KR101605565B1 - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display device, and process for producing liquid crystal display device - Google Patents

Abstract

(화학식 1 중, R^I은 (메트)아크릴로일기를 갖는 1가의 유기기이고, R^II는 1가의 유기기임)An object of the present invention is to provide a liquid crystal aligning agent which is excellent in vertical alignment properties and long-term stability, has less deterioration in voltage holding ratio when exposed to heat and light for a long time, and is capable of forming a liquid crystal alignment film having excellent afterimage characteristics.
Wherein the liquid crystal aligning agent is at least one selected from the group consisting of (A) a polyorganosiloxane obtained by hydrolyzing and condensing a silane compound containing a compound represented by the following formula (1), and (B) a polyorganic acid and a polyimide Or more.
≪ Formula 1 >

(Wherein R ^I is a monovalent organic group having a (meth) acryloyl group and R ^II is a monovalent organic group)

Description

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

The present invention relates to a liquid crystal aligning agent, a liquid crystal display element and a method for producing the same.

At present, as a liquid crystal display element, a liquid crystal alignment film is formed on a surface of a substrate on which a transparent conductive film is provided to form a substrate for a liquid crystal display element. Two liquid crystal alignment films are disposed opposite to each other, and a nematic liquid crystal layer having positive dielectric constant anisotropy Called twisted nematic liquid crystal cell in which the long axis of the liquid crystal molecules is twisted by 90 ° continuously from one substrate toward the other substrate is known as a TN type liquid crystal display device having a twisted nematic liquid crystal cell. In addition, a liquid crystal display device such as an STN (Super Twisted Nematic) type liquid crystal display device or an IPS (In-Plane Switching) type liquid crystal display device which can realize a higher contrast ratio than a TN type liquid crystal display device, A VA (Vertical Alignment) type liquid crystal display device using a tick-type liquid crystal has been developed.

The operation principle of such various liquid crystal display elements is largely classified into a transmission type and a reflection type. The transmissive liquid crystal display element performs display using the change in the intensity of the transmitted light of the backlight source from the back surface of the element at the time of device driving. On the other hand, a reflection type liquid crystal display device performs display by using a change in the intensity of light reflected from the outside such as sunlight at the time of device driving without using a light source for backlight. Since the power consumption is smaller than that of the transmission type, Which is particularly advantageous for use.

In the transmissive liquid crystal display device, the liquid crystal alignment film provided in the transmissive liquid crystal display device is exposed to light from the backlight source for a long time. Particularly, in a liquid crystal projector application in which demand for a home theater is increasing not only for a business purpose but also a metal halide lamp or the like, a highly illuminated light source is used. It is also believed that the temperature of the liquid crystal display element itself rises at the time of driving according to the light irradiation with high intensity. In the case of a reflective liquid crystal display device, there is a high possibility of being used outdoors. In this case, sunlight including strong ultraviolet light becomes a light source. Further, in the reflection type, the distance through which light passes through the device becomes longer in comparison with the transmission type in principle. In addition, both of the transmission type liquid crystal display device and the reflection type liquid crystal display device tends to be widely installed in, for example, an automobile, and the use and installation environment under a high temperature It became real.

However, liquid crystal dropping method, that is, ODF (One Drop Fill) method, has begun to be used from the viewpoint of process shortening and yield improvement in a liquid crystal display device manufacturing process. Unlike the conventional method in which liquid crystal is injected into an empty liquid crystal cell assembled using a thermosetting sealant in advance, the ODF method is a method in which an ultraviolet curable sealant is applied to a necessary portion of one substrate coated with a liquid crystal alignment film, The liquid crystal is dropped to a necessary portion and the other substrate is bonded, and ultraviolet light is irradiated on the entire surface to cure the sealing agent to manufacture a liquid crystal cell. The ultraviolet light to be irradiated at this time is usually stronger than a few lines per 1 cm < 2 > (J). That is, in the liquid crystal display element manufacturing process, the liquid crystal alignment film is exposed to the strong ultraviolet light together with the liquid crystal.

As described above, the liquid crystal display device is exposed to harsh environments such as high-intensity light irradiation, high-temperature environment, long-time driving, and the like, which can not be expected in the past due to its high functionality, versatility, and improved manufacturing process. It is demanded that the liquid crystal display element has a longer lifetime even when the liquid crystal display element is required to have better electric characteristics such as orientation and voltage retention and display characteristics.

Conventionally, organic resins such as polyimide, polyamic acid, polyamide, and polyester have been known as materials for a liquid crystal alignment film constituting a liquid crystal display element. In particular, polyimides are used in many liquid crystal display devices because they exhibit excellent physical properties such as heat resistance, affinity with liquid crystals, and mechanical strength among organic resins (Patent Documents 1 to 3). However, in recent liquid crystal display devices, a new demand for a manufacturing environment and an environment in which the use environment is severer as described above is intensified, and the heat resistance and the light resistance to such an extent that the organic resin which has been allowed in the prior art have been achieved still insufficient.

Therefore, a liquid crystal alignment film excellent in heat resistance and light resistance has been studied. For example, Patent Document 4 discloses a vertical alignment type liquid crystal alignment film formed of a polysiloxane solution obtained from a silicon compound having four alkoxyl groups and a silicon compound having three alkoxyl groups, and has a vertical alignment property, heat resistance and uniformity And excellent in stability as a coating liquid. However, the liquid crystal alignment film according to the technique of Patent Document 4 does not satisfy the required performance due to the harshness of the current manufacturing environment and the use environment, and the storage stability of the coating liquid is insufficient. Therefore, there is a problem.

A liquid crystal alignment film capable of providing a liquid crystal alignment film having a very harsh current manufacturing environment and sufficient heat resistance and light resistance in a use environment, and a liquid crystal aligning agent having excellent storage stability are not yet known.

In addition, an MVA (Multi-Domain Vertical Alignment) type panel is known in which protrusions are formed in a liquid crystal panel in order to enlarge a viewing angle in a VA type liquid crystal panel, thereby regulating the direction of conduction of liquid crystal molecules. However, according to this method, insufficient transmittance and contrast derived from protrusions are inevitable, and there is a problem that the response speed of liquid crystal molecules is slow.

In order to solve the problems of the MVA type panel, recently, a PSA (Polymer Sustained Alignment) mode has been proposed. The PSA mode is a mode in which a polymerizable compound is applied to a gap between a pair of substrates composed of a substrate with a patterned conductive film and a substrate with a conductive film having no pattern or between a pair of substrates composed of two patterned conductive film- And then polymerizing the polymerizable compound by irradiating ultraviolet rays while applying a voltage between the conductive films to thereby express the pretilt angle characteristics and controlling the alignment direction of the liquid crystal. According to this technique, the viewing angle can be increased and the response time of liquid crystal molecules can be increased by making the conductive film have a specific constitution, and the problems of the transmissivity and the contrast shortage, which were unavoidable in the MVA type panel, are also solved. However, in order to polymerize the above-mentioned polymerizable compound, irradiation with a large amount of ultraviolet rays of, for example, 100,000 J / m 2 is required, resulting in the problem that the liquid crystal molecules are decomposed, It is clear that the compounds remain in the liquid crystal layer and that they act to each other to cause display irregularities, adversely affect the voltage holding characteristics, or cause problems in long-term reliability of the panel.

In contrast, Non-Patent Document 1 proposes a method of using a liquid crystal alignment film formed of a polyimide-based liquid crystal aligning agent containing a reactive mesogen. According to Non-Patent Document 1, the response of liquid crystal molecules is high in a liquid crystal display element having a liquid crystal alignment film formed by such a method. However, in the non-patent reference 1, there is no description as to how much reactive mesogen is to be used, and there is still a large amount of ultraviolet rays to be irradiated, so there is no concern about display characteristics, particularly voltage holding characteristics .

Japanese Patent Laid-Open Publication No. 9-197411 Japanese Patent Application Laid-Open No. 2003-149648 Japanese Patent Application Laid-Open No. 2003-107486 Japanese Patent Application Laid-Open No. 9-281502 Japanese Patent Application Laid-Open No. 6-222366 Japanese Patent Application Laid-Open (JP-A) No. 6-281937 Japanese Patent Application Laid-Open No. 5-107544

 Y. -J. Lee et. al., SID 09 DIGEST, p.666 (2009)  T. J. Scheffer et. al. J. Appl. Phys. vol. 19, p. 2013 (1980)

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to provide a liquid crystal alignment film having excellent vertical orientation and long-term stability, less deterioration of voltage holding ratio when exposed to heat and light for a long time, And to provide a liquid crystal aligning agent capable of being obtained.

It is still another object of the present invention to provide a liquid crystal display element in which display quality is not deteriorated even when exposed to heat and light for a long time, and a method of manufacturing the same.

Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are achieved by firstly,

(A) a polyorganosiloxane obtained by hydrolyzing and condensing a silane compound containing a compound represented by the following formula (1), and

(B) at least one polymer selected from the group consisting of polyamic acid and polyimide

And a liquid crystal aligning agent.

(Wherein R ^I is a monovalent organic group having a (meth) acryloyl group and R ^II is a monovalent organic group)

The above-mentioned liquid crystal aligning agent can be suitably used for a liquid crystal display element having a known structure such as a TN type, an STN type, an IPS type, a VA type, and the like. In addition, in order to manufacture a new liquid crystal display element Can be used.

The above objects and advantages of the present invention are, secondly,

And a liquid crystal alignment layer formed of the liquid crystal aligning agent,

Third,

The liquid crystal aligning agent is applied onto the conductive film of a pair of substrates having a conductive film to form a coated film,

Forming a liquid crystal cell having a configuration in which the coating film of the pair of substrates on which the coating film is formed faces the liquid crystal molecules facing each other through the layer of liquid crystal molecules,

And a step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films of the pair of substrates.

The liquid crystal aligning agent of the present invention is excellent in vertical alignment properties and long-term stability, and is capable of forming a liquid crystal alignment film having less deterioration of the voltage holding ratio when exposed to heat and light for a long time and having excellent afterimage characteristics. A liquid crystal display device having a liquid crystal alignment film formed with zero can be effectively applied to various devices.

In addition, the novel liquid crystal display device manufactured by the method of manufacturing a liquid crystal display element of the present invention has a wide viewing angle, a fast response time of liquid crystal molecules, good electric characteristics, sufficient transmittance and contrast, , The display characteristics are not impaired even when the liquid crystal display element is continuously driven for a long time, and the amount of light required for irradiation of the liquid crystal display element is small.

The liquid crystal display device can be suitably used for various devices such as, for example, a tabletop calculator, a wristwatch, a desk clock, a coefficient display board, a word processor, a personal computer, and a liquid crystal television.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an explanatory view showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film manufactured in Examples 12 to 14. FIG.

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of the present invention comprises

(A) a polyorganosiloxane (hereinafter referred to as "polyorganosiloxane (A)") obtained by hydrolyzing and condensing a silane compound containing a compound represented by the formula (1)

(B) at least one polymer selected from the group consisting of polyamic acid and polyimide (hereinafter referred to as "polymer (B)"),

Lt; / RTI >

≪ Polyorganosiloxane (A) >

The polyorganosiloxane (A) in the present invention is a polyorganosiloxane obtained by hydrolyzing and condensing a silane compound containing a compound represented by the formula (1) (hereinafter referred to as "silane compound (1)").

Examples of R ^{I in the} above formula (1) include a group represented by the following formula (R ^I -1).

(Formula (R ^I -1), R is a hydrogen atom or a methyl group, a is an integer from 1 to 10, and b is 0 or 1, c is an integer from 0 to 2, d is 0 or 1, e is an integer of 0 to 3, with the proviso that c, d and e are not simultaneously 0, b and d together are 0 and e is 0 when c is not 0)

Specific examples of such R ^I include (meth) acryloxymethyl group, 2 - ((meth) acryloxy) ethyl group, 3- (Meth) acryloxy) pentyl, 6 - ((meth) acryloxy) hexyl, 7 - ((meth) acryloxy) heptyl, (Meth) acryloxy) decyl group, 9 - ((meth) acryloxy) nonyl group, 10 - (Meth) acryloxyphenylmethyl group, 4- (3 - ((meth) acryloxy) propyl) phenyl group, 3- (4- (Meth) acryloxyphenyl) propyl group, 4- ((meth) acryloxymethoxy) phenyl group, 4- (Meth) acryloxy methoxy methyl group, 2- ((meth) acryloxy methoxy) ethyl group, 2- (2- Group, 2 there may be mentioned - (((meth) acryloxy) propoxy 3) a propyl group such as (2- (2 ((meth) acryloxy) ethoxy) ethoxy) ethyl group, 3-.

Examples of R ^I in formula (I), wherein R is hydrogen atom or a methyl group in the general formula (R ^I -1), a is an integer from 1 to 10, and c is 1, b, d and e are each zero group (Meth) acryloxy) propyl group, 4 - ((meth) acryloxy) butyl group, 5 - (Meth) acryloxy) pentyl group or a 6 - ((meth) acryloxy) hexyl group, particularly preferably a 3 - ((meth) acryloxy) propyl group.

Examples of R ^II in the formula (1) include an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylsulfonyl group having an aryl group having 6 to 12 carbon atoms, an alkylsulfonyl group having an alkyl group having 1 to 4 carbon atoms And the like,

Specific examples thereof include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl, , Undecyl group, dodecyl group and the like;

Examples of the aryl group having 6 to 12 carbon atoms include phenyl, 4-methylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 4-methoxyphenyl, 3,5-dimethoxyphenyl, , 4,6-trimethoxyphenyl group and the like;

Examples of the arylsulfonyl group having an aryl group having 6 to 12 carbon atoms include p-toluenesulfonyl group and the like;

Examples of the alkylsulfonyl group having an alkyl group having 1 to 4 carbon atoms include a methylsulfonyl group and the like.

As R ^II in the above formula (1), an alkyl group having 1 to 12 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group or a t-butyl group is more preferable, butyl group, and particularly preferably a methyl group.

Specific examples of the silane compound (1) include (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethyltri-n-propoxysilane, (Meth) acryloxymethyltri-i-propoxysilane, (meth) acryloxymethyltri-n-butoxysilane, (meth) acryloxymethylpropyltri-

Acrylates such as 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 2- (meth) acryloxyethyltri-n-propoxysilane, 2- (Meth) acryloxyethyltri-n-butoxysilane, 2- (meth) acryloxyethylpropyltri-sec-butoxysilane, 2-

(Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (Meth) acryloxypropyltri-sec-butoxysilane, tri-i-propoxysilane, 3- (meth) acryloxypropyltri-

4- (meth) acryloxybutyltriethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, 4- (Meth) acryloxybutyltri-n-butoxysilane, 4- (meth) acryloxybutylpropyltri-sec-butoxysilane,

(Meth) acryloxypentyltrimethoxysilane, 5- (meth) acryloxypentyltriethoxysilane, 5- (meth) acryloxypentyltri-n-propoxysilane, 5- Propoxysilane, 5- (meth) acryloxypentyltri-n-butoxysilane, 5- (meth) acryloxypentyltri-sec-butoxysilane,

(Meth) acryloxyhexyltrimethoxysilane, 6- (meth) acryloxyhexyltrimethoxysilane, 6- (meth) acryloxyhexyltrimethoxysilane, 6- (Meth) acryloxyhexyltri-n-butoxysilane, 6- (meth) acryloxyhexylpropyltri-sec-butoxysilane, and the like.

In the synthesis of the polyorganosiloxane (A) in the present invention, only the silane compound (1) can be hydrolyzed and condensed, or a mixture of the silane compound (1) and the silane compound other than the silane compound (1) Decomposition and condensation.

Examples of the silane compound other than the silane compound (1) which can be used herein include compounds represented by the following formula (2) (hereinafter referred to as "silane compound (2)") and other silane compounds ) ").

(Wherein R ^III is a linear alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 24 carbon atoms, and R ^IV is a monovalent organic group)

Examples of the straight chain alkyl group having 1 to 18 carbon atoms represented by R < ^{III &} gt ^; in the general formula (2) include a methyl group, an ethyl group, a n-propyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and n-octadecyl group. The straight-chain alkyl group having 1 to 18 carbon atoms for R < ^III > is preferably a straight-chain alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

Examples of the straight chain fluoroalkyl group having 1 to 18 carbon atoms for R < ^III > include a trifluoromethyl group, a 2- (trifluoromethyl) ethyl group, a 3- (trifluoromethyl) propyl group, a perfluoro- N-hexyl group, perfluoro-n-octyl group, 2- (perfluoro-n-octyl) ethyl group, perfluoro-n-dodecyl group and perfluoro-n-octadecyl group. As the straight-chain fluoroalkyl group having 1 to 18 carbon atoms for R ^III , a straight-chain fluoroalkyl group having 1 to 6 carbon atoms is preferable, and a trifluoromethyl group, a 2- (trifluoromethyl) ethyl group, a 3- Methyl) propyl group or a perfluoro-n-hexyl group is more preferable, and a trifluoromethyl group is particularly preferable.

Examples of the aryl group having 6 to 24 carbon atoms for R < ^III > include a phenyl group, a 4-methylphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 3,5-dimethylphenyl group, , 4-n-hexylphenyl group, 4-n-octylphenyl group, 4-n-dodecylphenyl group and 4-n-octadecylphenyl group. Of these, phenyl group, 4-methylphenyl group, A 2-methylphenyl group is preferable, and a phenyl group is particularly preferable.

Examples of the monovalent organic group of R ^IV include an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylsulfonyl group having an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms Sulfonyl group and the like.

Examples of the alkyl group having 1 to 12 carbon atoms for R ^IV include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, ;

Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a methoxyphenyl group, a dimethoxyphenyl group, and a trimethoxyphenyl group;

Examples of the alkylsulfonyl group having an alkyl group having 1 to 6 carbon atoms include a methylsulfonyl group, an ethylsulfonyl group and an n-hexylsulfonyl group;

Examples of the arylsulfonyl group having an aryl group having 6 to 8 carbon atoms include a p-toluenesulfonyl group and a 3,5-dimethylphenylsulfonyl group. Among them, R ^IV in the above formula (2) is preferably an alkyl group having 1 to 6 carbon atoms.

Specific examples of the silane compound (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxy Methyltri-sec-butoxysilane, methyltri-sec-butoxysilane, methyltri-sec-butoxysilane, methyltriphenoxysilane, methyltri-

Ethyl tri-n-propoxysilane, ethyl tri-sec-butoxysilane, ethyl tri-sec-butoxysilane, ethyl tri-n-propoxysilane, ethyl tri- n-pentoxysilane, ethyltri-sec-butoxysilane, ethyltriphenoxysilane, ethyltri-p-methylphenoxysilane,

propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-i-propoxysilane, n-propyltri-n-butoxysilane, n -Propyltri-sec-butoxysilane, n-propyltri-n-pentoxysilane, n-propyltri-sec-butoxysilane, n-propyltriphenoxysilane, n- Silane,

butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-i-propoxysilane, n-butyltri-n-butoxysilane, n -Butyltri-sec-butoxysilane, n-butyltri-n-pentoxysilane, n-butyltri-sec-butoxysilane, n-butyltriphenoxysilane, n- Silane,

pentyltrimethoxysilane, n-pentyltriethoxysilane, n-pentyltri-n-propoxysilane, n-pentyltri-i-propoxysilane, n-pentyltri- Silane, n-pentyltri-sec-butoxysilane, n-pentyltrimethoxysilane, n-pentyltri-sec-butoxysilane, n-pentyltriphenoxysilane, n- T-butyl-p-methylphenoxysilane,

2- (trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- Butoxysilane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri- (Perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- N-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane, 2- (perfluoro- (Perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltrimethoxysilane, 2- n-octyl) ethyl tri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyl N-octyl) ethyl tri-sec-butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyl Tri-n-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane and the like.

The silane compound (3) is a silane compound other than the silane compound (1) and the silane compound (2), and specific examples thereof include trichlorosilane, trimethoxysilane, triethoxysilane, tri- Propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, Butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, 2- (trifluoromethyl) ethyl trichlorosilane, fluorotri-i-propoxysilane, (Perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyl Trimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propyl (Meth) acryloxypropyltrichlorosilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropylsiloxane, 3-mercaptopropyltrimethoxysilane, Mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltriethoxysilane, Butoxysilane, 3-mercaptopropyltris-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, Propoxysilane, allyltri-n-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane , Methyl trichlorosilane, methyl trichlorosilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxy silane, methyl di- butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyldi- methoxy silane, dimethyl diethoxy 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- (Methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, Propoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, Diethoxysilane, (methyl) (vinyl) di-n- (Methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, (vinyl) di- Divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec- Silane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, di Ethoxytrimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propyltrimethylsilane, n-propyltrimethylsilane, Propoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (Methyl) diphenylsilane, (ethoxy) (methyl) diphenylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (Meth) acryloxypropyl) dimethoxysilane, bis (3- (meth) acryloxypropyl) diethoxysilane, bis (3- Butoxysilane, bis (3- (meth) acryloxypropyl) di-n-butoxysilane, bis (3- (meth) acryloxypropyl) (Meth) acryloxypropyl) -n-propyl) diphenoxysilane, tris (3- (meth) acryloxypropyl) methoxysilane, tris -Propoxysilane, tris (3- (meth) acryloxypropyl) -i-propoxysilane, tris (3- (meth) acryloxypropyl) Propyl) -i-butoxy silane, tris (3- (meth) acryloxyphenyl Ropil) phenoxysilane,

Dimethyldimethoxysilane, diethyldimethoxysilane, di-n-propyldimethoxysilane, di-i-propyldimethoxysilane, di-n-butyldimethoxysilane, di- Di-n-propyldiethoxysilane, di-n-propyldiethoxysilane, di-n-butyldiethoxysilane, di-n-butyldiethoxysilane, Di-sec-butyldiethoxysilane, di-n-pentyldiethoxysilane, dihexyldiethoxysilane, dimethyl-di-i-propoxysilane, diethyl- Propyl-di-i-propoxysilane, di-i-propyl-di-i-propoxysilane, di- Di-sec-butoxysilane, dimethyl-di-sec-butoxysilane, di-n-pentyl-di-i-propoxysilane, Di-sec-butoxy silane, di-i-propyl-di-sec-butoxy silane, di- Butyl-di-sec-butoxysilane, di-n-pentyl-di-sec-butoxysilane, di-hexyl-di- sec-butoxysilane, trimethylmethoxysilane, triethyl Tri-n-butylmethoxysilane, tri-n-hexylmethoxysilane, tri-n-butylmethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylethoxysilane, tri-sec-ethoxysilane, tri- N-hexyl ethoxysilane, tri-n-dodecylethoxysilane, trimethyl-n-propoxysilane, triethyl-n-propoxysilane, tri- N-propoxysilane, tri-n-butyl-n-propoxysilane, tri-sec-butyl-n-propoxysilane, tri- , Tri-n-dodecyl-n-propoxysilane, trimethyl-i-propoxysilane, tri Propyl-i-propoxysilane, tri-n-butyl-i-propoxysilane, tri-sec- i-propoxysilane, tri-n-hexyl-i-propoxysilane, tri-n-dodecyl-i-propoxysilane, trimethyl- sec-butoxysilane, triethyl- butyl-sec-butoxysilane, tri-sec-butyl-sec-butoxysilane, tri-n-butyl- Hexyl-sec-butoxysilane, tri-n-dodecyl-sec-butoxysilane and the like.

Of these silane compounds (3), preferred are tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane are preferred.

The silane compound used in the synthesis of the polyorganosiloxane (A) in the present invention preferably has a silane compound (1) in an amount of 20 to 80 wt% based on the total silane compound %, More preferably 30 to 70 wt%, particularly preferably 40 to 60 wt%.

The silane compound used in synthesizing the polyorganosiloxane (A) in the present invention preferably contains 20 to 80% by weight of the silane compound (2) based on the total silane compound from the viewpoint of improving the reliability by proper crosslinking , More preferably 30 to 70 wt%, and particularly preferably 40 to 60 wt%.

The proportion of the silane compound (3) in the silane compound used in the synthesis of the polyorganosiloxane (A) in the present invention is preferably 30% by weight or less, more preferably 10% by weight or less based on the total silane compound Do. It is most preferable that the silane compound used in synthesizing the polyorganosiloxane (A) in the present invention does not contain the silane compound (3).

The polyorganosiloxane (A) in the present invention can be synthesized by using the above-described silane compound as a raw material, preferably by hydrolysis and condensation in the presence of water and a catalyst in a suitable organic solvent.

Examples of the organic solvent which can optionally be used in the synthesis of the polyorganosiloxane (A) include an alcohol compound, a ketone compound, an amide compound or an ester compound or other aprotic compound. These may be used alone or in combination of two or more.

Examples of the alcohol compound include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, sec-pentanol, sec-heptanol, heptanol-3, n-hexanol, Octanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, monoalcohol compounds such as sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol- Polyhydric alcohol compounds such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;

Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene And partial ethers of polyhydric alcohol compounds such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether. These alcohol compounds may be used singly or in combination of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, Butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone, ;

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

Examples of the amide compound include N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N -Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. These amide compounds may be used singly or in combination of two or more.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate,? -Butyrolactone,? -Valerolactone, Butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetoacetate, Benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, Glycol monoethyl ether, acetic acid diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, methoxytriglycol acetate, ethyl propionate Butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like can be used. . These ester compounds may be used singly or in combination of two or more.

Examples of the other aprotic compound include acetonitrile, dimethylsulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, Methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4- Pyridone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro- And the like.

Of these solvents, polyhydric alcohol compounds and partial ethers or ester compounds of polyhydric alcohol compounds are particularly preferred.

The proportion of water used in the synthesis of the polyorganosiloxane (A) is preferably 0.5 to 100 moles, more preferably 1 to 10 moles, per 1 mole of the total amount of the alkoxyl group and the halogen atom contained in the raw silane compound 30 mol, and more preferably 1 to 1.5 mol.

Examples of the catalyst that can be used in the synthesis of the polyorganosiloxane (A) include metal chelate compounds, organic acids, inorganic acids, organic bases, ammonia, and alkali metal compounds.

Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium , Tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, (Acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di- (Acetylacetonate) titanium, di-sec-butoxy-bis (acetylacetonate) titanium, di-t-butoxy-bis (acetylacetonate) titanium, monoethoxy tris Tris (acetylacetonate) titanium, mono-i-propoxy tris (acetyl (Acetyl acetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium (Ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (Ethylacetoacetate) titanium, di-n-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis Titanium, di-sec-butoxy-bis (ethyl acetoacetate Mono-n-propoxy tris (ethylacetoacetate) titanium, di-t-butoxy-bis (ethyl acetoacetate) titanium, monoethoxy tris Propoxy tris (ethylacetoacetate) titanium, mono-n-butoxy tris (ethylacetoacetate) titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-t-butoxy tris Ethyl acetoacetate) titanium, bis (acetylacetonate) titanium, tris (acetylacetonate) mono (acetylacetonate) titanium, bis (Ethyl acetoacetate) titanium;

Mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri-i-propoxy mono (acetylacetonate) zirconium, tri-n-butoxy mono (Acetylacetonate) zirconium, diethoxy bis (acetylacetonate) zirconium, di-tert-butoxy mono (acetylacetonate) zirconium, di (n-butoxy) bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di- Bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonate) zirconium, Mono-i-propoxy Tris (acetylacetonate) zirconium, mono-n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris ) Zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri- Acetate) zirconium, tri-n-butoxy mono (ethylacetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, (Ethylacetoacetate) zirconium, di-n-propoxy bis (ethylacetoacetate) zirconium, di-i-propoxy bis (ethylacetoacetate) zirconium, di- (Ethyl acetoacetate) zirconium, di-sec-butoxy-bis (ethylacetoacetate) zirconium, di-t-butoxy-bis (ethylacetoacetate) zirconium, monoethoxy tris (Ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (Ethylacetoacetate) zirconium, tris (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, Bis (acetylacetonate) bis (ethylacetoacetate) zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium, Zirconium chelate compounds;

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

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, But are not limited to, butyric acid, butyric acid, melitoic acid, arachidonic acid, meqic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p- aminobenzoic acid, p- toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, , Trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

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

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanol Amine, triethanolamine, diazabicyclooctane, diazabicyclo-nonane, diazabicyclo-undecene, tetramethylammonium hydroxide, and the like.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

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

Of these catalysts, metal chelate compounds, organic acids or inorganic acids are preferable, and titanium chelate compounds or organic acids are more preferable.

The amount of the catalyst to be used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the total amount of the silane compound as the raw material.

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

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

The reaction temperature in the synthesis of the polyorganosiloxane (A) is preferably 0 to 100 占 폚, more preferably 15 to 80 占 폚. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

The weight average molecular weight of the polyorganosiloxane (A) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 500 to 1,000,000, more preferably 1,000 to 100,000, and most preferably 1,000 to 50,000 More preferable.

≪ Polymer (B) >

The polymer (B) in the liquid crystal aligning agent of the present invention is at least one polymer selected from the group consisting of polyamic acid and polyimide.

The polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine, and the polyimide can be obtained by subjecting the polyamic acid to dehydration cyclization.

[Tetracarboxylic acid dianhydride]

Examples of the tetracarboxylic acid dianhydride that can be used in the synthesis of the polymer (B) include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro- 2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4- -Cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3 , 5-tricarboxycyclopentylacetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] 5,9-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ ] - furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro- , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, bicyclo [2.2.2] Tetracarboxylic acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3 , 5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- Aliphatic tetracarboxylic acid dianhydride and alicyclic tetracarboxylic acid dianhydride such as 8,10-tetraone, compounds represented by the following formulas (TI) and (T-II), respectively;

(Formula (TI) and (T-II) of, R ¹ and R ³ is a divalent organic group having each an aromatic ring, R ² and R ⁴ are R ² and R each is a hydrogen atom or an alkyl group, a plurality of present ^{4 &lt}; / RTI > may each be the same or different)

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5 , 8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxyl Acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3' '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) dianhydride, m-phenylene- (Anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydroglycidyl) Bis (4-hydroxyphenyl) propane-1,6-hexanediol-bis (anhydrotrimellitate) Aromatic tetracarboxylic acid dianhydrides such as bis (anhydrotrimellitate) and compounds represented by the following formulas (T-1) to (T-4). The benzene ring of the aromatic tetracarboxylic dianhydride may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).

These tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polymer (B) in the present invention include butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclo 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 1,3,3a, 4,5,9b-hexahydro- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- -Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b - hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro- 3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: , 9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxyl Acid dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8 (T-5) to (T-7) and the compound represented by the formula (T-II) in the compound represented by the formula (TI) (Hereinafter referred to as "specific tetracarboxylic acid dianhydride") selected from the group consisting of compounds represented by the following formula (T-8) Is preferable from the viewpoint of being able to exhibit good liquid crystal alignment properties.

Specific tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5, (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-fura Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: A group consisting of 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride and the compound represented by the above formula (T-1) Is preferable.

The tetracarboxylic acid dianhydride used for synthesizing the polymer (B) used in the present invention may be obtained by reacting a specific tetracarboxylic dianhydride as described above in an amount of 30 mol% or more with respect to the total tetracarboxylic dianhydride , More preferably 40 mol% or more, and particularly preferably 45 mol% or more.

[Diamine]

Examples of diamines usable in the synthesis of the polymer (B) include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, Diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'- 1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diamino Benzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, bis [4- (4-aminophenoxy) benzene, 4,4'-bis (4-amino Bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene Diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, bis (4-amino-2-chlorophenyl) Methane, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 4,4'-diaminobiphenyl, 4,4'- (p-phenylenediisopropylidene) bisaniline, 4,4 '- (m-phenylene diisopropylidene) bis Aniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'- Bis (trifluoromethyl) biphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, (D-1) to (D-5), wherein R < And the like;

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5)

But are not limited to, 1,1-hexanediol, 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanedanilinedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethylenediamine, 4,4'-methylene Aliphatic diamines and alicyclic diamines such as bis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane;

Diaminopyridine, 5, 6-diamino-2,3-dicyanopyrimidine, 5, 6-diamino-2,3-dicyanopyrimidine, Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4- 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6- Vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacrylidine, N, N'-bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N- 6-diamino (4-aminophenyl) -N, N'-dimethyl-benzidine, a compound represented by the following formula (DI) A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in a molecule such as a compound represented by the following formula (D-II);

(In the formula (DI), R ⁵ is a monovalent organic group having a ring structure including a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, X ¹ is a divalent organic group , R ⁶ is an alkyl group having 1 to 4 carbon atoms, and a 1 is an integer of 0 to 3)

(In the formula (D-II), R ⁷ is a divalent organic group having a ring structure including a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, X ² is a divalent X ² in the plurality of groups may be the same or different, R ⁸ is an alkyl group having 1 to 4 carbon atoms, and a 2 is an integer of 0 to 4,

A mono-substituted phenylenediamine such as a compound represented by the following formula (D-III);

(Wherein, in the formula (D-III), R ⁹ represents -O-, -COO- *, -OCO- *, -NHCO- *, -CONH- * ¹⁰ ) or -CO-, R ¹⁰ is a monovalent organic group having a skeleton or a group selected from a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group and a fluorophenyl group, or an alkyl group having 6 to 30 carbon atoms , R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a3 is an integer of 0 to 3)

A diaminoorganosiloxane such as a compound represented by the following formula (D-IV), and the like. The benzene ring of the aromatic diamine may be substituted with one or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).

(Wherein R ¹² is a hydrocarbon group having 1 to 12 carbon atoms, plural R ^{12 s} may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 3, 20)

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

Examples of the diamine used for synthesizing the polymer (B) in the present invention include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2'-dimethyl-4,4'- Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) benzene, (D-1) to (D-5) described above, a compound represented by the following general formula (D-1) A compound represented by each of the following formulas: 2, 6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N N, N'-bis (4-aminophenyl) -methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, (D-6) among the compounds represented by the formula (DI), the compound represented by the formula (D), the compound represented by the formula (D-7) among the compounds represented by the formula (D-III), the dodecanoxy-2,4-diaminobenzene, the pentadecanoxy- 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecanoxy- Diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene (3-aminopropyl) -tetramethyldisiloxane among the compounds represented by the following formulas (D-8) to (D-15) and the compound represented by the above formula (Hereinafter referred to as "specific diamine") is preferable from the viewpoint of electrical characteristics.

The diamine used for synthesizing the polymer (B) used in the present invention preferably contains 30 mol% or more, more preferably 40 mol% or more, of the specific diamine as described above with respect to the total diamine, Particularly preferably 45 mol% or more.

[Synthesis of polyamic acid]

The ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic dianhydride is from 0.2 to 2 equivalents based on 1 equivalent of the amino group of the diamine, Preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably performed in an organic solvent at a temperature of preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C, preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours Time.

Examples of the organic solvent that can be used in the synthesis of polyamic acid include aprotic polar solvents, phenol and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons. Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, , Hexamethylphosphotriamide, and the like;

Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like. Examples of the alcohol include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like;

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like;

Examples of the esters include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate and diethyl malonate. Examples of the ether include ethers such as diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran and the like. ;

Examples of the halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;

Examples of the hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, and diisopentyl ether.

Among these organic solvents, at least one member selected from the group consisting of an aprotic polar solvent and a group consisting of a phenol and a derivative thereof (first group of organic solvents), or at least one member selected from organic solvents of the first group, , A ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon (an organic solvent of the second group). In the latter case, the ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less based on the total amount of the organic solvent of the first group and the organic solvent of the second group By weight, more preferably 30% by weight or less.

In this way, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be used as it is for preparing a liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and used for the preparation of a liquid crystal aligning agent, or after the isolated polyamic acid is purified, . When the polyamic acid is subjected to dehydration cyclization to form a polyimide, the reaction solution may be used in the dehydration ring-closing reaction as it is, or may be used in a dehydration ring-closure reaction after the polyamic acid contained in the reaction solution is isolated, May be used for the dehydration ring-closing reaction after purification.

The polyamic acid may be isolated by pouring the reaction solution into a large amount of a poor solvent to obtain a precipitate and drying the precipitate under reduced pressure, or by a method of distilling off the organic solvent in the reaction solution under reduced pressure using an evaporator. Alternatively, the step of dissolving the polyamic acid in an organic solvent followed by precipitation with a poor solvent, or a solution in which the polyamic acid is dissolved again in an organic solvent, washing the solution, and then distilling off the solution under reduced pressure using an evaporator, Alternatively, the polyamic acid can be purified by a method performed several times.

[Synthesis of polyimide]

The polyimide can be obtained by dehydrating and ring-closure of the polyamic acid obtained as described above to imidize it.

The polyimide in the present invention may be a completely imidized amide structure having all of the amic acid structure possessed by the polyamic acid which is a precursor and dehydrating and cyclizing only a part of the amamic acid structure so that the amic acid structure and the imidazole structure coexist It may be a partial imide cargo.

The imidization ratio of the polyimide is preferably 30% or more, and more preferably 40 to 90%. This imidization ratio is a numerical value as a percentage of the ratio of the number of imide ring structures to the sum of the number of amic acid structures and the number of imide ring structures of the polyimide. At this time, a part of the imide ring may be an isoimide ring.

The dehydration ring-closure of the polyamic acid is preferably carried out by heating the polyamic acid (i), or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, . ≪ / RTI >

The reaction temperature in the method of heating the polyamic acid of (i) is preferably 50 to 200 占 폚, more preferably 60 to 170 占 폚. 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 is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.

On the other hand, in the method of adding the dehydrating agent and dehydrating ring-closing catalyst to the solution of the polyamic acid of the above (ii), for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the amic acid structure of the polyamic acid although it differs depending on the desired imidization ratio. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The imidization rate can be increased as the amount of the dehydrating agent and the dehydrating ring closure agent used is larger. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

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

[Polymer of terminal modified type]

The polymer (B) contained in the liquid crystal aligning agent of the present invention may be a terminal-modified type having a controlled molecular weight. By using the polymer of the terminal modified type, the coating property and the like of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention. Such a terminal modified polymer can be produced by adding a molecular weight regulator to a polymerization reaction system when synthesizing a polyamic acid. Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds.

Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, and n-hexadecyl succinic anhydride;

Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, hexadecylamine, n-heptadecylamine, n-octadecylamine, n-octadecylamine, n-octadecylamine, Eicosylamine and the like;

Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride and diamine used for synthesizing the polyamic acid.

[Solution viscosity]

The polymer (B) obtained as described above preferably has a solution viscosity of 20 to 800 mPa 으로 when it is a 10 wt% solution, more preferably a solution viscosity of 30 to 500 mPa 하다 .

The solution viscosity (mPa.s) of the polymer is preferably 10% by weight of a polymer solution prepared by using a good solvent for the polymer (for example,? -Butyrolactone, N-methyl-2-pyrrolidone or the like) Measured at 25 캜 using an E-type rotational viscometer.

≪ Use ratio of polyorganosiloxane (A) and polymer (B) >

The ratio of the polyorganosiloxane (A) to the polymer (B) in the liquid crystal aligning agent of the present invention is such that the sum of the polymers (the sum of the polyorganosiloxane (A) and the polymer (B) Is preferably 0.01 to 30% by weight, more preferably 0.1 to 15% by weight, based on the weight of the polyorganosiloxane (A).

<Other additives>

The liquid crystal alignment film of the present invention contains the above-mentioned polyorganosiloxane (A) and polymer (B) as essential components, but may contain other components as needed as long as the effect of the present invention is not attenuated. Examples of such other components include (C) a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound (C)"), and (D) a functional silane compound.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl Ether, and the like, as well as compounds having a group represented by the following formula (3).

As the epoxy compound (C) in the present invention, a compound having a group represented by the formula (3) is preferable, and specific examples thereof include N, N, N ', N'-tetraglycidyl-m- , N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N (N, N-dimyridylaminomethyl) cyclohexane, -Diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine and the like.

The mixing ratio of these epoxy compounds (C) is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total amount of the polymers.

Examples of the functional silane compound (D) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N - (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3- N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N -Trimethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxy Silane-3,6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, 9- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, Phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2 -Glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.

The blending ratio of these (D) functional silane-containing compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total amount of the polymers.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is constituted as a liquid composition in which the polyorganosiloxane (A) and the polymer (B), and optionally other additives optionally mixed, are dissolved and contained in an organic solvent.

Examples of the organic solvent usable in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N, N -Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxypropionate, ethylene glycol methyl ether, N-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Isobutyl ketone, and the like can be mentioned isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate. These may be used alone or in combination of two or more.

The solid concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate as described later, and preferably, it is heated to form a coating film which becomes a liquid crystal alignment film. However, when the solid concentration is less than 1% by weight, On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, the viscosity of the liquid crystal aligning agent is increased, and the coating property is deteriorated .

Particularly preferable ranges of the solid concentration are different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 wt%. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9 wt%, and the solution viscosity is accordingly in the range of 12 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 wt% and the solution viscosity is in the range of 3 to 15 mPa · s accordingly.

The temperature at which the liquid crystal aligning agent of the present invention is prepared is preferably 10 to 50 캜, more preferably 20 to 30 캜.

The liquid crystal aligning agent of the present invention obtained as described above can be preferably used for forming a liquid crystal alignment layer of a liquid crystal display element having a known structure such as TN type, STN type, IPS type and VA type, It can be used for manufacturing a new liquid crystal display element in which the problem of the panel is solved.

Hereinafter, a method for forming a liquid crystal alignment film using the liquid crystal aligning agent of the present invention, a method for producing the liquid crystal display element having the liquid crystal alignment film, and a method for producing a new liquid crystal display element using the liquid crystal aligning agent of the present invention Will be described in order.

&Lt; Method of forming liquid crystal alignment film &

The liquid crystal alignment film can be formed, for example, by the following steps (1) and (2).

(1) First, the liquid crystal aligning agent of the present invention is applied onto a substrate, and then a coated film is formed on the substrate by heating the coated surface. Here, there is a difference between the case where the liquid crystal display element of the present invention is applied to a TN type, the STN type or VA type liquid crystal display element, and the case where the liquid crystal element is applied to an IPS type liquid crystal display element.

(1-1) In the case of producing a TN type, STN type or VA type liquid crystal display device, two pairs of substrates on which patterned transparent conductive films are provided are paired, and on the respective transparent conductive film forming surfaces thereof, The alignment agent is preferably applied by the offset printing method, the spin coating method or the inkjet printing method, respectively, and then the coated surfaces are heated to form a coating film. Examples of the substrate include glass such as float glass and soda glass; A transparent substrate containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film to be provided on one side of the substrate, an ITO film including indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), a NESA film containing tin oxide (SnO ₂ ) In order to obtain a patterned transparent conductive film, for example, a method of forming a transparent conductive film without a pattern and then forming a pattern by photo-etching, a method of forming a transparent conductive film by using a mask having a desired pattern Method or the like. In coating the liquid crystal aligning agent, in order to improve the adhesion of the substrate surface and the transparent conductive film to the coating film, a pretreatment of applying a functional silane compound, a functional titanium compound, .

After the application of the liquid crystal aligning agent, preliminary heating (prebaking) is preferably performed for the purpose of preventing the applied alignment agent from being dropped. The prebaking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amic acid unit of the polymer (B). The firing (post-bake) temperature is preferably 80 to 300 占 폚, more preferably 120 to 250 占 폚. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 占 퐉, more preferably 0.005 to 0.5 占 퐉.

(1-2) On the other hand, in the case of manufacturing an IPS type liquid crystal display element, the conductive film formation surface of the substrate on which the transparent conductive film patterned in the comb-like pattern is provided and the conductive film formation surface of the opposite substrate on which the conductive film is not provided The liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spinner method, or an inkjet printing method, respectively, and then each coating surface is heated to form a coating film.

The substrate, the material of the transparent conductive film, the patterning method of the transparent conductive film, the pretreatment of the substrate, and the heating method after applying the liquid crystal aligning agent are the same as those in the above (1-1).

The preferred film thickness of the coating film to be formed is the same as in (1-1) above.

(2) When the liquid crystal display element manufactured by the method of the present invention is a VA type liquid crystal display element, the coating film formed as described above can be used as it is as a liquid crystal alignment film, It can also be used afterwards.

On the other hand, when a liquid crystal display device other than the VA type is manufactured, a coating film formed as described above is subjected to rubbing treatment to form a liquid crystal alignment film.

The rubbing treatment can be performed by rubbing the coating film surface formed as described above in a predetermined direction with a roll of cloth made of fibers such as nylon, rayon or cotton. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.

The liquid crystal alignment film formed as described above is also disclosed in, for example, Patent Document 5 (Japanese Patent Application Laid-Open No. 6-222366) and Patent Document 6 (Japanese Patent Application Laid-Open No. 6-281937) A process of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film as described in the present invention with ultraviolet rays and a process of changing the pretilt angle of a part of the liquid crystal alignment film as described in Patent Document 7 (Japanese Patent Application Laid-open No. 5-107544 A liquid crystal alignment film is formed by performing a process of forming a resist film on a part of the surface of the same liquid crystal alignment film and then rubbing treatment in a direction different from the rubbing treatment performed previously to remove the resist film, It is possible to improve the field of view characteristics.

&Lt; Method of Manufacturing Liquid Crystal Display Device Having the Liquid Crystal Orientation Film &

Two liquid crystal alignment films are formed as described above, and a liquid crystal cell is prepared by arranging liquid crystal between two substrates arranged opposite to each other. Here, when the coating film is subjected to the rubbing treatment, the two substrates are opposed to each other so that the rubbing directions of the respective coating films are mutually opposed at a predetermined angle, for example, orthogonal or inversely.

In order to produce a liquid crystal cell, for example, the following two methods can be mentioned.

The first method is a conventionally known method. First, two substrates are opposed to each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, the peripheral portions of the two substrates are bonded together using a sealing agent, and a cell After the liquid crystal is injected and filled in the interval, the injection hole is sealed to manufacture the liquid crystal cell.

The second method is a method called ODF (One Drop Fill) method. An ultraviolet curable sealing material is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed and the liquid crystal is dropped on the liquid crystal alignment film surface and then the other substrate is bonded so that the liquid crystal alignment film is opposed And then irradiating ultraviolet light to the entire surface of the substrate to cure the sealing agent, thereby manufacturing a liquid crystal cell.

In any method, it is preferable that the liquid crystal used for the liquid crystal cell manufactured as described above is heated to a temperature at which the liquid crystal takes an isotropic phase, and then gradually cooled to room temperature to remove the flow alignment at the time of liquid crystal injection.

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

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

As the liquid crystal, for example, a nematic liquid crystal and a smectic liquid crystal can be used, and among them, a nematic liquid crystal is preferable. In the VA type liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferable. For example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff salt mechanical liquid crystal, an agar liquid crystal, , Phenylcyclohexane-based liquid crystal, and the like. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable. For example, biphenyl type liquid crystal, phenyl cyclohexane type liquid crystal, ester type liquid crystal, terphenyl type liquid crystal, Phenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, quartz-based liquid crystal and the like. Examples of the liquid crystal include cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonanoate, and cholesteryl carbonate; Chiral agents sold under the trade names C-15 and CB-15 (Merck); and a ferroelectric liquid crystal such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate may be further added.

As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called "H film " in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched polyvinyl alcohol is sandwiched between cellulose acetate protective films or a polarizing plate made of H film itself can be given.

&Lt; Method for producing new liquid crystal display element >

The method for producing a novel liquid crystal display element using the liquid crystal aligning agent of the present invention is characterized in that,

A liquid crystal aligning agent of the present invention as described above is applied onto the conductive film of a pair of substrates having a conductive film to form a coated film,

Forming a liquid crystal cell having a configuration in which the coating film of the pair of substrates on which the coating film is formed faces the liquid crystal molecules facing each other through the layer of liquid crystal molecules,

And irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates.

Here, the substrate used is the same as that of the liquid crystal display element having the liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention as described above.

As the conductive film, a transparent conductive film is preferably used. For example, a NESA film containing SnO ₂ , an ITO film containing In ₂ O ₃ -SnO ₂ , or the like can be used. The conductive film is preferably a patterned conductive film partitioned into a plurality of regions. With such a conductive film structure, when applying a voltage between conductive films (described later), a different voltage is applied to each region to change the pretilt angle direction of the liquid crystal molecules in each region, It becomes possible to expand it.

The method of applying the liquid crystal aligning agent on the conductive film of such a substrate, and the film thickness of the coated film after prebaking, post-baking and post-baking after application are as follows: the liquid crystal display having the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention Device. &Lt; / RTI &gt;

The thus formed coating film can be directly used for the production of a liquid crystal cell in a subsequent step, or rubbing treatment for the coating film surface may be carried out before production of the liquid crystal cell, if necessary. This rubbing treatment can be performed in the same manner as in the case of the liquid crystal display element having the liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention.

 Subsequently, a liquid crystal cell is formed which has a configuration in which the coating film of the pair of substrates on which the coating film is formed faces the liquid crystal molecules facing each other through the layer of liquid crystal molecules.

The liquid crystal molecules used herein are preferably nematic liquid crystals having negative dielectric anisotropy, and examples thereof include dicyanobenzene-based liquid crystals, pyridazine-based liquid crystals, Shiff salt mechanical liquid crystals, agar watch liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane Based liquid crystal or the like can be used. The thickness of the liquid crystal molecule layer is preferably 1 to 5 mu m.

The method of forming a liquid crystal cell using such a liquid crystal is the same as that of the liquid crystal display element having the liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention.

Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

The applied voltage may be, for example, 5 to 50 V DC or AC.

As the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable. As the light source of the irradiation light, 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 rays in the above-mentioned preferable wavelength range can be obtained by a means for using the light source in combination with a filter, a diffraction grating or the like.

The dose of light is preferably 1,000 J / m 2 or more and less than 100,000 J / m 2, and more preferably 1,000 to 50,000 J / m 2. It is necessary to irradiate light of about 100,000 J / m 2 in the conventionally known PSA mode liquid crystal display device. However, in the method of the present invention, when the light irradiation amount is 50,000 J / m 2 or less and further 10,000 J / It is possible not only to reduce the manufacturing cost of the liquid crystal display element but also to avoid the deterioration of the electric characteristics due to the strong light irradiation and the deterioration of the reliability for a long period of time.

In addition, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after the above-described processing. Examples of the polarizing plate used herein include a polarizing plate sandwiching the H film and protective film of cellulose acetate or a polarizing plate made of H film itself.

The liquid crystal display device manufactured as described above is preferably applied to various applications because it has wide viewing angle, very fast response time of liquid crystal molecules, excellent display characteristics and long-term reliability, and low manufacturing cost can do.

[Example]

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. Hereinafter, the weight average molecular weight of the polyorganosiloxane, the imidization rate of the polyimide, and the solution viscosity of the polymer were respectively evaluated by the following methods.

[Weight average molecular weight]

The weight average molecular weight of the polyorganosiloxane was determined as polystyrene conversion value using monodisperse polystyrene as a standard material from the results of measurement by gel permeation chromatography under the following conditions using the following apparatus.

Measuring apparatus: type "8120-GPC" manufactured by Tosoh Corporation

Column: "TSKgelGRCXLII ", manufactured by Tosoh Corporation,

Solvent: tetrahydrofuran

Sample concentration: 5 wt%

Sample injection amount: 100 μL

Column temperature: 40 DEG C

Column pressure: 68 kgf / cm 2

[Imidization Rate of Polyimide]

The polyimide was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, and was determined by ¹ H-NMR measurement using tetramethylsilane as a reference material at room temperature according to the following equation (1).

[Equation 1]

Imidization rate (%) = (1-A ¹ / A ² × α) × 100

(A ¹ is the peak area derived from the proton of the NH group near 10 ppm of the chemical shift, A ² is the peak area derived from the other protons, and? Is the peak area derived from the polyimide precursor (polyamic acid) The ratio of the number of other proton to one proton of the NH group)

[Solution viscosity]

The solution viscosity (mPa s) of the polymer was measured at 25 캜 using an E-type rotational viscometer for a solution having a polymer concentration of 10% by weight by using the solvent described in each Synthesis Example.

&Lt; Synthesis of polyorganosiloxane (A) >

Synthesis Example A-1

A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 50.0 g of 3-methacryloxypropyltrimethoxysilane, 45.0 g of methyltrimethoxysilane, 5.0 g of phenyltrimethoxysilane, 500 g of methyl isobutyl ketone 500 g and triethylamine (10.0 g) were charged and mixed at room temperature. Subsequently, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the reaction was carried out for 6 hours while mixing under reflux at 80 占 폚. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% ammonium nitrate aqueous solution until the water layer after washing became neutral. The solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane (A-1) 71.0 g as a viscous transparent liquid. The weight average molecular weight of the polyorganosiloxane (A-1) was 2,500.

Synthesis Examples A-2 to A-7

The polyorganosiloxanes (A-2) to (A-2) were obtained in the same manner as in Synthesis Example A-1 except that the kinds and amounts of the silane compounds used as the raw materials in the above-mentioned Synthesis Example A- A-7) were synthesized.

The yields and weight average molecular weights of these polyorganosiloxanes (A-2) to (A-7) are shown in Table 1, respectively.

&Lt; Comparative Synthesis Example of Polyorganosiloxane >

Comparative Synthesis Examples a-1 and a-2

(A-1) and (a-1) were prepared in the same manner as in Synthesis Example A-1, except that the kinds and amounts of the silane compounds used as the starting materials in Synthesis Example A- -2) were synthesized.

The yields and weight average molecular weights of these polyorganosiloxanes (a-1) and (a-2) are shown in Table 1, respectively.

The abbreviations of the silane compounds in Table 1 are as follows.

MPTMS: 3-methacryloxypropyltrimethoxysilane

APTMS: 3-acryloxypropyltrimethoxysilane

MTMS: methyltrimethoxysilane

PTMS: phenyltrimethoxysilane

MTES: methyltriethoxysilane

ETMS: Ethyltrimethoxysilane

TMS: tetramethoxysilane

DMPDMS: bis (3-methacryloxypropyl) dimethoxysilane

&Lt; Synthesis Example of Polymer (B)

[Synthesis of polyimide]

Synthesis Example B-1

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 43 g (0.40 mole) of p-phenylenediamine as diamine, and 3 (3,5-diaminobenzoyl Oxy) cholestane were dissolved in 830 g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at 60 DEG C for 6 hours to obtain a solution containing the polyamic acid. A small amount of the obtained polyamic acid solution was collected and the solution viscosity was measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP to be 60 mPa.s.

Next, 1,900 g of NMP was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added, followed by dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the polyimide (B-1) having an imidization rate of about 50% was obtained by replacing the solvent in the system with new NMP by solvent replacement (pyridine and acetic anhydride used in the dehydration ring- To obtain about 1,200 g of a solution containing 15% by weight of a solution.

The solution viscosity of this polyimide solution measured as a solution having a polyimide concentration of 10% by weight by taking a small amount of the solution and adding NMP was 47 mPa 占 퐏.

[Synthesis of polyamic acid]

Synthesis Example B-2

98 g (0.50 mol) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride and 110 g (0.50 mol) of pyromellitic dianhydride as a tetracarboxylic dianhydride, 4,4'-dia 200 g (1.0 mole) of minodiphenylmethane was dissolved in 2,330 g of N-methyl-2-pyrrolidone and the reaction was carried out at 40 DEG C for 3 hours. Then, 1,350 g of N-methyl- To obtain about 3,800 g of a solution containing 10 wt% of polyamic acid (B-2).

The solution viscosity of this polyamic acid solution was 135 mPa..

Example 1

&Lt; Preparation of liquid crystal aligning agent &

A solution containing the polyimide (B-1) obtained in Synthesis Example B-1 as the polymer (B) was converted into a polyimide (B-1) in an amount corresponding to 70 parts by weight, 30 parts by weight of the polyorganosiloxane (A-1) obtained in Synthesis Example A-1 as the siloxane (A), and 30 parts by weight of the (N, N, N ', N'-tetraglycidyl- (NMP: BC = 55: 45 (weight ratio), a solid content concentration of 4 weight% (weight ratio), and 10 parts by weight of a diamine were further added and N-methyl-2-pyrrolidone (NMP) and butyl cellosolve % Solution. This solution was filtered using a filter having a pore size of 1 占 퐉 to prepare a liquid crystal aligning agent.

Various evaluations were carried out as follows using this liquid crystal aligning agent. The evaluation results are shown in Table 1.

&Lt; Evaluation of liquid crystal aligning agent &

[Evaluation of storage stability]

The liquid crystal aligning agent was coated on the glass substrate by a spin coating method by varying the number of revolutions, pre-baked at 80 DEG C for 5 minutes and then baked at 200 DEG C for 60 minutes to form a coating film, Of the film thickness was 1,000 angstroms.

Subsequently, a part of the liquid crystal aligning agent was taken and stored at -15 DEG C for 5 weeks. The liquid crystal aligning agent after storage was visually observed, and when the precipitation of insoluble matter was observed, the storage stability was judged as "very poor ".

When no insoluble matter was observed after 5 weeks of storage, the preserved liquid crystal aligning agent was applied onto the glass substrate by spin coating at a revolution number of 1,000 Å before storage, and prebaked And post-baking were performed to form a coating film, and the film thickness thereof was measured. When the film thickness was deviated by more than 10% from 1,000 ANGSTROM, the storage stability was judged as "defective ", and when the film thickness deviation was less than 10%, the storage stability was judged as" good ".

The film thickness of the coating film was measured using a needle contact type step film thickness meter manufactured by KLA-Tencor Corporation.

&Lt; Preparation and evaluation of vertical alignment type liquid crystal display device >

[Production of vertical alignment type liquid crystal display device]

The liquid crystal aligning agent prepared above was coated on the transparent electrode surface of the glass substrate with a transparent electrode including the ITO film using a spinner, pre-baked at 80 DEG C for 5 minutes, and then heated in an oven at 200 DEG C for 1 hour To form a coating film (liquid crystal alignment film) having a thickness of 0.1 mu m. This operation was repeated to prepare a pair of substrates (two substrates) having a liquid crystal alignment film.

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied to the outer periphery of one of the substrates having the liquid crystal alignment film by screen printing and then the surface of the liquid crystal alignment film of the pair of substrates was reversed And the adhesive was thermally cured by heating at 150 DEG C for 1 hour. Subsequently, a negative type liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled in the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy adhesive, After heating for 10 minutes, it was gradually cooled to room temperature.

A vertical alignment type liquid crystal display device was prepared by bonding polarizers on both outer sides of the substrate so that the polarization directions thereof were at an angle of 45 degrees with respect to the rubbing direction of the liquid crystal alignment film and the polarization directions of the two polarizers were orthogonal to each other.

[Evaluation of vertical alignment type liquid crystal display device]

(1) Evaluation of liquid crystal alignment property

The presence or absence of an abnormal domain in a light / dark change when a voltage of 5 V was turned on / off (applied / released) to the liquid crystal display device manufactured as described above was observed. In the case of a vertically aligned liquid crystal display device, light leakage is not observed at the time of voltage OFF, when the voltage is applied, the drive region is displayed in white, and when there is no light leakage from other regions, The case where the leakage was observed was defined as "poor"

(2) Evaluation of voltage holding ratio

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

(3) Evaluation of heat resistance

The liquid crystal display device manufactured in the same manner as described above was left to stand in an oven at 80 캜 for 10 hours, then allowed to stand at room temperature and naturally cooled to room temperature. Subsequently, a voltage of 5 V was applied to the liquid crystal display element at an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the release was measured. VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device.

(4) Evaluation of ultraviolet ray property

Ultraviolet light of 10 J / cm &lt; 2 &gt; was irradiated to the liquid crystal display device produced in the same manner as above with a metal halide lamp having an illuminance of 80 mW / cm 2, then left at room temperature and naturally cooled to room temperature. Subsequently, a voltage of 5 V was applied with an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the release voltage was measured. VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device.

(5) Evaluation of the burning resistance

A voltage of 17 V DC was applied to the liquid crystal display device manufactured in the same manner as above for 20 hours at an environmental temperature of 100 DEG C and the voltage (residual DC voltage) remaining in the liquid crystal cell immediately after the DC voltage was cut was subjected to flicker elimination Respectively. When the value of the residual DC voltage was 1,000 mV or less, the resistance was determined to be "good" and the other cases were determined to be "poor".

Examples 2 to 11 and Comparative Examples 1 to 4

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that kinds and amounts of the polyorganosiloxane, the polymer (B) and the epoxy compound (C) were changed as shown in Table 2, Various evaluations were carried out. The evaluation results are shown in Table 2.

Further, in these Examples and Comparative Examples, Polymer (B) was all used in the preparation of liquid crystal aligning agent as the polymer solution obtained in Synthesis Example. The amount of the polymer (B) in Table 2 is a value converted into the amount of the polymer contained in the used polymer solution. In Example 10, a solvent was added so that the solvent composition was NMP: BC: gamma -butyrolactone = 50: 40: 10 (weight ratio).

The abbreviations of the epoxy compounds (C) in Table 2 are as follows.

C-1: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

C-2: N, N, N ', N'-tetraglycidyl-m-xylenediamine

C-3: Bisphenol A novolak type epoxy resin (trade name "Epicoat 157S65", manufactured by Japan Epoxy Resin Co., Ltd.)

"-" in the component column in Table 2 indicates that no component corresponding to the corresponding column is used.

As is apparent from the above examples, the liquid crystal aligning agent of the present invention containing the polyorganopolysiloxane (A) and the polymer (B) is excellent in storage stability, and has a liquid crystal alignment film formed therefrom, The display element exhibits excellent liquid crystal alignability and voltage retention, and is excellent in heat resistance, ultraviolet ray resistance, and resistance to fire.

The liquid crystal display element of the present invention provides a liquid crystal display element having especially excellent anti-sintering properties compared to a conventionally known liquid crystal aligning agent containing polysiloxane as a main component.

&Lt; Production of liquid crystal cell &

Example 12

Using the liquid crystal aligning agent prepared in Example 1, six liquid crystal display elements in total were produced and evaluated by changing the pattern (two kinds) of transparent electrodes and the amount of ultraviolet irradiation (three levels) as described below.

[Production of liquid crystal cell having transparent electrode without pattern]

The liquid crystal aligning agent prepared in Example 1 was coated on the transparent electrode surface of a glass substrate having a transparent electrode including an ITO film by using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Sein Insights Co., Ltd.) (Pre-baked) for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 150 DEG C for 10 minutes to form a coating film having an average film thickness of 600 ANGSTROM.

The coating film was subjected to a rubbing treatment at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a filament insertion length of 0.1 mm by a rubbing machine having a roll wound with a rayon spring. Thereafter, ultrasonic cleaning was performed for one minute in ultrapure water, and then the substrate was dried in a clean oven at 100 캜 for 10 minutes to obtain a substrate having a coated film rubbed. This operation was repeated to obtain a pair of substrates (two pieces) each having a rubbed coating film.

Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied to each of the outer edges of the coated substrate on which the pair of substrates had been rubbed, and then the adhesive was superimposed on the adhesive so as to face each other. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection hole was sealed with an acrylic light curing adhesive to manufacture a liquid crystal cell.

The above operation was repeated to produce three liquid crystal cells having transparent electrodes without a pattern. One of them was used for evaluation of the pretilt angle as described later. The remaining two liquid crystal cells were irradiated with light in a state in which a voltage was applied between the conductive films by the following method, and then used for evaluation of the pretilt angle and the voltage holding ratio.

Two of the liquid crystal cells obtained above were applied with an alternating current of 10 V at a frequency of 60 Hz between the electrodes and irradiated with ultraviolet rays of 10,000 J / m &lt; 2 &gt; or 100,000 J / m &lt; 2 &gt; This irradiation dose is a value measured using a photometer which is measured based on a wavelength of 365 nm.

[Evaluation of Pretilt Angle]

According to the method described in Non-Patent Document 2 (TJ Scheffer et al. J. Appl. Phys. Vol. 19, p. 2013 (1980)) for each liquid crystal cell prepared above, As a result of measuring the pretilt angle by the crystal rotation method using Ne laser light, the pretilt angle of the liquid crystal cell not irradiated with light was 89 °, the pretilt angle of the liquid crystal cell with the irradiation amount of 10,000 J / The pretilt angle of the liquid crystal cell having a dose of 100,000 J / m 2 was 84 °.

[Production of liquid crystal cell having patterned transparent electrode]

The liquid crystal aligning agent prepared in Example 1 was patterned in the form of a slit as shown in Fig. 1, and on each electrode surface of the glass substrates (A) and (B) having ITO electrodes partitioned into a plurality of regions, (Prebaked) on a hot plate at 80 DEG C for 1 minute to remove the solvent, and then heated on a hot plate at 150 DEG C for 10 minutes (after-baking ) To form a coating film having an average film thickness of 600 ANGSTROM. This coating film was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a coated film. This operation was repeated to obtain a pair of substrates (two pieces) having a coated film.

Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 탆 was applied to each of the outer edges of the pair of substrates having the coated film, and the adhesive was superimposed on the adhesive so as to face the coated film surface. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection hole was sealed with an acrylic light curing adhesive to manufacture a liquid crystal cell.

The above operation was repeated to produce three liquid crystal cells having patterned transparent electrodes. One of them was used to evaluate the response speed as will be described later. The remaining two liquid crystal cells were irradiated with light of 10,000 J / m 2 or 100,000 J / m 2 in a state of applying voltage between the conductive films by the same method as in the production of the liquid crystal cell having the transparent electrode without the pattern After irradiation with light, it was used to evaluate the response speed.

The electrode pattern used here is a pattern similar to the electrode pattern in the PSA mode.

[Evaluation of response speed]

For each of the liquid crystal cells prepared above, the luminance of the light transmitted through the liquid crystal cell was measured by irradiating a visible light lamp without applying a voltage at first, using a photomultimeter, and the relative transmittance was 0%. Subsequently, the transmittance when an AC voltage of 60 V was applied between the electrodes of the liquid crystal cell for 5 seconds was measured in the same manner as described above, and the relative transmittance was 100%.

At this time, the time from when the relative transmittance was changed from 10% to 90% when an alternating current of 60 V was applied to each liquid crystal cell was measured, and this time was defined as a response speed and evaluated.

As a result, the response speed of the liquid crystal cell not irradiated with light was 52 msec, and the response speed of the liquid crystal cell with the irradiation amount of 10,000 J / m 2 was 48 msec and the response speed of the liquid crystal cell with the irradiation amount of 100,000 J / m 2 was 27 msec.

Examples 13 and 14

As in Example 12, except that the liquid crystal aligning agent prepared in Example 2 was used as the liquid crystal aligning agent and the liquid crystal aligning agent prepared in Example 3 was used in Example 14, Cells were prepared and evaluated.

The evaluation results are shown in Table 3.

From the results shown in Table 3, in the method for producing a new liquid crystal display element in the present invention, when the ultraviolet irradiation amount is 100,000 J / m 2 (conventionally used in the PSA mode), the degree of pretilt angle obtained becomes excessive, It was found that a proper pretilt angle was obtained at an irradiation dose of J / m 2 or less. In addition, a sufficiently fast response speed was obtained even when the dose was small. From the results shown in Table 2, it was found that the liquid crystal aligning agent of the present invention had very excellent ultraviolet ray resistance.

Therefore, according to the method for manufacturing a liquid crystal display element of the present invention, it is possible to realize the advantage of the PSA mode even at a light amount of irradiation with a small amount of light. Therefore, occurrence of display irregularity due to high light exposure, deterioration of voltage holding characteristics, It is possible to manufacture a liquid crystal display element having a wide viewing angle, a fast response speed of liquid crystal molecules, a high transmittance and a high contrast without concern.

Claims (9)

(A) a polyorganosiloxane obtained by hydrolyzing and condensing a silane compound containing a compound represented by the following formula (1), and (B) a polyorganosiloxane and a polyimide A liquid crystal aligning agent containing at least one polymer selected from the group consisting of
Forming a liquid crystal cell having a configuration in which the coating film of the pair of substrates on which the coating film is formed faces the liquid crystal molecules facing each other through the layer of liquid crystal molecules,
And irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates.
&Lt; Formula 1 >

(Wherein R ^I is a monovalent organic group having a (meth) acryloyl group and R ^II is a monovalent organic group) The method for producing a liquid crystal display element according to claim 1, wherein the ratio of the polyorganosiloxane (A) to the sum of the polyorganosiloxane (A) and the polymer (B) is 0.01 to 30% by weight. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the silane compound further comprises a compound represented by the following formula (2) in addition to the compound represented by the formula (1).
(2)

(Wherein R ^III is a linear alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 24 carbon atoms, and R ^IV is a monovalent organic group) The polyorganosiloxane according to claim 1 or 2, wherein the polyorganosiloxane (A) is a polyorganosiloxane obtained by hydrolyzing and condensing a silane compound containing 20 to 80% by weight of a compound represented by the formula (1) A method of manufacturing a display device. The liquid crystal display element of claim 1 or 2, wherein the liquid crystal aligning agent (C) further contains a compound having at least one epoxy group in the molecule. The method for producing a liquid crystal display element according to claim 5, wherein the compound (C) is a compound having a group represented by the following formula (3).
(3)

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