12 g of the diamine represented by the formula (G-5) was dissolved in 200 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours. The viscosity of this polymerization solution was measured and found to be 1,300 mPa · s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried under reduced pressure at 40 DEG C for 24 hours to obtain a polyamic acid. All of the obtained polyamic acids were redissolved in 450 g of N-methyl-2-pyrrolidone, and 8.14 g of pyridine and 10.50 g of acetic anhydride were added and dehydrated and cyclized at 110 DEG C for 4 hours. The precipitates were washed, And dried to obtain 30.5 g of polyimide PI-1 having an imidization rate of 55%.

[Synthesis Example 43]

33.92 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 4.61 g of 3,5-diaminobenzoic acid as a diamine compound and 61.46 g of a diamine represented by the following formula (G-6) -Methyl-2-pyrrolidone, and the reaction was allowed to proceed at 60 DEG C for 4 hours. The viscosity of this polymerization solution was measured and found to be 50 mPa · s. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried at 40 캜 for 24 hours under reduced pressure to obtain 63.9 g of polyamic acid PA-2.

[Synthesis Example 44]

, 37.05 g of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride as tetracarboxylic dianhydride, 21.78 g of 3,5-diaminobenzoic acid as a diamine compound, 9.44 g of a diamine represented by the above formula (G-5) And 6.73 g of 1- (2,4-diaminophenyl) piperidine-4-carboxylic acid were dissolved in 425 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours. The viscosity of this polymerization solution was measured and found to be 180 mPa · s. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried under reduced pressure at 40 占 폚 for 24 hours to obtain 51.5 g of polyamic acid PA-3.

[Synthesis Example 45]

40.68 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 4.40 g of pyromellitic dianhydride and 11.05 g of p-phenylenediamine as a diamine compound, 32.05 g of the resulting diamine and 11.82 g of 4,4'-diamino-N- (4-methylphenyl) diphenylamine were dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours. The viscosity of this polymerization solution was measured and found to be 1,450 mPa · s. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried under reduced pressure at 40 DEG C for 24 hours to obtain 71.9 g of polyamic acid PA-4.

[Synthesis Example 46]

19.47 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 2.10 g of pyromellitic dianhydride, 7.44 g of 3,5-diaminobenzoic acid as a diamine compound, ) And 5.66 g of 4,4'-diamino-N- (4-methylphenyl) diphenylamine were dissolved in 200 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 4 hours. The viscosity of this polymerization solution was measured and found to be 1,100 mPa · s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried under reduced pressure at 40 DEG C for 24 hours to obtain a polyamic acid. All of the obtained polyamic acid was redissolved in 450 g of N-methyl-2-pyrrolidone, 7.63 g of pyridine and 9.85 g of acetic anhydride were added and the mixture was subjected to dehydration ring closure at 110 占 폚 for 4 hours to carry out precipitation, And dried to obtain 34.0 g of a polyimide PI-2 having an imidization ratio of 51%.

[Synthesis Example 47]

28.58 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 3.09 g of pyromellitic dianhydride, and 60.03 g of diamine represented by the above formula (G-4) as a diamine compound and 4,4 - diamino-N- (4-methylphenyl) diphenylamine were dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 4 hours. The viscosity of this polymer solution was measured and found to be 900 mPa · s. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried under reduced pressure at 40 DEG C for 24 hours to obtain 68.3 g of polyamic acid PA-5.

[Synthesis Example 48]

48.99 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 5.30 g of pyromellitic dianhydride, and 12.86 g of the diamine represented by the above formula (G-4) as a diamine compound, -Diamino-N- (4-methylphenyl) diphenylamine and 18.62 g of p-phenylenediamine were dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours. The viscosity of this polymer solution was measured and found to be 1,350 mPa · s. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 24 hours under reduced pressure to obtain 66.0 g of polyamic acid PA-6.

[Synthesis Example 49]

41.34 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 2.12 g of pyromellitic dianhydride, 14.79 g of 3,5-diaminobenzoic acid as a diamine compound, ) And 11.25 g of 4,4'-diamino-N- (4-methylphenyl) diphenylamine were dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 4 hours. The viscosity of this polymerization solution was measured and found to be 1,820 mPa · s. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried under reduced pressure at 40 占 폚 for 24 hours to obtain 62.8 g of polyamic acid PA-7.

[Synthesis Example 50]

18.85 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 8.84 g of a diamine represented by the above formula (G-4) as a diamine compound and 7.31 g of p-phenylenediamine were dissolved in N-methyl Pyrrolidone, and the reaction was allowed to proceed at 60 占 폚 for 4 hours. The viscosity of this polymer solution was measured and found to be 2,150 mPa · s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried under reduced pressure at 40 DEG C for 24 hours to obtain a polyamic acid. The resulting polyamic acid was redissolved in 465 g of N-methyl-2-pyrrolidone, and 6.65 g of pyridine and 8.59 g of acetic anhydride were added and subjected to dehydration cyclization at 110 DEG C for 4 hours, Followed by drying to obtain 23.1 g of polyimide PI-3 having an imidization rate of 50%.

[Synthesis Example 51]

24.94 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 11.24 g of the diamine represented by the above formula (G-5) as the diamine compound and 13.82 g of 3,5-diaminobenzoic acid were dissolved in N -Methyl-2-pyrrolidone, and the reaction was carried out at 60 DEG C for 4 hours. The viscosity of this polymerization solution was measured and found to be 1,400 mPa · s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried under reduced pressure at 40 DEG C for 24 hours to obtain a polyamic acid. The obtained polyamic acid was redissolved in 450 g of N-methyl-2-pyrrolidone, and 13.20 g of pyridine and 17.04 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours, And dried to obtain 27.8 g of a polyimide PI-4 having an imidization ratio of 69%.

&Lt; Preparation of liquid crystal aligning agent &

[Example 1]

As the [B] polymer, a solution containing the polyamic acid PA-1 obtained in Synthesis Example 41 was converted into a polyamic acid PA-1 in an amount corresponding to 100 parts by mass, 10 parts by mass of the [a] polyorganosiloxane compound A-1 obtained in Example 1, and further adding N-methyl-2-pyrrolidone and butyl cellosolve, : Butyl cellosolve = 50: 50 (mass ratio), and a solid content concentration of 3.5% by mass. This solution was filtered with a filter having a pore diameter of 0.2 mu m to prepare liquid crystal aligning agent S-1.

&Lt; Production of liquid crystal display device for evaluation of voltage holding ratio (VHR) and light resistance &gt;

For VHR and light resistance evaluation, a liquid crystal cell produced as described below was used for evaluation.

The prepared liquid crystal aligning agent S-1 was coated on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by means of a spinner, pre-baked at 80 DEG C for 1 minute on a hot plate, (Liquid crystal alignment film) having a film thickness of 0.08 mu m. This operation was repeated to prepare a pair of substrates (two substrates) each having a liquid crystal alignment film.

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 was applied to the periphery of the surface having one liquid crystal alignment film of the above substrate by screen printing and then the liquid crystal alignment film faces of the other pair of substrates were opposed to each other and pressed , And heated at 150 DEG C for 1 hour to thermally cure the adhesive. Subsequently, a positive type liquid crystal (ZLI-5081, manufactured by Merck Ltd.) was filled in the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy adhesive, and further, After being heated at 150 占 폚 for 10 minutes, it was slowly cooled to room temperature.

A polarizing plate was bonded to both outer sides of the prepared liquid crystal cell substrate so that the polarizing directions of the two polarizing plates were orthogonal to each other, thereby producing a liquid crystal display device.

&Lt; Preparation of liquid crystal display device for vertical orientation and evaluation of liquid crystal response speed &gt;

The vertical alignment properties and the liquid crystal response speed were measured for the liquid crystal cell produced as described below.

The prepared liquid crystal aligning agent S-1 was coated on the respective surfaces of the ITO electrode side of the glass substrate on which the ITO electrodes were patterned in the comb shape and one surface of the opposing glass substrate on which the electrodes were not provided using a spinner And pre-baked at 80 ° C for 1 minute on a hot plate, and then heated (post-baked) at 200 ° C for 1 hour in an oven where the inside of the apparatus was replaced with nitrogen to form a coating film (liquid crystal alignment film) having a film thickness of 0.08 μm.

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 mu m was applied to the periphery of the surface of the substrate having the liquid crystal alignment film of the opposite glass substrate on which the ITO electrode was not provided by screen printing and then the ITO electrode was patterned in a comb- The surface of the liquid crystal alignment film of the glass substrate was opposed to the glass substrate, and the adhesive was thermally cured at 150 占 폚 for 1 hour. Subsequently, a positive liquid crystal (ZLI-5081) manufactured by Merck was charged into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 150 캜 for 10 minutes and gradually cooled to room temperature. Next, a polarizing plate was bonded to both outer sides of the liquid crystal cell substrate prepared in the following manner so that the polarizing directions thereof were orthogonal to each other to produce a liquid crystal display device.

[Examples 2 to 26 and Comparative Examples 1 to 4]

2 to S-26 and CS-1 were prepared in the same manner as in Example 1 except that the combination of the [B] polymer and the [a] polyorganosiloxane compound was changed to the compounding ratio shown in Table 1 ~ CS-4. &Quot; - &quot; in Table 1 indicates that the corresponding component is not used. The liquid crystal display devices of Examples 2 to 26 and Comparative Examples 1 to 4 were produced in the same manner as in Example 1, using each of the prepared liquid crystal aligning agents.

<Evaluation>

The liquid crystal display device manufactured as described above was subjected to the following evaluations. The results are shown together in Table 1.

[Vertical Orientation]

The above-prepared liquid crystal display element was observed using an optical microscope. At this time, the absence of light leakage was evaluated by assuming that the vertical alignment property was &quot;? &Quot;, and the light leakage was confirmed to be &quot; x &quot;

[Voltage Conservation Rate (VHR (%))]

A voltage of 5 V was applied to the liquid crystal display device manufactured in the above-described manner at an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the release was measured. VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device.

[Response speed (electro-optical response at rising)]

The time of the rise of the liquid crystal response was measured by a device including a polarization microscope, a photodetector and a pulse generator. Here, the liquid crystal response speed is the time (unit: msec.) Required for the produced liquid crystal display element to change from a voltage unapplied state to a 90% transmittance at a transmittance of 10% when a voltage of 4V is applied for a maximum of one second. ), And evaluated.

[Light Resistance]

VHR after 3,000 hours of irradiation with a weather meter having a carbon arc as a light source was measured in the same manner as described above (voltage of 5 V was applied for 60 seconds and span of 167 milliseconds, voltage after 167 milliseconds The VHR variation of 1% or less was evaluated as &quot; Good &quot; and the value of less than 3% was evaluated as &quot; Good &quot;Quot;, and &quot; x &quot; for 3% or more.

As apparent from the results of Table 1, the liquid crystal display element of the embodiment can be a vertical alignment liquid crystal display element using a positive-type liquid crystal having a short electro-optic response time while satisfying generally required characteristics such as voltage holding ratio and light resistance.

According to the present invention, there is provided a vertically aligned liquid crystal device using a positive-type liquid crystal which satisfies generally required characteristics such as voltage holding ratio and light resistance, and has a short electro-optical response time.

Claims (7)

A pair of substrates disposed opposite to each other,
A liquid crystal layer disposed between the two substrates;
A pair of liquid crystal alignment layers disposed on both sides of the liquid crystal layer,
And electrodes for generating a transverse electric field which are arranged on at least one of the pair of substrates,
Wherein the liquid crystal layer contains a positive type liquid crystal, and
Wherein the liquid crystal alignment layer comprises,
[A] A liquid crystal composition comprising a liquid crystal aligning agent containing a polymer having a group represented by the following formula (A1)
Wherein the liquid crystal alignment layer is a vertical liquid crystal alignment layer:

(Wherein R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group, some or all of the hydrogen atoms of these groups may be substituted, R ² is a double 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 0 or 1. delete The method according to claim 1,
R ³ in the formula (A1) is a liquid crystal display element represented by the following formula (A2):

(In the formula (A2), R ⁴ is a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a divalent heterocyclic group; R ⁵ is a linking group containing at least one of a methylene group which may have a substituent and an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic group, all or part of which may be substituted; R ⁶ is a (c + 1) -valent group other than (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or a heterocyclic compound; R ⁷ represents a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group Or an alkylcarbonyloxy group, b is 0 or 1, c is an integer of 1 to 9, d is 1 or 2, and R ⁴ , R ^5, and R ⁷ are each a plurality of R ⁴ , R ⁵ and R &lt; ⁷ &gt; may be the same or different. The method according to claim 1 or 3,
[A] the liquid crystal display element in which the polymer has a polyorganosiloxane structure. The method according to claim 1 or 3,
Wherein the liquid crystal aligning agent further comprises at least one polymer selected from the group consisting of [B] polyamic acid and polyimide. 6. The method of claim 5,
A liquid crystal display element obtained by using the polymer [B] with a diamine containing a cholestanyl group, a diamine containing a cholesteryl group, or a diamine represented by the following formula (A-1)

( ^I ) wherein X ¹ and X ² are each independently a single bond, -O-, -COO- or -OCO-, R ¹ is a methylene group or an alkylene group having 2 or 3 carbon atoms ;? is 0 or 1;? is an integer of 0 to 2, provided that? and? are not 0 at the same time; and? is an integer of 1 to 20). delete