KR101788026B1 - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

It is an object of the present invention to provide a liquid crystal display device capable of forming a liquid crystal alignment film excellent in liquid crystal alignment performance and electrical characteristics in the case of a liquid crystal display device of the PSA type after continuous driving for a long time, And to provide a liquid crystal aligning agent. In particular, it is an object of the present invention to provide a liquid crystal aligning agent capable of achieving the above problems in a liquid crystal display element of a transverse electric field system such as an IPS mode and an FFS mode, a liquid crystal alignment film formed using the same and a liquid crystal display element.
[MEANS FOR SOLVING THE PROBLEMS] The present invention relates to a liquid crystal aligning agent for forming a liquid crystal alignment film in a liquid crystal display element of a PSA system, which comprises [A] a polyorganosiloxane having a photo-orientable group, [B] a polymer having a photo- , [C] at least one polymer selected from the group consisting of polyamic acid and / or polyimide having decomposable photo alignment property.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment material, a liquid crystal alignment film, and a liquid crystal display device,

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

Liquid crystal display devices of the MVA (Multi-domain Vertical Alignment) mode are widely used. However, as a method of improving the response delay thereof, a liquid crystal material containing a polymerizable monomer is injected between substrates and the monomers are polymerized, (Polymer Sustained Alignment (PSA)) is known (see Japanese Unexamined Patent Application Publication No. 2003-307720 and Japanese Unexamined Patent Application Publication No. 2008-076950) in which a polymer layer memorizing a falling direction is formed on an alignment film. In addition, PSA technology is also being applied to a TN (Twisted Nematic) mode and an IPS (In Plane Switching) mode (see International Publication No. 2010/116551).

On the other hand, in a liquid crystal display element which tends to become finer and finer, it is difficult to perform uniform rubbing treatment due to irregularities that are inevitably generated on the surface of a substrate in accordance with the increase in density of pixels. Therefore, a photo alignment method of imparting liquid crystal aligning ability by irradiating polarized light or non-polarized light to the photosensitive organic thin film formed on the substrate surface has been developed (see JP-A-2010-217868).

Although the liquid crystal display element is applied to a high-quality monitor such as a liquid crystal television, in a conventional liquid crystal display element, it is known that when the liquid crystal display element is continuously driven for a long time, the liquid crystal alignment film is exposed to heat and light for a long time, have. In the conventional liquid crystal display device to which the PSA technique is applied, no consideration is given to the maintenance of the liquid crystal alignment performance and the electric characteristics in the case of continuous exposure for a long period of time, particularly, exposure to long time light.

Japanese Patent Application Laid-Open No. 2003-307720 Japanese Laid-Open Patent Publication No. 2008-076950 International Publication No. 2010/116551 pamphlet Japanese Laid-Open Patent Publication No. 2010-217868

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid crystal display element of a PSA type which has excellent liquid crystal alignability and is capable of suppressing deterioration of electric characteristics after continuous driving for a long period of time, And a liquid crystal aligning agent. It is an object of the present invention to provide a liquid crystal aligning agent, a liquid crystal alignment layer and a liquid crystal display element formed by using such a liquid crystal aligning agent capable of achieving the above problems in liquid crystal display elements of a transverse electric field system such as IPS mode and FFS (Fringe Field Switching) We will do it.

According to an aspect of the present invention,

As a liquid crystal aligning agent for forming a liquid crystal alignment film in a PSA type liquid crystal display element,

[A] A polyorganosiloxane having a photo-aligning group (hereinafter also referred to as "[A] polyorganosiloxane"))

[B] a polymer having a photo-orientable group in its main chain (hereinafter also referred to as "[B] polymer"), and

(C) polyamic acid and / or polyimide having decomposable photo-alignment property (hereinafter also referred to as "[C] polyamic acid and / or polyimide"),

And at least one kind of polymer selected from the group consisting of

Since the liquid crystal aligning agent contains the above-mentioned specific polymer, it is possible to suppress the deterioration of the electric characteristics due to continuous driving for a long time in the liquid crystal display element of the PSA system, in addition to the excellent liquid crystal alignability.

The liquid crystal display element is preferably a transverse electric field type. When the liquid crystal aligning agent is used in a liquid crystal display element of a transverse electric field system, the effect of the invention can be more remarkably exhibited.

The polyorganosiloxane having a photo-aligned group [A] preferably has at least one group selected from the group consisting of a group represented by the following formula (A1 ') and a group represented by the following formula (A2').

(Wherein R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, R ¹ is a phenylene group or a cyclohexylene group, provided that the phenylene group or the cyclohexylene group R ² represents a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -CH = CH- or -NH-, and a hydrogen atom, a is an integer of 0 to 3, provided that when a is 2 or 3, plural R ¹ and R ² may be the same or different, R ³ is a fluorine atom or a cyano group, b is 0 to 4 Provided that when b is 2 or more, plural R < ³ > s may be the same or different; " * "

In the formula (A2 '), R' is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group; R ⁴ is a phenylene group or a cyclohexylene group; Provided that some or all of the hydrogen atoms of the phenylene group or the cyclohexylene group may be substituted with a fluorine atom or a cyano group; R ⁵ is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -OCO- or -NH-; c is an integer of 1 to 3; Provided that when c is 2 or 3, plural R ⁴ and R ⁵ may be the same or different; R ⁶ is a fluorine atom or a cyano group; d is an integer from 0 to 4; Provided that when d is 2 or more, plural R ^{6 s} may be the same or different; R ⁷ is an oxygen atom, -COO- or -OCO-; R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group; e is an integer from 0 to 3; Provided that when e is 2 or more, plural R ⁷ and R ⁸ may be the same or different; R ⁹ is a single bond, ** - OCO- (CH ₂ ) _f - or ** - O - (CH ₂ ) _g -; &Quot; ** " represents a moiety bonded to R ⁸ ; f and g are each independently an integer of 1 to 10; "*" Is a combination).

Since the liquid crystal aligning agent contains the polymer having the specific group, the liquid crystal aligning property of the PSA type liquid crystal display element is excellent, and deterioration of the electrical characteristics due to continuous driving for a long time can be further suppressed.

[A] The polyorganosiloxane having a photo-

A polyorganosiloxane having an epoxy group,

Is preferably a reaction product of at least one compound selected from the group consisting of a compound represented by the following formula (A1) and a compound represented by the following formula (A2).

(Wherein R, R ¹ to R ³ , a and b have the same meanings as in the formula (A1 '), R', R ⁴ to R ⁹ and c to e in the formula (A2) (A2 ')).

[A] The polyorganosiloxane is a polyorganosiloxane having an epoxy group,

Is a reaction product of at least one compound selected from the group consisting of the compound represented by the formula (A1) and the compound represented by the formula (A2), wherein the liquid crystal aligning agent is a liquid crystal display element of the PSA system, It is possible to further suppress the deterioration of the electric characteristics due to the continuous driving for a long period of time.

[B] The polymer having a photo-orientable group in its main chain preferably has a structure represented by the following formula (1).

(Formula (1) of, R ¹⁰ are each independently an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom or a cyano group and a; m and n are each independently an integer of 0 to 4; where, m and n are each Two or more R ^{10 s} may be the same or different; "*" is a bond).

By having the polymer [B] having the specific structure described above, the liquid crystal aligning agent of the present invention is superior in liquid crystal alignability in the PSA type liquid crystal display element and further suppresses deterioration of the electric characteristics due to continuous driving for a long time .

The polyamic acid and / or polyimide having decomposition type photo-alignment property of [C] preferably has a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton. When the [C] polyamic acid and / or the polyimide has such a specific skeleton, the liquid crystal aligning agent can further suppress the deterioration of the electrical characteristics due to the continuous driving for a long time, as well as the liquid crystal alignability.

The liquid crystal aligning agent may further comprise at least one kind of polymer selected from the group consisting of a polyamic acid having no photo-aligning group and a polyimide having no photo-aligning group (hereinafter also referred to as " [D] polymer & .

By further containing the liquid crystal aligning agent and the [D] polymer, it is possible to more effectively suppress deterioration of the electrical characteristics by continuous driving for a long time.

The liquid crystal alignment film of the present invention is formed by the liquid crystal aligning agent. Since the liquid crystal alignment film is formed by the liquid crystal aligning agent, it is difficult to cause deterioration of the electrical characteristics due to continuous driving for a long time, as well as excellent liquid crystal alignability.

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,

And a liquid crystal alignment layer disposed on an inner surface side of at least one of the substrates so as to be in contact with the liquid crystal layer,

Wherein:

A liquid crystal display element formed by a step of injecting a liquid crystal composition containing a polymerizable monomer between the two substrates and polymerizing the monomer,

Wherein the liquid crystal alignment layer comprises,

[A] A polyorganosiloxane having a photo-aligning group

[B] a polymer having a photo-orientable group in its main chain, and

[C] polyamic acid and / or polyimide having decomposable photo-alignment property

And a liquid crystal aligning agent containing at least one kind of polymer selected from the group consisting of

Since the liquid crystal display element is a PSA type liquid crystal display element having a liquid crystal alignment film formed using the liquid crystal aligning agent, it is difficult to cause deterioration of electrical characteristics due to continuous driving for a long time in addition to excellent liquid crystal alignability.

In the step of polymerizing the monomer, it is preferable that no voltage is applied.

In the step of polymerizing the monomer, a voltage may be applied.

In the step of polymerizing the monomer, it is preferable to irradiate polarized ultraviolet rays. The liquid crystal display element can improve the liquid crystal alignability by irradiating polarized ultraviolet rays to polymerize the monomer.

The pretilt angle of the liquid crystal forming the liquid crystal layer is preferably 10 DEG or less. When the pre-tilt angle of the liquid crystal panel of the electric field system is made small, the contrast is improved.

The liquid crystal display element is preferably a transverse electric field type. The liquid crystal alignment film formed of the liquid crystal aligning agent hardly causes deterioration of the electrical characteristics due to continuous driving for a long time when applied to a liquid crystal display device of a transverse electric field system such as an IPS mode or an FFS mode. Therefore, the liquid crystal display device including the liquid crystal alignment film formed from the liquid crystal aligning agent is suitably used for the transverse electric field system.

The liquid crystal aligning agent of the present invention is excellent in liquid crystal alignability when applied to a liquid crystal display element of the PSA type, particularly in the liquid crystal display element of the transverse electric field system (IPS mode, FFS mode), and is excellent in long- It is possible to form a liquid crystal alignment film which is less liable to cause deterioration of the electrical characteristics in the case of being exposed.

1 is an explanatory view showing an electrode pattern of a conductive film in a substrate having a comb-like conductive film used in Examples and Comparative Examples.
2 is a cross-sectional view showing the structure of a liquid crystal display element of the FFS mode manufactured in Examples and Comparative Examples.

(Mode for carrying out the invention)

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent for forming a liquid crystal alignment film in a liquid crystal display device of the PSA type, wherein the polyorganosiloxane, the [B] polymer and the [C] polyamic acid and / And at least one kind of polymer selected from the group consisting of amines. In addition to the above components, the liquid crystal aligning agent may contain other components as long as the effect of the present invention is not impaired. Each component will be described in detail below.

<[A] polyorganosiloxane>

The polyorganosiloxane [A] is not particularly limited as long as it is a polyorganosiloxane having a photo-orientable group, and known ones can be used. From the group consisting of the group represented by the formula (A1 ') and the group represented by the formula It is preferable to have at least one kind of group selected.

In the formula (A1 '), R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group. R ¹ is a phenylene group or a cyclohexylene group. However, a part or all of the hydrogen atoms of the phenylene group or the cyclohexylene group may be substituted with a fluorine atom or a cyano group. R ² is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -CH = CH- or -NH-. a is an integer of 0 to 3; Provided that when a is 2 or 3, plural R ¹ and R ² may be the same or different. R ³ is a fluorine atom or a cyano group. b is an integer of 0 to 4; Provided that when b is 2 or more, plural R ³ may be the same or different. "*" Is a combined hand.

In the formula (A2 '), R' is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group. R ⁴ is a phenylene group or a cyclohexylene group. However, a part or all of the hydrogen atoms of the phenylene group or the cyclohexylene group may be substituted with a fluorine atom or a cyano group. R ⁵ is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -OCO- or -NH-. and c is an integer of 1 to 3. Provided that when c is 2 or 3, plural R ⁴ and R ⁵ may be the same or different. R ⁶ is a fluorine atom or a cyano group. and d is an integer of 0 to 4. Provided that when d is 2 or more, plural R ^{6 s} may be the same or different. R ⁷ is an oxygen atom, -COO- or -OCO-. R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group. and e is an integer of 0 to 3. Provided that when e is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different. R ⁹ is a single bond, ** - OCO- (CH ₂ ) _f - or ** - O - (CH ₂ ) _g -. And &quot; ** &quot; represents a bonding site with R &lt; ⁸ &gt;. f and g are each independently an integer of 1 to 10; "*" Is a combined hand.

The alkyl group having 1 to 3 carbon atoms for R 'in the formula (A1') and the formula (A2 ') is preferably a methyl group, an ethyl group or an n-propyl group.

The phenylene group and the cyclohexylene group of R ⁴ in R ¹ and the formula (A2 ') in the formula (A1') are each a 1,4-phenylene group or a 1,4-cyclohexylene group desirable.

The R &lt; ² &gt; in the formula (A1 ') is preferably a single bond, an oxygen atom or -CH = CH-.

The bivalent aromatic group represented by R ⁸ in the formula (A2 ') includes, for example, a 1,4-phenylene group or a 4,4'-biphenylene group. Examples of the bivalent alicyclic group include a 1,4-cyclohexylene group and a 4,4'-bicyclohexylene group. Examples of the divalent heterocyclic group include a furan-2,5-diyl group, a thiophene-2,5-diyl group, and a 2,2'-bithiophene-5,5'-diyl group. Examples of the divalent condensed ring group include anthraquinone-2,6-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene- , 7-diyl group, anthracene-9,10-diyl group, carbazole-3,6-diyl group, dibenzothiophene-2,8-diyl group and the like.

It is preferable that e in the formula (A2 ') is 0.

Specific examples of the group of the [A] polyorganosiloxane contained in the liquid crystal aligning agent of the present invention include a group represented by the formula (A1 '), for example, a group represented by the following formula.

However, in the above expression, &quot; * &quot;

The group represented by the formula (A2 ') includes, for example, groups represented by the following formulas.

However, in the above expression, &quot; * &quot;

The total of the groups represented by the formula (A1 ') and the groups represented by the formula (A2') in the [A] polyorganosiloxane contained in the liquid crystal aligning agent of the present invention is preferably 0.2 mmol / Polymer is preferably not less than 6 millimoles / g-polymer, more preferably not less than 0.3 millimoles / g-polymer and not more than 5 millimoles / g-polymer.

The [A] polyorganosiloxane contained in the liquid crystal aligning agent of the present invention preferably has an epoxy group in addition to the group represented by the formula (A1 ') and the group represented by the formula (A2'). In this case, the epoxy equivalent of the [A] polyorganosiloxane is preferably 150 g / mole or more, more preferably 200 g / mole to 10,000 g / mole, further preferably 200 g / mole to 2,000 g / mole . By using the epoxy equivalent [A] polyorganosiloxane in such a ratio, the liquid crystal aligning agent of the present invention can form a liquid crystal alignment film excellent in liquid crystal alignability and excellent in after-image characteristics without impairing storage stability .

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the [A] polyorganosiloxane contained in the liquid crystal aligning agent of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, More preferably 3,000 or more and 30,000 or less.

<Synthesis of [A] polyorganosiloxane>

As the method for synthesizing the [A] polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, any method may be used as long as it is a method capable of synthesizing the polymer as described above.

Examples of the method for synthesizing the polyorganosiloxane [A] contained in the liquid crystal aligning agent of the present invention include a method of synthesizing a polyorganosiloxane containing at least one group selected from the group consisting of the group represented by the formula (A1 ') and the group represented by the formula (A2' A method of hydrolyzing and condensing a hydrolyzable silane compound having a species group or a mixture of the hydrolyzable silane compound and another hydrolyzable silane compound;

A method of reacting a polyorganosiloxane having an epoxy group with at least one compound selected from the group consisting of the compound represented by the formula (A1) and the compound represented by the formula (A2).

Among these synthesis methods, from the viewpoints of ease of synthesis of the starting compound, ease of reaction, and the like, it is preferable to follow the latter method. Hereinafter, the polyorganosiloxane having an epoxy group, the compound represented by the formula (A1) and the compound represented by the formula (A2), which are preferable methods for synthesizing the polyorganosiloxane [A] contained in the liquid crystal aligning agent of the present invention And at least one compound selected from the group consisting of the compounds shown below.

[Polyorganosiloxane Having an Epoxy Group]

The epoxy group in the polyorganosiloxane having an epoxy group is bonded to the silicon atom through an alkylene group in which an ethylene oxide skeleton or a 1,2-epoxycycloalkane skeleton may be directly or interrupted by an oxygen atom Is preferably present in the polyorganosiloxane as contained in the group (group having an epoxy group). Examples of the group having such an epoxy group include groups represented by the following formulas (EP-1) and (EP-2).

In the formulas (EP-1) and (EP-2), &quot; * &quot;

The epoxy equivalent of the polyorganosiloxane having an epoxy group is preferably 100 g / mol or more and 10,000 g / mol or less, and more preferably 150 g / mol or more and 1,000 g / mol or less.

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of an epoxy group-containing polyorganosiloxane is preferably 500 or more and 100,000 or less, more preferably 1,000 or more and 10,000 or less, still more preferably 1,000 or more and 5,000 or less.

Such a polyorganosiloxane having an epoxy group can be produced, for example, by reacting a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound, preferably in the presence of an appropriate organic solvent, And condensation.

Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra- -Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri- , Fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec -Methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltri- Tri-sec-butoxy silane, 2- (trifluoromethyl) ethyl trichlorosilane, 2- (Trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyl tri-n-butoxysilane, 2- (trifluoromethyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- N-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro- (Perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri- Octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- Methoxy silane, 2- (perfluoro-n-octyl) ethyl triethoxy silane,

Octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro- ) Ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyl trichlorosilane, hydroxymethyltrimethoxysilane, Hydroxymethyl tri-n-propoxysilane, hydroxymethyl tri-n-butoxysilane, hydroxymethyl tri-sec-butoxysilane, 3- ( (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (Meth) acryloxypropyltri-sec-butoxysilane, 3 (meth) acryloxypropyltri-i-propoxysilane, 3- - Me 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, Mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri- Silane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri- , Phenyl trichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriethoxysilane, butoxy silane, phenyl tri-sec-butoxy silane, methyldichlorosilane, methyl dimethoxy silane, methyl diethoxy silane, methyl di-n-propoxy silane, methyl di- butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl di-n-propoxysilane, dimethyl di-n-butoxysilane, dimethyl di-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, i-propoxy silane, dimethyl di-n-butoxy silane, dimethyl di-sec-butoxysilane,

(Perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, N-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] N-octyl) ethyl] di-i-propoxysilane, (methyl) [2- (perfluoro- Octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) Propoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, Diethoxysilane, (Vinyl) di-n-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) -Butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxy Silane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, di Phenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethyl Silane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (Vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, And a silane compound having one silicon atom such as methyl (meth) (methyl) diphenylsilane.

Examples of the trade names include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X- X-22-170B, X-22-170D, X-22-170DX, X-22-170B, X- X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X- 40-9292, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X- 1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR-212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, 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, 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.). The silane compound having an epoxy group and other silane compounds may be used singly or in combination of two or more kinds.

Examples of other silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxy Propyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxy It is preferable to use at least one member selected from the group consisting of silane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane desirable.

In the synthesis of the polyorganosiloxane having an epoxy group in the present invention, the use ratio of the silane compound having an epoxy group to the other silane compound is adjusted so that the epoxy equivalent of the resulting polyorganosiloxane is in the above- .

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

Examples of the hydrocarbons include toluene, xylene, and the like.

Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone.

Examples of the ester solvent 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 solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like.

Examples of the alcoholic solvent include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono- Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Of these, water-insoluble solvents are preferred.

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 or more and 10,000 parts by mass or less, more preferably 50 parts by mass or more and 1,000 parts by mass or more, based on 100 parts by mass of the total amount of the silane compound. Here, the total of the silane compounds refers to the sum of the silane compounds having an epoxy group and other silane compounds optionally used.

The amount of water used when synthesizing the polyorganosiloxane having an epoxy group is preferably 0.5 mol or more and 100 mol or less and more preferably 1 mol or more and 30 mol or less based on 1 mol of the total amount of the silane compound.

Examples of the catalyst include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. Of these, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, a desired polyorganosiloxane can be obtained at a high hydrolysis and condensation rate without causing a side reaction such as ring opening of an epoxy group, Do. The liquid crystal aligning agent of the present invention 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 cinnamic acid derivative is suitable because of its excellent storage stability. This is because, as indicated in Non-Patent Document 1 (Chemical Reviews, 95, p1409 (1995)), when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis and condensation reaction, Structure or a cage-like 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 of the present invention contains the other polymer described below, the condensation reaction between the silanol group and the other polymer is suppressed Therefore, it is deduced that the storage stability is excellent. Among them, organic bases are more preferable. The amount of the organic base to be used differs depending on the kind of the organic base, the reaction conditions such as the temperature, and the like, and is appropriately set. For example, it is preferably not less than 0.01 mole and not less than 3 mole per mole of the total silane compound, More preferably 1 mole or less.

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. Of 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.

The hydrolysis and condensation reaction in the synthesis 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 this solution with an organic base and water, For example, by heating using an appropriate heating device such as an oil bath.

The heating temperature in the hydrolysis and condensation reaction is preferably 130 占 폚 or lower, more preferably 40 占 폚 or higher and 100 占 폚 or lower. The heating time is preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During the heating, the mixed solution may be stirred or may not be stirred, or the mixed solution may be left under reflux.

After completion of the reaction, the organic solvent layer separated from the reaction mixture is preferably washed 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 washing becomes neutral, and then the organic solvent layer is dried with an appropriate desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain a desired polyol having an epoxy group To obtain a siloxane.

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).

[Compound represented by the formula (A1) and compound represented by the formula (A2)

Specific examples of the compound represented by each of the above formulas (A1) and (A2) include compounds represented by the formulas (A1 ') and (A2') in which hydrogen atoms are bonded to the bonds of the groups exemplified above Carbonic acid.

[Method for synthesizing [A] polyorganosiloxane]

The polyorganosiloxane [A] preferably contains at least one compound selected from the group consisting of the polyorganosiloxane having the epoxy group, the compound represented by the formula (A1) and the compound represented by the formula (A2) In the presence of a catalyst and an organic solvent.

The amount of the compound represented by the formula (A1) and the compound represented by the formula (A2) in the above reaction is preferably 0.001 mol to 10 mol relative to 1 mol of the epoxy group of the polyorganosiloxane, More preferably from 0.01 mol to 5 mol, still more preferably from 0.05 mol to 2 mol, and particularly preferably from 0.05 mol to 0.8 mol.

As the catalyst, known compounds can be used as so-called curing accelerators for promoting the reaction between an organic base or an epoxy compound and an acid anhydride.

As for the organic base, the description of the organic base used in the synthesis of the polyorganosiloxane having the epoxy group can be applied.

Examples of the curing accelerator include 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- (2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s - triazine, 2 , Isocyanuric acid adduct of 4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl- An isocyanuric acid adduct of phenylimidazole, an isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s- Imidazole compounds;

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 N-butylphosphonium tetra-n-butylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O-diethylphosphorothioate, tetra- Quaternary phosphonium salts such as fluoroborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate;

Diazabicyclo [5.4.0] undecene-7 and its organic acid salts;

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 dicyandiamide, an amine addition type accelerator such as an amine and an adduct with an epoxy resin;

A microcapsulated latent curing accelerator wherein 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.

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

The amount of the catalyst to be used is preferably 100 parts by mass or less, more preferably 0.01 parts by mass or more and 100 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the polyorganosiloxane having an epoxy group Do.

The reaction of the polyorganosiloxane having an epoxy group with at least one compound selected from the group consisting of the compound represented by the formula (A1) and the compound represented by the formula (A2) can be carried out in the presence of an organic solvent . Examples of the organic solvent include hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, amide solvents, alcohol solvents and the like. Of these, ether solvents, ester solvents and ketone solvents are preferable from the viewpoints of solubility of raw materials and products and ease of purification of products. The solvent is preferably used in a proportion such that the 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) is 0.1% by mass or more, and preferably 5% It is more preferable to use it.

The temperature in the reaction is preferably 0 to 200 占 폚, more preferably 50 to 150 占 폚. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

The method for synthesizing the [A] polyorganosiloxane is preferably a method of synthesizing a polyorganosiloxane having at least a group selected from the group consisting of the groups represented by each of the formulas (A1 ') and (A2') by the ring-opening part of the epoxy contained in the polyorganosiloxane having an epoxy group And introducing one kind of group. This synthesis method is very suitable in that it can be easily introduced and can increase the introduction ratio of at least one group selected from the group consisting of the groups represented by each of the formulas (A1 ') and (A2').

<[B] Polymer>

As the polymer [B], a known one that is a polymer having a photo-orientable group in its main chain can be used, but a polymer having a structure represented by the above formula (1) (hereinafter also referred to as &quot; structure (1) Polymer &quot;). Specific polymers will be described below.

&Lt; Specific polymer &

In the formula (1), R ¹⁰ is each independently an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom or a cyano group. a is independently an integer of 0 to 4; "*" Is a combined hand.

The R ¹⁰ in the formula (1) is preferably an alkyl group having 1 to 4 carbon atoms or a halogen atom, more preferably a methyl group or a fluorine atom. a is preferably 0 to 2, more preferably 0 or 1.

The specific polymer in the present invention preferably has, in addition to the structure (1), a structure having a methylene group or an alkylene group having 2 to 12 carbon atoms (hereinafter also referred to as "structure (2)"). Provided that at least one of the methylene group and (di) alkylmethylene group located at the terminal of the alkylene group is an oxygen atom, an ester bond, a divalent alicyclic group having 5 to 10 carbon atoms, a divalent alicyclic group having 6 to 24 carbon atoms An arylene group, a dialkylsilylene group or a dialkylsiloxylene group having 2 to 10 silicon atoms. By having the specific polymer additionally have such a structure, the liquid crystal alignment film formed from the liquid crystal aligning agent containing such a specific polymer is given an appropriate flexibility, and as a result, a good liquid crystal alignment property is exhibited. As the structure (2), a structure composed of an alkylene group having 2 to 12 carbon atoms is preferable.

Examples of the divalent alicyclic group having 5 to 10 carbon atoms include a 1,4-cyclohexylene group and the like.

Examples of the arylene group having 6 to 24 carbon atoms include a 1,3-phenylene group and a 1,4-phenylene group.

Examples of the dialkylsiloxylene group having 2 to 10 silicon atoms include groups represented by the following formulas.

Wherein b is, independently of each other, an integer of 1 to 8; and c is an integer of 1 to 9. "*" Indicates a combined hand.

Examples of the structure (2) include a 1,2-ethylene group, a 1,4-butylene group, a 1,6-hexylene group, a 1,8-octylene group, -Dodecylene group and a group represented by the following formula.

In the above formula, &quot; * &quot;

Content of the structure (1) in the specific polymer is, 5 × 10 ^{- 4} mol / g~4 × 10 ^{- 3} mol / g, and preferably, 1 × 10 ^{- 3} mol /g~3.5×10 ^{- 3} mol / g, and a more preferably, 1.5 × 10 ^- it is more preferably from ³ mol / g ^{- 3} mol / g~3 × 10.

Content of the structure (2) in the specific polymer, 6 × 10 ^-, and more preferably ³ mol / g ^{- 3} mol / g or less is preferable, and, 1 × 10 ^{- 3} mole / g~6 × 10 , 1.5 × 10 ^{- 3} mole / g~4 × 10 ^- that the ³ mole / g is more preferred.

The structures (1) and (2) in a specific polymer may be located at one or more positions selected from the main chain, side chain and terminal of the polymer, respectively. However, the main chain of the polymer is preferably a liquid crystal alignment film The pretilt angle can be reduced.

Examples of the main skeleton of the specific polymer in the present invention include polyorganosiloxane, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (Phenylmaleimide) derivatives, poly (meth) acrylates, and reaction products of polyfunctional carboxylic acids with polyfunctional epoxy compounds. Of these, a reaction product of a polyfunctional carboxylic acid and a polyfunctional epoxy compound is preferable.

The reaction product of the polyfunctional carboxylic acid as the specific polymer in the present invention with the polyfunctional epoxy compound may be produced by any method as long as it has the above-mentioned structure (1), but the polyfunctional epoxy containing a diepoxy compound Compound and a polyfunctional carboxylic acid containing a dicarboxylic acid having the structure (1) are preferable from the viewpoints of simplicity of the production method and easy isolation and purification of a specific polymer. Hereinafter, a preferred method for producing a specific polymer in the present invention will be described in detail.

&Lt; Synthesis method of specific polymer &

[Multifunctional epoxy compound]

The polyfunctional epoxy compound used for producing the specific polymer preferred in the present invention includes a diepoxy compound. The diepoxy compound is a compound having two epoxy groups and may be a compound having two epoxy groups bonded together, or a compound having two epoxy groups in addition to the structure (2). The diepoxy compound is preferable because the specific polymer to be obtained has the structure (2) in addition to the structure (1) by using a compound having the structure (2) in addition to the two epoxy groups.

Examples of such a diepoxy compound include compounds represented by the following formula (DE-1), such as compounds in which two epoxy groups are bonded. Examples of the compound having the structure (2) in addition to the two epoxy groups include compounds represented by the following formulas (DE-2) to (DE-11). The diepoxy compound may be used alone, or two or more diepoxy compounds may be used in combination.

As the polyfunctional epoxy compound in the present invention, other polyfunctional epoxy compounds may be used together with the above-mentioned diepoxy compound. Other polyfunctional epoxy compounds which can be used herein are preferably compounds having three or more epoxy groups, more preferably compounds having three or four epoxy groups, for example, trimethylolpropane triglycidyl ether , N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, '-Tetraglycidyl-4,4'-diaminodiphenylmethane, and the like can be preferably used. As the polyfunctional epoxy compound, at least one selected from the above can be used.

The proportion of the diepoxy compound used in the polyfunctional epoxy compound is preferably more than 0.5 mole, more preferably more than 0.5 mole but not more than 0.999 mole, more preferably more than 0.8 mole but not more than 0.998 mole per mole of the total amount of the polyfunctional epoxy compound Mole or less, and particularly preferably 0.9 mole or more and 0.995 mole or less. With such a use ratio, the light resistance of the electrical characteristics of the liquid crystal alignment film to be formed can be further improved without impairing the effect of the present invention.

[Polyfunctional carbonic acid]

The polyfunctional carboxylic acid used for producing the specific polymer preferred in the present invention includes a compound having at least one of the above structures (1) and two carboxyl groups (hereinafter also referred to as "dicarboxylic acid") . Examples of such dicarboxylic acids include compounds represented by the following formulas (DC-1) to (DC-4). The dicarboxylic acid may be used alone, or two or more dicarboxylic acids may be used in combination.

As the polyfunctional carboxylic acid in the present invention, other polyfunctional carboxylic acid may be used together with the above-mentioned dicarboxylic acid. The other polyfunctional carbonic acid that can be used herein is a polyfunctional carboxylic acid having no structure (1), preferably a compound having three or more carboxyl groups, more preferably three or four carboxyl groups / RTI &gt;

Examples of other polyfunctional carboxylic acid include trimellitic acid, pyromellitic acid, 1,3,5-tris (4-carboxyphenyl) benzene, 1,2,4-cyclohexanetricarboxylic acid, 1,2 , 4,5-cyclohexanetetracarboxylic acid, and the like. Further, as the other polyfunctional carbonic acid, at least one selected from the above can be used.

The proportion of the dicarboxylic acid used in the polyfunctional carboxylic acid is preferably more than 0.5 mole, more preferably more than 0.5 mole and not more than 0.999 mole, more preferably not less than 0.8 mole and not more than 0.998 mole per mole of the total amount of the polyfunctional epoxy compound Or less, more preferably 0.9 mol or more and 0.995 mol or less. By using such a use ratio, the light resistance and heat resistance of the electric characteristics can be further improved without impairing the effect of the present invention.

[Production method of specific polymer]

The specific polymer preferred in the present invention can be obtained by reacting the polyfunctional epoxy compound with a polyfunctional carboxylic acid, preferably in an appropriate organic solvent.

The ratio of the polyfunctional epoxy compound to the polyfunctional carboxylic acid used in the preparation of the specific polymer is preferably 0.8 mol or more and 1.2 mol or less and more preferably 0.9 or more More preferably 1.1 mol or less.

Examples of the organic solvent that can be used in the reaction between the polyfunctional epoxy compound and the polyfunctional carboxylic acid include an aliphatic hydrocarbon, a phenolic solvent, an ether, an ester, a ketone, a nonprotonic polar solvent, and the like . Among them, it is preferable to use a phenolic solvent or aprotic polar solvent in view of the solubility of raw materials and products.

Examples of the preferable organic solvent include phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol; N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethylsulfoxide, gamma -butyrolactone, tetramethylurea, And aprotic polar solvents such as hexamethylphosphotriamide.

The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the mass of components other than the organic solvent in the reaction solution to the total mass of the solution) is 5 mass% or more, and preferably 10 mass% or more and 50 mass% Is more preferable.

The reaction between the polyfunctional epoxy compound and the polyfunctional carboxylic acid can be carried out in the presence of a catalyst, if necessary. As such a catalyst, known compounds can be used as so-called curing accelerators for accelerating the reaction between the epoxy compound and the acid anhydride in addition to the organic base.

Examples of the organic base include the same organic base used in the synthesis of [A] polyorganosiloxane.

The use ratio of the catalyst is preferably 30 parts by mass or less based on 100 parts by mass of the total amount of the polyfunctional epoxy compound and the polyfunctional carboxylic acid.

The reaction temperature between the polyfunctional epoxy compound and the polyfunctional carboxylic acid is preferably 25 ° C or more and 200 ° C or less, more preferably 40 ° C or more and 180 ° C or less. The reaction time is preferably from 10 minutes to 48 hours, more preferably from 1 hour to 24 hours.

The terminal of the specific polymer in the present invention may be a carboxyl group, an epoxy group, or an epoxy group converted by hydrolysis or the like. In the present invention, a specific polymer can be provided in the preparation of an alignment agent without particularly modifying its terminal. However, during or after the production of the specific polymer of the present invention, monocarboxylic acid such as benzoic acid or monoepoxy compound such as benzyl glycidyl ether is added and reacted to obtain a specific polymer modified at the terminal, May be provided to the preparation of

<[C] Polyamic acid and / or polyimide>

The liquid crystal aligning agent contains a polyamic acid and / or a polyimide having a [C] decomposition type optical alignment property. Here, the decomposition type photo-alignment property means that when a photo-cleavage reaction occurs in a part of the polymer main chain or side chain in the case of irradiating polarized light or unpolarized ultraviolet light, a liquid crystal aligning function is developed .

The conditions under which the photocleaching reaction takes place include, for example, those in which the wavelength of ultraviolet light of polarized light or unpolarized light to be irradiated is 200 nm or more and 300 nm or less and the irradiation amount is 2,000 J / m 2 or more. Further, as the condition where the photocleavage reaction is likely to occur more, the wavelength is preferably 220 nm or more and 280 nm or less, and particularly preferably 254 nm. The irradiation dose is preferably 4,000 J / m 2 or more, more preferably 6,000 J / m 2 or more, and still more preferably 8,000 J / m 2 or more.

As the [C] polyamic acid and / or the polyimide, known ones can be used, the polyamic acid preferably has any of the structural units represented by the following formulas (c-1) to (c-4) It is preferable that the polyimide has a structural unit represented by the following formula (c-5) or (c-6).

In the formulas (c-1) to (c-6), R ^c1 and R ^c2 each independently represent a divalent organic group.

The polyamic acid in the [C] polyamic acid and / or polyimide is preferably a polymer having a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton. The polyamic acid can be synthesized by, for example, reacting a tetracarboxylic acid dianhydride having a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton with a diamine compound in an organic solvent.

Examples of the tetracarboxylic acid dianhydride having a bicyclo [2.2.2] octene skeleton include bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 7- Methyl-bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 7-ethyl-bicyclo [2.2.2] oct- Tetracyanoic acid dianhydride, 7-n-propyl-bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, Cyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 7-sec-butyl- bicyclo [2.2.2] Tetracarboxylic acid dianhydride, 1-methyl-bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 1-methyl- [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 1-methyl-7-ethyl-bicyclo [2.2.2] Tetracyanoic acid dianhydride, 5,6-tetracarboxylic acid dianhydride, 1-methyl-7-n-propyl-bicyclo [2.2.2] Methyl-7-sec-butyl-bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, .2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride. Of these, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-methyl-bicyclo [2.2.2] , 5,6-tetracarboxylic dianhydride, 7-methyl-bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, Bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride is preferable, and bicyclo [2.2.2] oct-7-ene-2,3,5,6 -Tetracarboxylic acid dianhydride and 7-methyl-bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride are more preferable, and bicyclo [2.2.2] -7-ene-2,3,5,6-tetracarboxylic dianhydride is more preferable.

Examples of the tetracarboxylic acid dianhydride having a cyclobutane skeleton include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid 2-anhydride and the like. Of these, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride is preferable.

The content ratio of the tetracarboxylic acid dianhydride having a bicyclo [2.2.2] octene skeleton or the cyclobutane skeleton in the polyamic acid to the diamine-derived arctic acid structural unit is preferably 10 mol Or more, more preferably 30 mol% or more, and still more preferably 50 mol% or more.

The method of synthesizing other tetracarboxylic acid dianhydrides, diamine compounds and polyamic acid used in the synthesis of polyamic acid in the [C] polyamic acid and / or polyimide is the same as that of the other polyamic acid .

The polyimide in the [C] polyamic acid and / or the polyimide can be synthesized by dehydrating and ring-closing the acid structure of the polyamic acid, and can be obtained in the same manner as the polyimide shown as the other polymer described later.

<Other components>

Examples of other components that may contain the liquid crystal aligning agent include polymers other than [A] to [C] (hereinafter also referred to as "other polymers"), curing agents, curing catalysts, curing accelerators, (Excluding those corresponding to the [A] polyorganosiloxane, hereinafter also referred to as an &quot; epoxy compound &quot;), a functional silane compound (excluding those corresponding to the polyorganosiloxane [A] ), A surfactant, and the like. Each component will be described in detail below.

[Other Polymers]

The other polymer can be used to further improve the solution characteristics of the liquid crystal aligning agent of the present invention and the electrical characteristics of the resulting liquid crystal alignment film. Examples of the other polymer include at least one polymer selected from the group consisting of a polyamic acid having no photo-aligning group and a polyimide having no photo-aligning group, a polyorganosiloxane other than the [A] polyorganosiloxane ( Hereinafter also referred to as &quot; other polyorganosiloxane &quot;) is suitably used. In addition to these, poly (amic acid ester), polyester, polyamide, cellulose derivatives, polyacetal, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives and poly (meth) acrylates. Hereinafter, [D] polymers and other polyorganosiloxanes will be described.

[[D] polymer]

The [D] polymer is at least one polymer selected from the group consisting of a polyamic acid having no photo-aligning group and a polyimide having no photo-aligning group.

(Polyamic acid)

The polyamic acid can be obtained by reacting a tetracarboxylic acid dianhydride with a diamine.

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, and the like.

Examples of the aliphatic tetracarboxylic acid dianhydride include butane tetracarboxylic dianhydride.

Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4 , 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3,9- -Tetrahydrofuran-2 &apos;, 5 ' -dione), 5- (2,5-dioxotetrahydro- 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: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- 3,5,8,10-tetraon, and the like.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride and the like.

In addition to the tetracarboxylic acid dianhydride, tetracarboxylic acid dianhydrides described in Japanese Patent Application No. 2009-157556, No. 2009-169224, and No. 2008-20899 can be used.

Among the tetracarboxylic acid dianhydrides used for synthesizing the polyamic acid, those containing an alicyclic tetracarboxylic dianhydride are preferred, and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1 , And 2,3,4-cyclobutanetetracarboxylic acid dianhydride, and more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. Do.

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid may be selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride. Of the total tetracarboxylic acid 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 and / And more preferably at least one selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride.

Examples of diamines used for synthesizing polyamic acid include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like.

Examples of the aliphatic diamines include 1,1-meta-xylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and the like.

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 p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'- Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamine Bis (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2- (4-aminophenyl) hexafluoropropane, 4,4 '- (p-phenylenediisopropylidene) bisaniline, 4,4' - (m Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, Diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl- 3,6-diaminocarbazole , N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecanoxy- Oxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy- 2,5-diaminobenzene, tetradecanoxy- 2,5-diaminobenzene,

Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, Stearyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-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- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate , 1, 1 -bis (4 - ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1, , 1-bis (4 - ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1- ), And the compound represented by such as phenyl) -4- (4-heptyl cyclohexyl) cyclohexane, the following formula (D-1).

In the formula (D-1), X ^I is an alkyl group, ^* -O-, ^* -COO- or ^* -OCO- of 1 to 3 carbons. Here, &quot; * &quot; represents a site bonding with a diaminophenyl group. h is 0 or 1; i is an integer of 0 to 2. j is an integer of 1 to 20;

Formula ^I wherein X is 1 to 3 carbons of the alkyl group of the (D-1), ^* is preferably -O- or -COO- ^*.

Examples of the group C _j H _{2j +1} - in the above formula (D-1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, , n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, , n-octadecyl group, n-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.

In the formula (D-1), it is preferable that h and i are not 0 at the same time.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-4).

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like.

As the diamine used for synthesizing polyamic acid, diamines described in Japanese Patent Application Nos. 2009-157556, 2009-169224 and 2008-20899 may be used in addition to the above.

These diamines may be used alone or in combination of two or more.

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used for the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic acid dianhydride is 0.2 to 2 equivalents based on 1 equivalent of the amino group contained in the diamine compound , More preferably 0.3 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, halogenated phenol and the like.

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 (b) of the tetracarboxylic acid dianhydride and the diamine compound and the total amount % To 30% by mass.

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, .

When the polyamic acid is subjected to dehydration ring closure to form a polyimide, the reaction solution may be directly supplied to the dehydration ring-closing reaction. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration ring- May be purified and then subjected to a dehydration ring-closing reaction. The polyamic acid may be isolated by a method in which the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate and the precipitate is dried under reduced pressure or a method in which an organic solvent in the reaction solution is distilled off under reduced pressure . 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 synthesized by dehydration ring closure of the arboric acid structure of the polyamic acid obtained as described above. At this time, all of the arctic structure may be completely imidized by dehydrating and ring closure, or only a part of the arid acid structure may be dehydrated and ring-closed to form a partial imide having an acid structure and an imide structure. The dehydration ring-closure of the polyamic acid can be carried out by a method comprising the steps of (i) heating a polyamic acid, or (ii) dissolving a polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring- .

The reaction temperature in the method of heating the polyamic acid of (i) is preferably 50 to 200 캜, more preferably 60 to 170 캜. If the reaction temperature is less than 50 캜, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 캜, the molecular weight of the obtained polyimide may be lowered. 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, the present invention 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 .

The polyimide obtained in the above method (i) may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided in the preparation of the liquid crystal aligning agent after the obtained polyimide is purified. On the other hand, in the method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent. After removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, the reaction solution may be supplied to the preparation of the liquid crystal aligning agent. 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 performing the same operation as described above as a method for isolating and purifying polyamic acid.

(Other polyorganosiloxane)

Other polyorganosiloxanes in the present invention are polyorganosiloxanes other than the above [A] polyorganosiloxane. Such other polyorganosiloxanes are obtained by reacting at least one silane compound (hereinafter also referred to as a &quot; raw silane compound &quot;) selected from the group consisting of an alkoxysilane compound and a halogenated silane compound, preferably in an appropriate organic solvent , Water, and a catalyst.

Examples of the raw material silane compound used herein include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra- Butoxysilane, tetra-tert-butoxysilane, tetrachlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriiso- propoxysilane, methyltri-n Butoxysilane, methyltri-sec-butoxysilane, methyltri-butoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n -Propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxy Silane, phenyltriethoxysilane, phenyltrichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Dimethyl dichlorosilane, trimethyl silane, and the like can be given to trimethyl silane, trimethyl chlorosilane. It is preferable to use at least one of them. In particular, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxy It is preferable to use at least one member selected from the group consisting of silane, dimethyldiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane. Other polyorganosiloxanes in the present invention can be synthesized in the same manner as described above as a method for synthesizing a polyorganosiloxane having an epoxy group, except that the raw silane compound as described above is used.

For other polyorganosiloxanes, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is preferably 1,000 to 100,000, more preferably 5,000 to 50,000.

In addition, in the case of the liquid crystal aligning agent containing the [A] polyorganosiloxane or the [B] polymer, in the case where the liquid crystal aligning agent is used under the condition that the photocleaching reaction of the [C] polyamic acid and / or the polyimide does not occur, Since the effect of the invention due to the decomposition type photo-alignment property is not obtained, the [C] polyamic acid and / or polyimide may be contained as other polymer.

(Ratio of use of other polymer)

When the liquid crystal aligning agent of the present invention contains at least one of the above-mentioned [A] to [C] together with other polymer, the proportion of the other polymer used is preferably 100 parts by mass in total of [A] to [C] By mass to 10,000 parts by mass or less. A more preferable use ratio of the other polymer differs depending on the kind of the other polymer. In the case where the liquid crystal aligning agent of the present invention contains at least one of [A] to [C] and the polymer [D], the more preferable ratio of use of both is from [A] to [C] , The total amount of the [D] polymer is preferably 10 to 5,000 parts by mass, and more preferably 100 to 2,000 parts by mass. Further, in the case where the liquid crystal aligning agent of the present invention contains at least one of [A] to [C] and other polyorganosiloxane, the more preferable ratio of both of them is [A] to [C ], The amount of other polyorganosiloxane is 5 to 2,000 parts by mass.

[Curing agent and curing catalyst]

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

Examples of the polyvalent carboxylic anhydrides 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 anhydrides include 4-methyl tetrahydrophthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, ), And Diels-Alder reaction products of an alicyclic compound having a conjugated double bond such as a tetracarboxylic acid dianhydride,? -Terpinene, and allocimene and maleic anhydride, which are commonly used in the synthesis of a polyamic acid, Hydrogenated products, and the like.

In the above formula (CA-1), k is an integer of 1 to 20.

As the curing catalyst, for example, an antimony hexafluoride compound, a hexafluorophosphate compound, aluminum trisacetylacetonate and the like can be used. These catalysts can catalyze the cationic polymerization of epoxy groups 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 contained in the liquid crystal aligning agent of the present invention from the viewpoint of improving the adhesiveness of the formed liquid crystal alignment film to the substrate surface. Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) Hexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- Methyl cyclohexane is preferred.

When the liquid crystal aligning agent of the present invention contains an epoxy compound, the content thereof is preferably 40 parts by mass or less based on 100 parts by mass of the total of the above-mentioned [A] to [C] More preferably 0.1 to 30 parts by mass.

When the liquid crystal aligning agent of the present invention 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 further improving the adhesion of the resulting liquid crystal alignment film to the substrate. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, 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- Bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Also, a reaction product of the tetracarboxylic acid dianhydride described in JP-A-63-291922 and a silane compound having an amino group can be used.

When the liquid crystal aligning agent of the present invention contains a functional silane compound, the content thereof is preferably 50 mass% or more based on 100 mass parts of the total of [A] to [C] and optionally other polymer Or less, and 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 of the present invention 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.

The liquid crystal aligning agent for forming a liquid crystal alignment film in the liquid crystal display element of the PSA system of the present invention,

[A] A polyorganosiloxane having a photo-aligning group

[B] a polymer having a photo-orientable group in its main chain, and

[C] polyamic acid and / or polyimide having decomposition type optical orientation,

[A] at least one polymer selected from the group consisting of polyorganosiloxane and [B] polymer is preferable, and [A] at least one polymer selected from the group consisting of poly More preferably, it contains an organosiloxane.

The liquid crystal aligning agent of the present invention preferably further contains a polymer [D], and the use ratio thereof is 10 parts by mass to 5,000 parts by mass when the total solid content of the polymers [A] to [C] is 100 parts by mass Parts by mass, and preferably 100 parts by mass to 2,000 parts by mass.

[menstruum]

The liquid crystal aligning agent is preferably prepared as a solution-like composition in which each component is dissolved in an organic solvent. As the organic solvent that can be used for preparing the liquid crystal aligning agent of the present invention, it is preferable to dissolve the polymer of [A] to [C] contained in the liquid crystal aligning agent and other optional components to be used, Do.

The organic solvent which can be preferably used in the liquid crystal aligning agent of the present invention differs depending on the kind of other polymer optionally added. When the liquid crystal aligning agent of the present invention contains the [A] polyorganosiloxane and the [D] polymer, the organic solvent used is not limited to the organic solvent used for the synthesis of the 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 of the present invention is a polymer containing only [A] a polyorganosiloxane or [A] containing a polyorganosiloxane and other polyorganosiloxane, but containing [D] Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monomethyl ether. Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, Monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, Propylcarbitol, butylcarbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, n-butyl acetate, Butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, acetic acid n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, and isoamyl acetate. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-

The preferred solvent used in the preparation of the liquid crystal aligning agent of the present invention is one obtained by combining one or more of the above organic solvents depending on whether or not other polymers are used and the kind thereof. , The components contained in the liquid crystal aligning agent are not precipitated, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mN / m.

The solid concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the mass of all components other than the solvent in the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., Mass%. The liquid crystal aligning agent of the present invention is applied to the surface of a substrate to form a coating film which becomes a liquid crystal alignment film. When the solid concentration is less than 1% by mass, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film have. On the other hand, when the solid concentration exceeds 10% by mass, the film thickness of the coating film becomes excessively large, and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased and the coating property is sometimes insufficient. A particularly preferable range of the solid concentration is different depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the range of 1.5 to 4.5 mass% is particularly preferable. In the case of the printing method, it is particularly preferable to set the solids concentration in the range of 3 to 9 mass% and accordingly the solution viscosity 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 to 5 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 of the present invention is preferably 0 ° C to 200 ° C, and more preferably 0 ° C to 40 ° C.

&Lt; Liquid crystal alignment film &

The liquid crystal alignment film of the present invention is a liquid crystal alignment film in a PSA type liquid crystal display device, and is formed by, for example, the photo alignment method using the liquid crystal aligning agent. The liquid crystal alignment film of the present invention is preferable because the effects of the present invention are maximized when applied to a liquid crystal display device of a transverse electric field system such as an IPS mode or an FFS mode.

In order to form the liquid crystal alignment film, the liquid crystal aligning agent may be applied on the substrate to form a coating film, and the formed coating film may be irradiated with radiation.

Here, when the liquid crystal aligning agent of the present invention is applied to a liquid crystal display element having a liquid crystal cell of a transverse electric field system, a substrate having a transparent conductive film or a metal film patterned in a comb shape on one side, A pair of opposed substrates on which electrodes are not formed are formed as a pair, and a liquid crystal aligning agent of the present invention is applied to the surface of the comb-shaped electrode and the surface of the opposed substrate, respectively, to form a coated film.

As the above substrate, for example, glass such as float glass or soda glass, transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, or polycarbonate can be used.

As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ -SnO ₂ , a NESA (registered trademark) film made of SnO ₂ , or the like can be used.

As the metal film, for example, a film made of a metal such as chromium can be used. The patterning of the transparent conductive film and the metal film includes, for example, a method of forming a pattern by a photo-etching method or a sputtering method after forming a transparent conductive film without a pattern, a method of forming a transparent conductive film by using a mask having a desired pattern Method and the like.

In the case of the FFS mode, a common electrode, an insulating layer, a signal electrode and a liquid crystal alignment film are formed in this order on the surface of one of the pair of substrates on the liquid crystal layer side in the liquid crystal display element of the present invention. As the common electrode, for example, an NESA film (a registered trademark of PPG Corporation, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. The shape of the common electrode may be a so-called &quot; solid film &quot; having no pattern formed on one surface of the substrate, or a patterned electrode having an arbitrary pattern. The thickness of the common electrode is preferably 10 nm to 200 nm, more preferably 20 nm to 100 nm. The common electrode can be formed on the substrate by a known method, for example, a sputtering method.

The insulating layer may be made of, for example, silicon nitride. The thickness of the insulating layer is preferably 100 nm to 1,000 nm, more preferably 150 nm to 750 nm. The insulating layer can be formed on the common electrode by a known method, for example, a chemical vapor deposition method or the like.

The signal electrode may be made of the same material as the common electrode. The signal electrode may be, for example, a comb-like electrode having a plurality of comb teeth. Each of the comb teeth of the comb-like electrode may have, for example, a linear shape, a &quot; k &quot; shape, or the like.

A functional silane compound, titanate, or the like is previously coated on the substrate and the electrode in order to improve the adhesion between the substrate, the conductive film or the electrode and the coating film upon application of the liquid crystal aligning agent onto the substrate You can leave it. The application of the liquid crystal aligning agent onto the substrate can be preferably carried out by an appropriate application method such as offset printing, spin coating, roll coatering or inkjet printing, and then the coated surface is preheated (prebaked) , Followed by baking (post baking) to form a coating film. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 占 폚, and postbaking conditions are preferably 120 to 300 占 폚, more preferably 150 to 250 占 폚, preferably 5 minutes To 200 minutes, and more preferably from 10 minutes to 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 mu m to 1 mu m, more preferably 0.005 mu m to 0.5 mu m.

The coating film thus formed is irradiated with linearly polarized light or partially polarized radiation or non-polarized radiation, thereby imparting liquid crystal aligning ability. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet rays including light having a wavelength of 200 nm to 400 nm are preferable. When the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed in a direction perpendicular to the substrate surface, in an oblique direction, or in combination. In the case of irradiating non-polarized radiation, the irradiation direction needs to be an oblique direction.

As the light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp and an excimer laser can be used. The ultraviolet ray of the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with a filter, a diffraction grating, or the like.

[A] In the case of a liquid crystal aligning agent containing a polyorganosiloxane, it is preferable to use radiation of 300 to 400 nm for exposure. The irradiation dose of the radiation is not less than 1 J / m 2 and not more than 10,000 J / m 2, and preferably not less than 10 J / m 2 and not more than 4,000 J / m 2. [B] In the case of a liquid crystal aligning agent containing a polymer, it is preferable to use radiation of 300 to 400 nm for exposure. The irradiation dose of the above radiation is preferably 1 J / m 2 or more and 20,000 J / m 2 or less, and more preferably 10 J / m 2 or more and 10,000 J / m 2 or less. [C] In the case of a liquid crystal aligning agent containing a polyamic acid and / or a polyimide, it is preferable to use radiation of 200 to 300 nm for exposure. The irradiation dose of the radiation is preferably 1 J / m 2 or more and 20,000 J / m 2 or less, more preferably 10 J / m 2 or more and 10,000 J / m 2 or less.

<Liquid crystal display element>

A liquid crystal display element of the present invention comprises a pair of substrates arranged to face each other,

A liquid crystal layer disposed between the two substrates,

And a liquid crystal alignment layer disposed on an inner surface side of at least one of the substrates so as to be in contact with the liquid crystal layer,

Wherein:

A liquid crystal display element formed by a step of injecting a liquid crystal composition containing a polymerizable monomer between the two substrates and polymerizing the monomer,

Wherein the liquid crystal alignment layer comprises,

[A] A polyorganosiloxane having a photo-aligning group

[B] a polymer having a photo-orientable group in its main chain, and

[C] polyamic acid and / or polyimide having decomposable photo-alignment property

And a liquid crystal aligning agent containing at least one kind of polymer selected from the group consisting of

This liquid crystal display element can be manufactured, for example, as follows. First, a pair of substrates on which a liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell having a structure in which a polymerizable liquid crystal composition is sandwiched is formed between the pair of substrates. The polymerizable liquid crystal composition of the present invention is composed of a mixture of a liquid crystal and a polymerizable compound, for example, a liquid crystal mixture described in JP-A-2009-102639. The liquid crystal is composed of a positive type liquid crystal or a negative type liquid crystal. As the positive type liquid crystal or the negative type liquid crystal, a stick type positive type liquid crystal is preferable. As the polymerizable compound, those known in the liquid crystal display device of the PSA type can be used.

The thickness of the liquid crystal layer (distance between the signal electrode and the counter substrate) is preferably 3 to 10 mu m.

As a method for producing the liquid crystal cell, for example, the following two methods can be given. 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 polymerizable liquid crystal composition is filled 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 so-called ODF (One Drop Fill) method. For example, an ultraviolet curable sealant is applied to a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed and the polymerizable liquid crystal composition is further dripped on the liquid crystal alignment film side, The liquid crystal cell can be manufactured by bonding one substrate to the other so as to face each other and then curing the sealing agent by irradiating ultraviolet light to the entire surface of the substrate. In either case, it is preferable to remove the flow alignment at the time of filling the liquid crystal by gradually cooling the liquid crystal cell to the temperature at which the liquid crystal using the liquid crystal takes an isotropic phase and gradually cooling to room temperature.

Next, a step of curing (polymerizing) the polymerizable liquid crystal composition with no voltage applied or with a voltage applied is required. When a transverse electric field type liquid crystal display device is manufactured, it is preferable to cure the polymerizable liquid crystal composition without applying a voltage.

Examples of the curing method of the polymerizable liquid crystal composition include photo-curing using ultraviolet rays or thermal curing by heat application. In the case of photo-curing, polarization may be used even when non-polarized light is used. However, when non-polarized light is used, sufficient curing occurs with low irradiation (low irradiation). In the case of using polarized light, The liquid crystal alignability of the liquid crystal layer can be improved. The irradiation dose in the case of photocuring is not particularly limited, but is preferably 1,000 mJ / cm 2 to 5,000 mJ / cm 2 as the unpolarized ultraviolet irradiation dose and 5000 mJ / cm 2 to 10 J / cm 2 as the ultraviolet irradiation dose of polarized light. In the case of curing in a state in which a voltage is applied, the applied voltage at the time of polymerization is not particularly limited, but is preferably 0.1 V to 20 V and preferably 2 V to 5 V.

The pretilt angle of the liquid crystal forming the liquid crystal layer is preferably 10 degrees or less, more preferably 5 degrees or less. Here, the pretilt angle refers to the inclination angle of the liquid crystal molecules with respect to the substrate. In an electric field type liquid crystal panel, the smaller the pretilt angle is, the better the contrast is.

Then, 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. Here, a desired liquid crystal display element can be obtained by appropriately adjusting the angle formed by the polarization direction of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate in the two substrates on which the liquid crystal alignment film is formed.

As the sealing agent, for example, an aluminum oxide spheres as a spacer and an epoxy resin containing a curing agent can be used. Examples of the polarizer used for the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state is sandwiched between cellulose acetate protective films or a polarizing plate made of H film itself .

The liquid crystal display of the present invention manufactured as described above is excellent in various properties such as display characteristics and electrical characteristics.

(Example)

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

The weight average molecular weight in the following Synthesis Examples is a polystyrene reduced value measured by gel permeation chromatography under the following conditions.

Column: TSKgelGRCXLII, manufactured by Toso K.K.

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / c㎡

Further, in the following synthesis examples, the synthesis of the raw material compound and the polymer was repeated as necessary with the following synthesis scale to ensure the required amount in the following examples.

<Synthesis of [A] polyorganosiloxane>

(Synthesis Example of Polyorganosiloxane Having an Epoxy Group)

[Synthesis Example 1]

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 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, And 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 (ES -1) as a viscous transparent liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane having the epoxy group, it was found that a peak based on the epoxy group was obtained at a theoretical intensity in the vicinity of the chemical shift (?) = 3.2 ppm, and a side reaction of the epoxy group occurred during the reaction . The viscosity, Mw, and epoxy equivalent of the polyorganosiloxane (ES-1) having the epoxy group are shown in Table 1.

[Synthesis Examples 2 to 3]

Polyorganosiloxanes (ES-2) and (ES-3) each having an epoxy group were obtained as viscous transparent liquids in the same manner as in Synthesis Example 1, except that the starting materials were as shown in Table 1. The Mw and the epoxy equivalent of the polyorganosiloxane having the epoxy group are shown in Table 1. In Table 1, the abbreviations of the raw material silane compounds have the following meanings respectively.

ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

MTMS: methyltrimethoxysilane

PTMS: phenyltrimethoxysilane

(Synthesis Example of Compound Represented by Formula (A1) above)

(A1-1), &quot; (A1-2) &quot;, &quot; (A1-2) &quot;, &quot; Compound (A1-3) "and" compound (A1-4) ") were synthesized.

[Synthesis Example 4]

20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine and 135 mL of dimethylacetamide were added to a 500-mL three-necked flask equipped with a cooling tube and mixed , As a solution. Next, 7 g of acrylic acid was added to the above solution using a syringe and stirred, followed by reaction at 120 ° C for 3 hours under stirring. After completion of the reaction was confirmed by thin layer chromatography (TLC), the reaction solution was cooled to room temperature. The insoluble matter was separated by filtration, and the filtrate was poured into 300 mL of 1N hydrochloric acid to recover the precipitate. This precipitate was recrystallized from a mixed solvent consisting of ethyl acetate and hexane (ethyl acetate: hexane = 1: 1 (volume ratio)) to obtain 8.4 g of compound (A1-1).

[Synthesis Example 5]

6.5 g of 4-fluorophenylboronic acid, 10 g of 4-bromominic acid, 2.7 g of tetrakistriphenylphosphine palladium, 4 g of sodium carbonate, 80 mL of tetrahydrofuran and 100 mL of pure water (100 mL) were added to a 300 mL three- Pure water) were added and mixed, and the reaction was carried out at 80 ° C for 8 hours with stirring. After completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature. The cooled reaction mixture was poured into 200 mL of 1N hydrochloric acid, and the precipitate was collected. A solution of the resulting precipitate dissolved in ethyl acetate was washed successively with 100 mL of 1 N hydrochloric acid, 100 mL of pure water and 100 mL of saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The obtained solid was vacuum-dried to obtain 9 g of the compound (A1-2).

[Synthesis Example 6]

In a 200 mL three-necked flask equipped with a cooling tube, 3.6 g of 4-fluorostyrene, 6 g of 4-bromominic acid, 0.059 g of palladium acetate, 0.32 g of tris (2-tolyl) phosphine, 11 g of triethylamine, 50 mL of amide was added and mixed to obtain a solution. This solution was stirred at 120 ° C for 3 hours to carry out the reaction. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature, insoluble matter was separated by filtration, and the filtrate was poured into 300 mL of 1N hydrochloric acid, and the precipitate was collected. This precipitate was recrystallized from ethyl acetate to obtain 4.1 g of the compound (A1-3).

[Synthesis Example 7]

In a 200 mL three-necked flask equipped with a condenser tube, 9.5 g of 4-vinylbiphenyl, 10 g of 4-bromominic acid, 0.099 g of palladium acetate, 0.54 g of tris (2-tolyl) phosphine, 18 g of triethylamine, 80 mL of amide was added and mixed to obtain a solution. This solution was stirred at 120 ° C for 3 hours for reaction. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature, insoluble matter was filtered off, and the filtrate was poured into 500 mL of 1N hydrochloric acid to recover the precipitate. This precipitate was recrystallized from a mixed solvent consisting of dimethylacetamide and ethanol (dimethylacetamide: ethanol = 1: 1 (volume ratio)) to obtain 11 g of the compound (A1-4).

(Synthesis Example of Compound Represented by Formula (A2)) [

(A2-1) and (A2-2), respectively, as in the following Synthesis Examples 8 and 9, respectively. ).

[Synthesis Example 8]

10 g of phenyl acrylate, 11.3 g of 4-bromobenzoic acid, 0.13 g of palladium acetate, 0.68 g of tris (2-tolyl) phosphine, 23 g of triethylamine and 100 mL of dimethylacetamide were placed in a 200 mL three- And mixed to prepare a solution. This solution was subjected to a reaction under stirring at 120 ° C for 3 hours. After the completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature, insoluble matter was separated by filtration, and the filtrate was poured into 500 mL of 1N hydrochloric acid, and the precipitate was collected. This precipitate was recrystallized from ethyl acetate to obtain 9.3 g of the compound (A2-1).

[Synthesis Example 9]

10 g of 4-cyclohexylphenol, 6.3 g of triethylamine and 80 mL of dehydrated tetrahydrofuran were added to a 200 mL three-necked flask equipped with a dropping funnel and mixed. This was cooled with an ice bath, and a solution composed of 5.7 g of acryloyl chloride and 40 mL of dehydrated tetrahydrofuran was added dropwise from a dropping funnel. After completion of dropwise addition, the mixture was further stirred in an ice bath for 1 hour, then returned to room temperature, and the reaction was further carried out for 2 hours with stirring. After completion of the reaction, the reaction mixture was filtered and the resulting salt was removed. Ethyl acetate was added to the filtrate, and the organic layer was washed with water. The solvent was removed under reduced pressure, and the residue was dried (dried) to obtain 12.3 g of 4-cyclohexylphenyl acrylate as an intermediate. Subsequently, to a 100 mL three-necked flask equipped with a cooling tube, 6 g of the acrylic acid 4-cyclohexylphenyl obtained above, 5.7 g of 2-fluoro-4-bromobenzoic acid, 0.06 g of palladium acetate, 0.32 g of phosphine, 11 g of triethylamine and 50 mL of dimethylacetamide were mixed and mixed to obtain a solution. This solution was subjected to a reaction under stirring at 120 DEG C for 3 hours. After completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature. The insoluble matter was separated by filtration, and the filtrate was poured into 300 mL of 1N hydrochloric acid , And the resulting precipitate was recovered. This precipitate was recrystallized from ethyl acetate to obtain 3.4 g of the compound (A2-2).

(Synthesis Example of [A] polyorganosiloxane)

[Synthesis Example 10]

9.3 g of a polyorganosiloxane (ES-1) having an epoxy group, 26 g of methyl isobutyl ketone, 3 g of a compound (A1-1) and 4 g of UCAT 18X (trade name, manufactured by San A Pro Co., Amine salt), and the reaction was carried out at 80 占 폚 for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into methanol to recover precipitates. The resulting precipitates were dissolved in ethyl acetate to give a solution. The solution was washed three times with water and then the solvent was distilled off to obtain [A] Siloxane (S-1) as a white powder. The weight average molecular weight (Mw) of the [A] polyorganosiloxane (S-1) was 3,500.

[Synthesis Example 11]

7.0 g of white powder of polyorganosiloxane (S-2) was obtained in the same manner as in Synthesis Example 10 except that 3 g of the compound (A1-2) was used instead of the compound (A1-1). The weight average molecular weight (Mw) of this [A] polyorganosiloxane (S-2) was 4,900.

[Synthesis Example 12]

10 g of white powder of polyorganosiloxane (S-3) was obtained in the same manner as in Synthesis Example 10 except that 4 g of the compound (A1-3) was used instead of the compound (A1-1). The weight average molecular weight (Mw) of the [A] polyorganosiloxane (S-3) was 5,000.

[Synthesis Example 13]

10 g of a white powder of polyorganosiloxane (S-4) [A] was obtained in the same manner as in Synthesis Example 10 except that 4 g of the compound (A1-4) was used instead of the compound (A1-1). The weight average molecular weight (Mw) of this [A] polyorganosiloxane (S-4) was 4,200.

[Synthesis Example 14]

10.5 g of a polyorganosiloxane (ES-2) having an epoxy group instead of the polyorganosiloxane (ES-1) having an epoxy group was used in place of the compound (A1-1) and 3.35 g of the compound (A2-1) , 7.0 g of a white powder of the polyorganosiloxane (A-5) was obtained in the same manner as in the above Synthesis Example 10. [ The weight average molecular weight (Mw) of the [A] polyorganosiloxane (S-5) was 5,500.

[Synthesis Example 15]

11.4 g of a polyorganosiloxane (ES-3) having an epoxy group instead of the polyorganosiloxane (ES-1) having an epoxy group and 4.6 g of the compound (A2-2) instead of the compound (A1-1) , 9.6 g of white powder of polyorganosiloxane (S-6) [A] was obtained in the same manner as in Synthesis Example 10. The weight average molecular weight (Mw) of the [A] polyorganosiloxane (S-6) was 7,400.

<Synthesis of [B] polymer>

(Dicarboxylic acid compound)

A dicarboxylic acid compound represented by the following formulas (DC-1) to (DC-5) (hereinafter also referred to as "compounds (DC-1) to (DC-5)") was used. Hereinafter, a method of synthesizing the compounds (DC-1) to (DC-4) will be described.

[Synthesis Example 16]

13.8 g (100 mmol) of 4-hydroxybenzoic acid, 8 g (200 mmol) of sodium hydroxide and 400 mL of pure water were placed in a 1 L three-necked flask equipped with a dropping funnel and cooled with an ice bath. A 120 mL solution of methylene chloride solution containing 10.86 g (120 mmol) of acrylic acid chloride was added dropwise over 1.5 hours from the dropping funnel. After completion of the dropwise addition, the mixture was stirred in an ice bath for 2 hours, and then the temperature of the reaction mixture was returned to room temperature and further stirred for 3 hours to carry out the reaction. Subsequently, the reaction mixture was again ice-cooled, and 1N hydrochloric acid was added dropwise until the liquidity of the reaction mixture became acidic. The precipitated solid was collected using a suction lot and recrystallized from ethanol to obtain 16 g of 4-acryloyloxybenzoic acid.

Next, under an inert atmosphere, 5 g of the 4-acryloyloxybenzoic acid obtained above, 5.3 g of 4-bromobenzoic acid, 60 mg of palladium acetate, 0.32 g of tris (o-tolyl) phosphine, 11 g of triethylamine, Amide were mixed in a 200 mL flask, and the reaction was carried out at 140 DEG C for 6 hours with stirring. After the temperature of the reaction mixture was returned to room temperature, 200 mL of 1N hydrochloric acid was added. The precipitated solid was collected by filtration and recrystallized from ethanol to obtain 6 g of a compound (DC-1).

[Synthesis Example 17]

10 g of 4-hydroxydiphenylmethane, 11 g of triethylamine and 60 mL of tetrahydrofuran were placed in a 200-mL three-necked flask equipped with a dropping funnel to prepare a solution. After thawing the solution, 50 mL of a tetrahydrofuran solution containing 10 g of acrylic acid chloride was added dropwise from the dropping funnel. After completion of the dropwise addition, the reaction was carried out in an ice bath under stirring for further 3 hours, and then the reaction mixture was subjected to liquid separation with a mixed solvent composed of ethyl acetate and water. The organic layer was recovered, dried over magnesium sulfate, and then the organic solvent was distilled off to obtain 15 g of bis (4-acryloyloxyphenyl) methane.

Subsequently, under an inert atmosphere, 8 g of the bis (4-acryloyloxyphenyl) methane obtained above, 10.5 g of 4-bromobenzoic acid, 120 mg of palladium acetate, 0.63 g of tris (o-tolyl) Amine and 90 mL of dimethylacetamide were mixed in a 300 mL flask, and the reaction was carried out at 140 DEG C for 6 hours with stirring. The temperature of the reaction mixture was returned to room temperature, and 500 mL of 1 N hydrochloric acid was added. The precipitated solid was collected by filtration and recrystallized from ethanol to obtain 4 g of a compound (DC-2).

[Synthesis Example 18]

10 g of hydroquinone, 20 g of triethylamine and 100 mL of tetrahydrofuran were placed in a 300 mL three-necked flask equipped with a dropping funnel to prepare a solution. This solution was ice-cooled, and 90 mL of a tetrahydrofuran solution containing 19 g of acrylic acid chloride was added dropwise thereto. After conducting a reaction in an ice bath under stirring for further 3 hours, the obtained reaction mixture was subjected to liquid separation with a mixed solvent composed of ethyl acetate and water. The organic layer was recovered, dried over magnesium sulfate, and then the organic solvent was distilled off to obtain 16 g of 1,4-diacryloyloxybenzene.

Next, in an inert atmosphere, 8 g of the 1,4-diacryloyloxybenzene obtained above, 15 g of 4-bromobenzoic acid, 165 mg of palladium acetate, 0.9 g of tris (o-tolyl) phosphine and 30 g of triethylamine And 130 mL of dimethylacetamide were mixed in a 500 mL flask, and the reaction was carried out at 140 DEG C for 6 hours with stirring. After completion of the reaction, the temperature of the reaction mixture was returned to room temperature, and 700 mL of 1 N hydrochloric acid was added. The precipitated solid was collected by filtration and recrystallized from ethanol to obtain 8 g of a compound (DC-3).

[Synthesis Example 19]

(DC-4) was obtained in the same manner as in Synthesis Example 17 except that 11.4 g of 2-fluoro-4-bromobenzoic acid was used instead of 4-bromobenzoic acid.

(Diepoxy compound)

A diepoxy compound represented by the following formula was used.

(Synthesis of [B] polymer)

[Synthesis Example 20]

(0.01 mole) of the above compound (DC-1) as a dicarboxylic acid, 0.83 g (0.01 mole) of the compound represented by the above formula (DE-1) as a diepoxy compound, and N-methyl- 10 g of lauridol was added and the mixture was stirred at 140 DEG C for 6 hours to carry out a reaction to obtain a solution containing a polymer (SP-1) as a specific polymer. The weight average molecular weight (Mw) of the polymer (SP-1) contained in this solution was 4,200.

[Synthesis Examples 21 to 38]

(SP-2) to (SP-18) and (rp-1) were obtained in the same manner as in Synthesis Example 20, except that 0.01 mol of each of the dicarboxylic acid and diepoxy compound described in Table 2 was used. Respectively. Further, in Synthesis Example 28, two kinds of compounds as a diepoxy compound were mixed in an amount of 50 mol%. Table 2 shows the molecular weights of the polymers contained in each solution.

&Lt; Synthesis of [C] component &gt;

(Synthesis example of polyamic acid)

[Synthesis Example 39]

19.61 g (0.1 mole) of cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mole) of 4,4'-diamino-2,2'-dimethylbiphenyl were dissolved in 367.6 g of N-methyl-2-pyrrolidone And the reaction was carried out at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 35 g of polyamic acid (PA-1). Further, even when a polyamic acid having a structure capable of causing photocleaning reaction in a part of the structure of the polymer main chain or side chain when irradiated with ultraviolet light of polarized light or unpolarized light is used under the condition [A] When used together with polyorganosiloxane or [B] polymer, it is classified as other polymer.

[Synthesis Example 40]

(0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g (0.1 mol) of cyclohexane bis (methylamine) were dissolved in 329.3 g of N-methyl-2-pyrrolidone, Lt; 0 &gt; C for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 32 g of polyamic acid (PA-2) as the component [D].

[Synthesis Example 41]

Bis [4- (4-aminophenoxy) phenyl] bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride and 0.1 mol 0.1 mol (41.05 g) of propane was dissolved in 373.26 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction mixture was then mixed with excess methanol and the reaction product was precipitated. Thereafter, the resultant was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 65 g (yield: 98.7%) of polyamic acid (X-1).

[Synthesis Example 42]

A polyamic acid polymer (X-2) was obtained in the same manner as in Synthesis Example 41 except that p-phenylenediamine was used as the diamine compound.

[Synthesis Example 43]

A polyamic acid polymer (X-3) was obtained in the same manner as in Synthesis Example 41 except that 4,4'-diaminodiphenyl ether was used as the diamine compound.

[Synthesis Example 44]

0.1 mole (19.61 g) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 0.1 mole (41.05 g) of 2,2-bis [4- (4-aminophenoxy) phenyl] Methyl-2-pyrrolidone, and the reaction was allowed to proceed at room temperature for 6 hours. The reaction mixture was then mixed with a large excess of methanol to precipitate the reaction product. Thereafter, the resultant was washed with methanol and dried under reduced pressure at 40 占 폚 for 15 hours to obtain 60 g (yield: 98.9%) of polyamic acid (Y-1).

[Synthesis Example 45]

A polyamic acid polymer (Y-2) was obtained in the same manner as in Synthesis Example 44 except that p-phenylenediamine was used as the diamine compound.

[Synthesis Example 46]

A polyamic acid polymer (Y-3) was obtained in the same manner as in Synthesis Example 44 except that 4,4'-diaminodiphenyl ether was used as the diamine compound.

[Synthesis Example 47]

0.08 mole (15.71 g) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 0.02 mole (4.48 g) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 4,4'- 0.1 mol (20.02 g) of phenyl ether was dissolved in 227 g of N-methyl-2-pyrrolidone, and the reaction was carried out at room temperature for 4 hours. The reaction mixture was then mixed with a large excess of methanol to precipitate the reaction product. Thereafter, the resultant was washed with methanol and dried under reduced pressure at 40 占 폚 for 15 hours to obtain 36 g of polyamic acid (Y-4).

[Synthesis Example 48]

0.05 mol (9.81 g) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 0.05 mol (11.21 g) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 4,4'- 0.1 mol (20.02 g) of phenyl ether was dissolved in 232 g of N-methyl-2-pyrrolidone, and the reaction was carried out at room temperature for 4 hours. The reaction mixture was then mixed with a large excess of methanol to precipitate the reaction product. Thereafter, the resultant was washed with methanol, and dried at 40 캜 for 15 hours under reduced pressure to obtain 37 g of polyamic acid (Y-5).

[Synthesis Example 49]

0.043 mol (5.88 g) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 0.07 mol (15.69 g) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 4,4'- 0.1 mol (20.02 g) of phenyl ether was dissolved in 236 g of N-methyl-2-pyrrolidone, and the reaction was carried out at room temperature for 4 hours. The reaction mixture was then mixed with a large excess of methanol to precipitate the reaction product. Thereafter, the resultant was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 36 g of polyamic acid (Y-6).

[Synthesis Example 50]

(0.106 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 36.19 g (0.106 mol) of a diamine having a side chain cinnamate structure represented by the following formula were dissolved in 150 g of N-methyl-2-pyrrolidone And the reaction was carried out at 40 ° C for 12 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 51 g of polyamic acid (rpa-1).

<Synthesis Example of Polyimide>

[Synthesis Example 51]

17.5 g of the polyamic acid (PA-2) was dissolved in 232.5 g of N-methyl-2-pyrrolidone, and further 3.8 g of pyridine and 4.9 g of acetic anhydride were added thereto. The reaction was carried out. After completion of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was collected, washed with methanol, and then dried under reduced pressure for 15 hours to obtain 15 g of polyimide (PI-1).

&Lt; Preparation of liquid crystal aligning agent and production of transverse electric field type liquid crystal display element (light alignment IPS)

(Preparation of liquid crystal aligning agent containing [A] polyorganosiloxane and production of transverse electric field type liquid crystal display element (light alignment IPS)

[Example 1]

100 parts by mass of the polyorganosiloxane (S-1) and 1,000 parts by mass of the polyamic acid (PA-1) were combined, and N-methyl-2-pyrrolidone and butyl cellosolve were added thereto, A solution having a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio) and a solid content concentration of 3.0% by mass. This solution was filtered with a filter having a pore size of 0.2 mu m to prepare a liquid crystal aligning agent. In addition, in the case of irradiating the polarized ultraviolet ray containing 313 nm of the bright line to the polyamic acid (PA-1) at a rate of 300 J / m 2, the photocatalytic reaction does not occur. -1) are classified as other polymers.

A pair of glass substrates having one metal electrode on one side and an opposing glass substrate on which no electrode is formed are sandwiched between a surface having electrodes of the glass substrate and a surface of the opposing glass substrate, The liquid crystal aligning agent prepared above was applied by using a spinner, pre-baked for 1 minute on a hot plate at 80 DEG C, and then heated in a nitrogen-substituted oven at 200 DEG C for 1 hour (post baking) To form a coating film having a thickness of 0.1 mu m. Fig. 1 is a schematic view showing the electrode pattern configuration on the glass substrate. Two conductive film patterns (metal electrodes) of the liquid crystal display element of the transverse electric field system are hereinafter referred to as an electrode 101 and an electrode 102, respectively. Subsequently, polarizing ultraviolet rays of 300 J / m &lt; 2 &gt; containing a bright line of 313 nm were irradiated from the direction of the substrate normal to the surface of these coating films using Hg-Xe lamps and Gantry prism respectively to obtain a pair of substrates having liquid crystal alignment films. An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 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 polarizing ultraviolet ray was irradiated , And the adhesive was thermally cured at 150 DEG C for 1 hour.

Subsequently, a liquid crystal mixture in which 0.3 wt% of a polymerizable liquid crystal represented by the following formula was added to the gap between the substrates from the liquid crystal injection port was filled in a liquid crystal made by Merck & Co., Ltd., MLC-7028, and then a liquid crystal injection port was sealed with an epoxy adhesive. Thereafter, in order to remove the flow orientation at the time of liquid crystal injection, it was heated at 150 占 폚 and gradually cooled to room temperature. Further, UV light irradiation (irradiation amount: 2,000 mJ / cm2 (? = 365 nm) ). Next, a polarizing plate was bonded to both outer sides of the substrate so that the polarization directions thereof were orthogonal to each other, and the optical axis of the polarized ultraviolet ray of the liquid crystal alignment film was orthogonal to the projection direction on the substrate surface. This liquid crystal display element was used for the evaluation of liquid crystal alignability, burn-in characteristics and contrast shown below.

The liquid crystal aligning agent prepared above was coated on the transparent electrode surface of the glass substrate with transparent electrode made of ITO film using a spinner so that the film thickness became 0.1 탆 and prebaked for 1 minute on a hot plate at 80 캜 (Post-baking) in an oven in which the inside of the tube was replaced with nitrogen at 200 DEG C for 1 hour to form a coating film having a thickness of 0.1 mu m. A polarizing ultraviolet ray of 300 J / m 2 containing a bright line of 313 nm was irradiated from the substrate normal direction on the surface of the thin film using a Hg-Xe lamp and a gantry prism respectively to obtain a pair of substrates having a liquid crystal alignment film. Next, on the pair of substrates subjected to the light irradiation treatment, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied by screen printing to the surface on which the liquid crystal alignment film was formed, and then the substrate And the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a liquid crystal mixture in which 0.3 wt% of the polymerizable liquid crystal represented by the above formula was added to the gap between the substrates from the liquid crystal injection port, MLC-manufactured liquid crystal, MLC-7028 was charged and then the liquid crystal injection port was sealed with an epoxy adhesive. Thereafter, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 150 占 폚 for 10 minutes and gradually cooled to room temperature. Further, UV light irradiation (irradiation amount: 2,000 mJ / Nm)). Next, a polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions thereof were orthogonal to each other, and the optical axis of the polarized ultraviolet ray of the liquid crystal alignment film was orthogonal to the projection direction on the substrate surface. This liquid crystal display element was used for the evaluation of light resistance as described below.

[Examples 2 to 12 and Comparative Examples 1 to 4]

The liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the polyorganosiloxane [A] and the polymer of the type and amount described in Table 3 were used as the [A] polyorganosiloxane and the other polymers, respectively, A liquid crystal display device was manufactured.

[Example 13]

(10J / cm &lt; 2 &gt; (lambda = 365nm)) instead of irradiating the liquid crystal mixture from the outside of the liquid crystal cell with UV light (irradiation amount: 2,000mJ / 365 nm)), a liquid crystal display device was produced in the same manner as in Example 1. [

<Evaluation Method of Liquid Crystal Display Element>

Each liquid crystal display device manufactured as described above was evaluated by the following method. The evaluation results are shown in Table 3. Also, for each of the later-described liquid crystal display elements, the same evaluation was made by the following method. The evaluation results are shown in Tables 4 to 8, respectively.

[Evaluation of liquid crystal alignment property]

With respect to the liquid crystal display device manufactured as described above, the presence or absence of an abnormal (abnormal) domain in a change in light and dark when a voltage of 5 V was turned ON / OFF (applied / released) was observed with an optical microscope, crystal orientation, if that is not observed "right (a ^+)", the liquid crystal alignment over the domain is not substantially observed "amount (a)", the liquid crystal orientation when the above domains observed a plurality of places "poor (B)" .

[Evaluation of burn-in characteristics]

A voltage of 3.5 V AC and a voltage of 5 V DC was applied to the electrode 101 for 2 hours without applying voltage to the electrode 102 under the environment of 25 占 폚 and 1 atm in the transverse electric field type liquid crystal display device manufactured as described above " Immediately thereafter, a voltage of 4 V of alternating current was applied to both the electrode 101 and the electrode 102. The time from when the application of the voltage of 4 V of AC to the both electrodes until the voltage difference between the electrodes 101 and 102 was not visually confirmed was measured. The burn-in characteristic when the time was less than 20 seconds was defined as "number (A)", the burn-in characteristic when the time was less than 60 seconds and 20 seconds or less was defined as " (D) &quot; and the burn-in characteristic when the amount was more than 150 seconds was evaluated as &quot; bad (E) &quot;.

[Evaluation of light resistance]

Each of the liquid crystal display devices prepared above was measured for VHR after 3,000 hours of irradiation with a weather meter using a carbon arc as a light source in the same manner as described above (voltage of 5 V was applied for 60 seconds and span of 167 milliseconds (VHR-1 manufactured by Toyo Technica Co., Ltd.) was used as a measurement device, and the VHR variation amount within 2% was compared with the measured value before irradiation, ), "Those with 2 to 5% or more are classified as" (B) ", and those with the percentage exceeding 5% as" not (C) ".

[Evaluation of contrast]

The black level was evaluated by evaluating the degree of light leakage based on the orientation deficiency in the manufactured liquid crystal cell as follows, and the evaluation was made as a substitute evaluation of the contrast evaluation. First, the liquid crystal cell was observed under a polarizing microscope under the cross-Nicol condition and the liquid crystal cell was arranged so as to have the darkest field of view, and the image was photographed. The obtained data was divided into 0.2 mm × 25 pixels, and the luminance of each pixel was numerically expressed by 255 gradations using an image processing software. (A) ", the case of 10 to 20 is referred to as" quantity B ", the case of 20 to 30 is referred to as" (C) ", and the case where the gradation of each pixel (25 pixels) (D) &quot; in the case where the system total is greater than 30,

As shown in Table 3, in the IPS mode liquid crystal display device comprising the liquid crystal alignment film formed using the liquid crystal aligning agent containing [A] polyorganosiloxane, the liquid crystal alignment property was sufficiently satisfied, , Light resistance, and contrast. Further, it was found that the liquid crystal alignability was further improved in Example 13 in which polarized UV was irradiated to the liquid crystal mixture. Therefore, the liquid crystal display element of the present invention satisfies the liquid crystal alignment property and is hard to cause deterioration of the electric characteristics by continuous driving for a long time.

(Preparation of liquid crystal aligning agent containing [B] polymer and production of transverse electric field type liquid crystal display element (light alignment IPS)

[Example 14]

N-methyl-2-pyrrolidone and butyl cellosolve were added to 100 parts by mass of (SP-1) as a specific polymer, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio), and a solid content concentration of 3.0% by mass. This solution was filtered with a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent. Using the liquid crystal aligning agent, the coating film surface was irradiated with polarizing ultraviolet rays of 10,000 J / m 2 containing a bright line of 313 nm using Hg-Xe lamp and Gantail prism from the substrate normal direction, In the same manner, a liquid crystal display device was manufactured and evaluated. The evaluation results are shown in Table 4, respectively.

[Examples 15 to 31, 38 to 39 and Comparative Examples 5 to 6]

A liquid crystal aligning agent was prepared in the same manner as in Example 14 except that a polymer of the type and amount described in Table 4 was used as the polymer in Example 14, and a liquid crystal display device was produced and evaluated. The evaluation results are shown in Table 4. In Comparative Example 5, other polymer was used in place of the specific polymer.

[Example 32]

In the present embodiment, specific polymer and other polymer were mixed and used. The solution containing the polyamic acid (PA-1) was taken in an amount corresponding to 80 parts by mass in terms of polyamic acid (PA-1) contained therein, and 20 parts by mass of the specific polymer (SP-10) In addition, N-methyl-2-pyrrolidone and butyl cellosolve were further added to obtain a solution having a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio) Mass% solution. This solution was filtered with a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent. Further, a liquid crystal display element was produced and evaluated by using this liquid crystal aligning agent. The evaluation results are shown in Table 4.

[Examples 33 to 37]

A liquid crystal aligning agent was prepared in the same manner as in Example 32 except that a polymer of the kind and the amount described in Table 4 was used as the specific polymer and the other polymer, respectively, and a liquid crystal display element was produced and evaluated. The other polymers were all provided in the preparation of a liquid crystal aligning agent as a solution containing a polymer of the kind described in Table 4. [ For the other polymers, the amounts shown in Table 4 are the amounts of other polymers contained in the polymer solution used. In Examples 34 and 37, two kinds of other polymers were used respectively.

As shown in Table 4, in the IPS mode liquid crystal display device comprising the liquid crystal alignment film formed using the liquid crystal aligning agent containing the [B] polymer, the liquid crystal alignment properties sufficiently satisfying the liquid crystal alignability, It was found that the contrast was excellent. Therefore, the liquid crystal display element of the present invention satisfies the liquid crystal alignment property and is hard to cause deterioration of the electric characteristics by continuous driving for a long time.

(Preparation of liquid crystal aligning agent containing [C] component and production of transverse electric field type liquid crystal display element (light alignment IPS)

[Example 40]

N-methyl-2-pyrrolidone and butyl cellosolve were added to 100 parts by mass of the above (X-1) as a polymer, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: (Mass ratio), and a solid content concentration of 3.0% by mass. This solution was filtered with a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent.

Except that the liquid crystal aligning agent was used to irradiate the surface of the coating film from the direction of the normal to the substrate with 10,000 J / m 2 of polarized ultraviolet rays containing a 254 nm bright line using an Hg-Xe lamp and a gantry prism respectively, In the same manner, a liquid crystal display device was manufactured and evaluated. The evaluation results are shown in Table 5, respectively.

[Examples 41 to 48]

A liquid crystal aligning agent was prepared in the same manner as in Example 40 except that the polymer of the kind and amount shown in Table 5 was used as the polymer, respectively, and a liquid crystal display device was produced and evaluated. The evaluation results are shown in Table 5.

As shown in Table 5, when the liquid crystal display element comprising the liquid crystal alignment film formed using the liquid crystal aligning agent containing [C] polyamic acid and / or polyimide is used in the IPS mode, the liquid crystal alignability is sufficiently satisfied , The burn-in characteristics, the light resistance, and the contrast were excellent. Therefore, the liquid crystal display element of the present invention sufficiently satisfies the liquid crystal alignment property and does not easily cause deterioration of electrical characteristics due to continuous driving for a long time.

&Lt; Fabrication of lateral electric field type liquid crystal display element (photo-alignment FFS)

[Example 49]

As shown below, the optically-oriented FFS liquid crystal display element of the present invention was manufactured and its operation was confirmed. 2 is a cross-sectional view for explaining the structures of the optically-oriented FFS liquid crystal display elements manufactured in Examples and Comparative Examples. This photo-aligned FFS liquid crystal display element has a structure in which only the glass substrate 201b in which the common electrode 205, the insulating layer 206, the signal electrode 204 and the liquid crystal alignment film 202b are formed in this order and the liquid crystal alignment film 202a And the liquid crystal layer 203 is sandwiched between the opposing glass substrate 201a. The signal electrode 204 of this photo-aligned FFS liquid crystal display element is a comb electrode having a straight comb. The common electrode 205 is a &quot; solid film &quot; having no pattern. In this photo-aligned FFS liquid crystal display element, a polarizing plate (not shown) is disposed on both outer sides of the glass substrates 201a and 201b, and a backlight (not shown) is disposed below the glass substrate 201b on the lower side in Fig. (Not shown) are arranged and used in combination with each other.

(Formation of liquid crystal alignment film)

A liquid crystal aligning agent prepared in Example 1 was applied to the surface of the substrate on which the common electrode, the insulating layer and the signal electrode were formed in this order, and the other surface of the opposite substrate on which the electrodes were formed, And the coating film was pre-baked at 80 DEG C for 1 minute and post baked at 200 DEG C for 1 hour to form a liquid crystal alignment film having an average film thickness of 0.1 mu m. Subsequently, polarizing ultraviolet rays of 300 J / m &lt; 2 &gt; including a bright line of 313 nm were irradiated from the normal direction of the substrate to the surface of these coating films using a Hg-Xe lamp and a Glane Taylor prism to obtain a pair of substrates each having a liquid crystal alignment film.

(Production of liquid crystal display element)

A pair of substrates each having a liquid crystal alignment film formed thereon as described above was disposed opposite to each other with a spacer having a thickness of 10 m therebetween so as to face the liquid crystal alignment film surface, and the side was sealed by leaving the liquid crystal injection port. A liquid crystal mixture in which 0.3 wt% of the polymerizable liquid crystal shown in Example 1 was added to a liquid crystal made by Merck Co., Ltd., MLC-7028 was charged from the liquid crystal injection port, and then the liquid crystal injection port was sealed. Thereafter, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 120 캜 for 10 minutes and then slowly cooled to room temperature. Further, UV light irradiation (dose: 2,000 mJ / )). Subsequently, a polarizing plate was bonded to the outer surface of both substrates, thereby producing a liquid crystal display element of the FFS mode. Here, the two polarizing plates were bonded such that their polarization directions were orthogonal to each other and parallel to or perpendicular to the direction of comb teeth of the signal electrode. This liquid crystal display element was used for evaluating liquid crystal alignment properties, burn-in characteristics and contrast shown below.

[Examples 50 to 60 and Comparative Examples 7 to 10]

An FFS liquid crystal display device was prepared and evaluated in the same manner as in Example 48 except that a liquid crystal aligning film was formed using a liquid crystal aligning agent containing the kinds and amounts of components described in Table 6. [ The results are shown in Table 6 together.

[Example 61]

(10 J / cm &lt; 2 &gt; (=? 365 nm (= 1300 nm)) instead of irradiating the liquid crystal mixture with UV light from the outside of the liquid crystal cell )), A liquid crystal display device was produced in the same manner as in Example 49 and evaluated. The results are shown in Table 6 together.

[Examples 62 to 87 and Comparative Examples 11 to 12]

A liquid crystal aligning agent containing a kind and a quantity of components described in Table 7 was used and a bright line of 313 nm was contained in place of irradiating the polarizing ultraviolet ray containing 313 nm of polarized ultraviolet ray at 300 J / FFS liquid crystal display device was prepared and evaluated by using the same method as in Example 49 except that the polarizing ultraviolet ray was irradiated at 10,000 J / m 2. The results are shown in Table 7 together.

[Examples 88 to 96]

A liquid crystal aligning agent containing the kind and the amount of components described in Table 8 was used and a 254 nm bright line was included instead of irradiating the polarized ultraviolet ray containing 313 nm of polarized ultraviolet ray at 300 J / FFS liquid crystal display device was prepared and evaluated by using the same method as in Example 49 except that the polarizing ultraviolet ray was irradiated at 10,000 J / m 2. The results are shown in Table 8 together.

As shown in Tables 6 to 8, when the liquid crystal display device comprising the liquid crystal alignment film formed using the liquid crystal aligning agent is used in the FFS mode transverse electric field system, the liquid crystal alignability is sufficiently satisfied, the burn-in property and the contrast are excellent . It was also found that the liquid crystal alignability was further improved in Example 61 in which polarized UV was irradiated to the liquid crystal mixture. Therefore, the liquid crystal display element satisfies the liquid crystal alignment property even in the FFS mode, and it is difficult to cause deterioration of the electric characteristics by continuous driving for a long time.

(Industrial availability)

The liquid crystal aligning agent of the present invention can be suitably applied to liquid crystal display elements of the PSA type, particularly to a liquid crystal display element of a transverse electric field system (IPS mode, FFS mode) It is possible to form a liquid crystal alignment film excellent in the liquid crystal alignment performance and electrical characteristics.

101: Electrode A
102: Electrode B
201a: glass substrate
201b: glass substrate
202a: liquid crystal alignment film
202b: liquid crystal alignment film
203: liquid crystal layer
204: signal electrode (ITO)
205: Common electrode (ITO)
206: insulating layer (silicon nitride)

Claims (14)

As a liquid crystal aligning agent for forming a liquid crystal alignment film in a PSA type liquid crystal display element,
[A] A polyorganosiloxane having a photo-aligning group
[B] a polymer having a photo-orientable group in its main chain, and
[C] polyamic acid, polyimide, or polyamic acid having decomposition type optical orientation and polyimide
At least one kind of polymer selected from the group consisting of
The polyorganosiloxane having a photo-aligned group [A] is at least one kind of group selected from the group consisting of a group represented by the following formula (A1 ') and a group represented by the following formula (A2'
[B] A polymer having a photo-orientable group in its main chain has a structure represented by the following formula (1)
A liquid crystal aligning agent characterized in that a polyamic acid, a polyimide, or a polyamic acid and a polyimide having a decomposition type optical alignment property [C] have a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton,

(Wherein R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, R ¹ is a phenylene group or a cyclohexylene group, provided that the phenylene group or the cyclohexylene group R ² represents a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -CH = CH- or -NH-, and a hydrogen atom, a is an integer of 0 to 3, provided that when a is 2 or 3, plural R ¹ and R ² may be the same or different, R ³ is a fluorine atom or a cyano group, b is 0 to 4 Provided that when b is 2 or more, plural R &lt; ³ &gt; s may be the same or different; &quot; * &quot;
In the formula (A2 '), R' is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group; R ⁴ is a phenylene group or a cyclohexylene group; Provided that some or all of the hydrogen atoms of the phenylene group or the cyclohexylene group may be substituted with a fluorine atom or a cyano group; R ⁵ is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -OCO- or -NH-; c is an integer of 1 to 3; Provided that when c is 2 or 3, plural R ⁴ and R ⁵ may be the same or different; R ⁶ is a fluorine atom or a cyano group; d is an integer from 0 to 4; Provided that when d is 2 or more, plural R ^{6 s} may be the same or different; R ⁷ is an oxygen atom, -COO- or -OCO-; R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group; e is an integer from 0 to 3; Provided that when e is 2 or more, plural R ⁷ and R ⁸ may be the same or different; R ⁹ is a single bond, ** - OCO- (CH ₂ ) _f - or ** - O - (CH ₂ ) _g -; &Quot; ** &quot; represents a moiety bonded to R ⁸ ; f and g are each independently an integer of 1 to 10; "*" Is a combination);

(Formula (1) of, R ¹⁰ are each independently an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom or a cyano group; m and n are each independently an integer of 0 to 4; two, m and n When each is 2 or more, plural R &lt; ¹⁰ &gt; may be the same or different, and &quot; * &quot; The method according to claim 1,
Wherein the liquid crystal display element is a transverse electric field system. delete 3. The method according to claim 1 or 2,
A polyorganosiloxane having at least an optically-oriented group [A]
[A] The polyorganosiloxane having a photo-
A polyorganosiloxane having an epoxy group,
A liquid crystal aligning agent which is a reaction product of at least one compound selected from the group consisting of a compound represented by the following formula (A1) and a compound represented by the following formula (A2)

(Wherein R, R ¹ to R ³ , a and b have the same meanings as in the formula (A1 '), R', R ⁴ to R ⁹ and c to e in the formula (A2) (A2 ')). delete delete 3. The method according to claim 1 or 2,
[D] A liquid crystal aligning agent further comprising at least one polymer selected from the group consisting of polyamic acid having no photo-aligning group and polyimide having no photo-aligning group. A liquid crystal alignment film formed by the liquid crystal aligning agent according to claim 1 or 2. A pair of substrates disposed opposite to each other,
A liquid crystal layer disposed between the two substrates,
And a liquid crystal alignment layer disposed on an inner surface side of at least one of the substrates so as to be in contact with the liquid crystal layer,
Wherein:
A liquid crystal display element formed by a step of injecting a liquid crystal composition containing a polymerizable monomer between the two substrates and polymerizing the monomer,
Wherein the liquid crystal alignment layer comprises,
[A] A polyorganosiloxane having a photo-aligning group
[B] a polymer having a photo-orientable group in its main chain, and
[C] polyamic acid, polyimide, or polyamic acid having decomposition type optical orientation and polyimide
At least one kind of polymer selected from the group consisting of
The polyorganosiloxane having a photo-aligned group [A] is at least one kind of group selected from the group consisting of a group represented by the following formula (A1 ') and a group represented by the following formula (A2'
[B] A polymer having a photo-orientable group in its main chain has a structure represented by the following formula (1)
The liquid crystal display device according to any one of claims 1 to 3, wherein the polyamic acid, the polyimide, or the polyamic acid and the polyimide having the decomposition type photo-alignment property are formed from a liquid crystal aligning agent having a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton. :

(Wherein R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, R ¹ is a phenylene group or a cyclohexylene group, provided that the phenylene group or the cyclohexylene group R ² represents a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -CH = CH- or -NH-, and a hydrogen atom, a is an integer of 0 to 3, provided that when a is 2 or 3, plural R ¹ and R ² may be the same or different, R ³ is a fluorine atom or a cyano group, b is 0 to 4 Provided that when b is 2 or more, plural R &lt; ³ &gt; s may be the same or different; &quot; * &quot;
In the formula (A2 '), R' is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group; R ⁴ is a phenylene group or a cyclohexylene group; Provided that some or all of the hydrogen atoms of the phenylene group or the cyclohexylene group may be substituted with a fluorine atom or a cyano group; R ⁵ is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -OCO- or -NH-; c is an integer of 1 to 3; Provided that when c is 2 or 3, plural R ⁴ and R ⁵ may be the same or different; R ⁶ is a fluorine atom or a cyano group; d is an integer from 0 to 4; Provided that when d is 2 or more, plural R ^{6 s} may be the same or different; R ⁷ is an oxygen atom, -COO- or -OCO-; R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group; e is an integer from 0 to 3; Provided that when e is 2 or more, plural R ⁷ and R ⁸ may be the same or different; R ⁹ is a single bond, ** - OCO- (CH ₂ ) _f - or ** - O - (CH ₂ ) _g -; &Quot; ** &quot; represents a moiety bonded to R ⁸ ; f and g are each independently an integer of 1 to 10; "*" Is a combination);

(Formula (1) of, R ¹⁰ are each independently an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom or a cyano group; m and n are each independently an integer of 0 to 4; two, m and n When each is 2 or more, plural R &lt; ¹⁰ &gt; may be the same or different, and &quot; * &quot; 10. The method of claim 9,
In the step of polymerizing the monomer, no voltage is applied to the liquid crystal display element. 10. The method of claim 9,
In the step of polymerizing the monomer, a voltage is applied to the liquid crystal display element. 12. The method according to any one of claims 9 to 11,
A liquid crystal display element which irradiates polarized ultraviolet rays in the step of polymerizing the monomer. 12. The method according to any one of claims 9 to 11,
Wherein the pretilt angle of the liquid crystal forming the liquid crystal layer is 10 DEG or less. 12. The method according to any one of claims 9 to 11,
Liquid crystal display device of transverse electric field system.

Images