KR20100094954A - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display device, and process for producing liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal aligning agent is provided to obtain excellent vertical orientation and stability for a long term, to prevent the degradation of a voltage holding ratio, and to form a liquid crystal alignment layer having excellent an after image property. CONSTITUTION: A liquid crystal aligning agent contains polyorganosiloxane(A), which is obtained through hydrolysis and condensation of a silane compound including a compound which is marked by chemical formula 1 of R^ISi(OR^II)_3, and a polymer(B) which is selected from a group comprising polyamic acid and polyimide. In chemical formula 1, R^I is a monovalent organic group having a (meth)acryloyl group and R^II is a monovalent organic group. The ratio of the polyorganosiloxane is 0.01-30 weight% based on the total weight of the polyorganosiloxane and the polymer.

Description

Liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, and the manufacturing method of a liquid crystal display element

This invention relates to a liquid crystal aligning agent, a liquid crystal display element, and its manufacturing method.

Currently, as a liquid crystal display element, the liquid crystal aligning film is formed in the surface of the board | substrate with which the transparent conductive film is provided, and it is set as the board | substrate for liquid crystal display elements, the two sheets are mutually arrange | positioned, and the layer of the nematic liquid crystal which has positive dielectric anisotropy in the clearance gap. A TN type liquid crystal display element having a so-called TN type (Twisted Nematic) liquid crystal cell in which a long axis of liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other substrate is formed so as to form a sandwich cell. In addition, a super twisted nematic (STN) type liquid crystal display element capable of achieving a high contrast ratio compared to a TN type liquid crystal display element, an IPS (In-Plane Switching) type liquid crystal display element having a low viewing angle dependency, and a nema having negative dielectric anisotropy VA (Vertical Alignment) type liquid crystal display elements using tick liquid crystals, etc. have been developed.

The operating principle of these various liquid crystal display elements is largely divided into a transmission type and a reflection type. The transmissive liquid crystal display element displays using the intensity change of the transmitted light of the backlight light source from the back of an element at the time of element drive. On the other hand, the reflective liquid crystal display element does not use a light source for a backlight, and performs display by using the intensity change of the reflected light of the light from the outside, such as sunlight, when the element is driven. It is considered particularly advantageous for the use of.

In a transmissive liquid crystal display element, the liquid crystal aligning film provided in this is exposed to light from a backlight light source for a long time. In particular, not only for business use but also for liquid crystal projector use, which has recently been increasing in demand as a home theater, a very high light source such as a metal halide lamp is used. Moreover, it is thought that the temperature of the liquid crystal display element itself rises at the time of driving with light irradiation with strong intensity. In the case of a reflective liquid crystal display element, it is highly likely to be used outdoors, and in this case, sunlight containing strong ultraviolet light becomes a light source. In addition, in the reflection type, the distance that light passes through the element is longer than that of the transmission type. In addition, both the transmissive liquid crystal display element and the reflective liquid crystal display element tend to be widely used in installation in, for example, automobiles, and the like. Realized.

However, in the manufacturing process of a liquid crystal display element, what started to be used from a viewpoint of process shortening and a yield improvement is a liquid crystal dropping method, ie, an ODF (One Drop Fill) system. Unlike the conventional method of injecting a liquid crystal into an empty liquid crystal cell assembled using a thermosetting sealant in advance, the ODF method applies an ultraviolet light curable sealant to a required location of one substrate to which a liquid crystal alignment film is applied. After dropping a liquid crystal to a required location and bonding the other board | substrate, ultraviolet light is irradiated to the whole surface, hardening a sealing agent, and manufacturing a liquid crystal cell. Ultraviolet light irradiated at this time is generally stronger than several joules (J) per cm 2. That is, in the liquid crystal display element manufacturing process, a liquid crystal aligning film is exposed to this strong ultraviolet light with a 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 are unprecedented due to its high functionality, versatility, and improvement of manufacturing processes. Electrical properties such as orientation, voltage retention, or display characteristics are required to be superior to those of the prior art, and furthermore, longer lifetimes are required for liquid crystal display elements.

As a material of the liquid crystal aligning film which comprises a liquid crystal display element, organic resins, such as a polyimide, a polyamic acid, polyamide, and polyester, are known conventionally. In particular, polyimide is used in many liquid crystal display elements because it exhibits excellent physical properties such as heat resistance, affinity with liquid crystals, mechanical strength, and the like in organic resins (Patent Documents 1 to 3). However, in recent liquid crystal display devices, new demands are increasing due to the severer production environment and use environment as described above, and the heat resistance and light resistance to the extent that an organic resin that has been conventionally accepted can be achieved.

Therefore, examination of the liquid crystal aligning film excellent in heat resistance and light resistance is performed. For example, Patent Document 4 discloses a vertically oriented 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 the vertical alignment, heat resistance and uniformity are disclosed. It is demonstrated that it is excellent and the stability as a coating liquid is also excellent. However, the liquid crystal aligning film which concerns on the technique of patent document 4 does not satisfy | fill the required performance by the severeness of the current manufacturing environment and use environment, and since the storage stability of a coating liquid is lacking, it is convenient for industrial use. there is a problem.

It is possible to provide a liquid crystal aligning film having sufficient heat resistance and light resistance in a very harsh current production environment and use environment, and a liquid crystal aligning agent having excellent storage stability is not yet known.

In addition, a multi-domain vertical alignment (MVA) panel is known which forms projections in the liquid crystal panel in order to increase the viewing angle in the VA type liquid crystal panel, thereby regulating the conduction direction of the liquid crystal molecules. However, according to this system, there is a problem that the lack of transmittance and contrast derived from the projections is inevitable, and the response speed of the liquid crystal molecules is slow.

In order to solve the problem of the MVA panel, a PSA (Polymer Sustained Alignment) mode has recently been proposed. The PSA mode uses a polymerizable compound in a gap between a pair of substrates formed of a substrate with a patterned conductive film and a substrate with a conductive film having no pattern, or a pair of substrate gaps composed of two substrates with a patterned conductive film. It is the technique which clamps the liquid crystal composition containing, superposes | polymerizes a polymeric compound by irradiating an ultraviolet-ray in the state which applied the voltage between electrically conductive films, and expresses a pretilt angle characteristic by this, and controls the orientation direction of a liquid crystal. According to this technique, the conductive film has a specific configuration, which can increase the viewing angle and speed up the response of the liquid crystal molecules, and also solves the problems of lack of transmittance and contrast, which are inevitable in the MVA panel. However, for the polymerization of the polymerizable compound, for example, irradiation of a large amount of ultraviolet light of 100,000 J / m 2 is required, which causes not only the problem of decomposing liquid crystal molecules, but also unreacted unpolymerized by ultraviolet light irradiation. Since the compounds remain in the liquid crystal layer, and they interact with each other to generate display unevenness, adversely affect voltage retention characteristics, or problems with long-term reliability of the panel, it has not yet been practical.

Non-patent document 1 has proposed the method of using the liquid crystal aligning film formed from the polyimide-type liquid crystal aligning agent containing a reactive mesogen. According to Non-Patent Document 1, in the liquid crystal display element provided with the liquid crystal aligning film formed by such a method, the response of liquid crystal molecules is high speed. However, in Non-Patent Document 1, there are no guidelines on how much reactive mesogen to be used, and since the amount of ultraviolet irradiation required is still large, concern about display characteristics, in particular voltage holding characteristics, is not dismissed. .

Japanese Patent Publication No. 9-197411 Japanese Patent Laid-Open No. 2003-149648 Japanese Patent Laid-Open No. 2003-107486 Japanese Patent Laid-Open No. 9-281502 Japanese Patent Publication No. 6-222366 Japanese Patent Laid-Open No. 6-281937 Japanese Patent Publication 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)

This invention is made | formed in view of the above situation, The objective is to form the liquid crystal aligning film excellent in the vertical alignment property and long-term stability, the fall of the voltage retention in case of being exposed to heat and light for a long time, and excellent in an afterimage characteristic. It is to provide the liquid crystal aligning agent which can be provided.

Still another object of the present invention is to provide a liquid crystal display device and a method of manufacturing the same, in which the display quality does not deteriorate even when exposed to heat and light for a long time.

Still 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, firstly,

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

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

It is achieved by the liquid crystal aligning agent containing.

(In Formula 1, R ^I is a monovalent organic group having a (meth) acryloyl group, and R ^II is a monovalent organic group.)

The liquid crystal aligning agent described above can be suitably used for liquid crystal display elements having a known structure such as TN type, STN type, IPS type, VA type, etc., and to manufacture novel liquid crystal display elements in which problems of the MVA panel are solved. Can be used.

Therefore, the above objects and advantages of the present invention are second,

It is achieved by the liquid crystal display element provided with the liquid crystal aligning film formed from the said liquid crystal aligning agent,

Third,

On the said conductive film of a pair of board | substrates which have a conductive film, each said liquid crystal aligning agent is apply | coated and a coating film is formed,

Forming a liquid crystal cell of a structure in which the coating films of the pair of substrates on which the coating films are formed face each other through a layer of liquid crystal molecules,

It is achieved by a method for manufacturing a liquid crystal display device which undergoes a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates.

Since the liquid crystal aligning agent of this invention is excellent in a perpendicular alignment property and long term stability, there is little fall of the voltage retention when it is exposed to heat and light for a long time, and can form the liquid crystal aligning film excellent in afterimage characteristic, the liquid crystal aligning property of this invention The liquid crystal display element provided with the liquid crystal aligning film formed by zero can be effectively applied to various apparatus.

In addition, the novel liquid crystal display device manufactured by the above-described method for manufacturing a liquid crystal display device of the present invention has a wide viewing angle, fast response speed of liquid crystal molecules, good electrical properties and sufficient transmittance and contrast, and excellent display specificity. Since the display characteristics are not impaired even after continuous driving for a long time, and the amount of light required for irradiation of the liquid crystal display element is small, it is effective for reducing the manufacturing cost.

The said liquid crystal display element can be used suitably for various apparatuses, such as a table calculator, a wristwatch, a table clock, a coefficient display board, a word processor, a personal computer, a liquid crystal television, respectively, for example.

BRIEF DESCRIPTION OF THE DRAWINGS Explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell which has the patterned transparent conductive film manufactured in Examples 12-14.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The liquid crystal aligning agent of this invention is at least

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

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

It contains.

<Polyorganosiloxane (A)>

The polyorganosiloxane (A) in this invention is a polyorganosiloxane obtained by hydrolyzing and condensing the silane compound containing the compound represented by the said Formula (Hereinafter, a "silane compound (1)").

Examples of R ^I in formula (I), for example to the like group represented by general formula (R ^I -1).

(In formula (R ^I- 1), R is a hydrogen atom or a methyl group, a is an integer of 1 to 10, b is 0 or 1, c is an integer of 0 to 2, d is 0 or 1, e is an integer from 0 to 3, except that c, d, and e are not 0 at the same time, and e is 0 when b and d are 0 and c is not 0.

As a specific example of such R <^I> , a (meth) acryloxymethyl group, 2-((meth) acryloxy) ethyl group, 3-((meth) acryloxy) propyl group, 4-((meth) acryloxy) butyl Group, 5-((meth) acryloxy) pentyl group, 6-((meth) acryloxy) hexyl group, 7-((meth) acryloxy) heptyl group, 8-((meth) acryloxy) octyl group, 9-((meth) acryloxy) nonyl group, 10-((meth) acryloxy) decyl group, 4- (2-((meth) acryloxy) ethyl) phenyl group, 2-((4- (meth) acryl Oxy) phenyl) ethyl group, 4-((meth) acryloxymethyl) phenyl group, 4- (meth) acryloxyphenylmethyl group, 4- (3-((meth) acryloxy) propyl) phenyl group, 3- (4- ( (Meth) acryloxyphenyl) propyl group, 4-((meth) acryloxymethoxy) phenyl group, 4- (2-((meth) acryloxy) ethoxy) phenyl group, 4- (3-((meth) acryloxy ) Propoxy) phenyl group, (meth) acryloxymethoxymethyl group, 2-((meth) acryloxymethoxy) ethyl group, 2- (2-((meth) acryloxy) ethoxy) 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 1 include a group in which R is a hydrogen atom or a methyl group, a is an integer of 1 to 10, c is 1, and b, d and e are each 0 in Formula (R ^I- 1). Preferably, More preferably, it is (meth) acryloxymethyl group, 2-((meth) acryloxy) ethyl group, 3-((meth) acryloxy) propyl group, 4-((meth) acryloxy) butyl group, 5 It is a-((meth) acryloxy) pentyl group or a 6-((meth) acryloxy) hexyl group, Especially preferably, it is a 3-((meth) acryloxy) propyl group.

As R ^II in the general formula (1), for example, an alkylsulfonyl group having an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylsulfonyl group having 6 to 12 carbon atoms and an alkyl group having 1 to 4 carbon atoms Etc.,

As these specific examples, it is a C1-C12 alkyl group, for example, a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group, a pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group , Undecyl group, dodecyl group, etc .;

As an aryl group having 6 to 12 carbon atoms, for example, a phenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group, 2 A 4,6-trimethoxyphenyl group and the like;

As an arylsulfonyl group which has a C6-C12 aryl group, For example, p-toluenesulfonyl group etc .;

As an alkylsulfonyl group which has a C1-C4 alkyl group, a methylsulfonyl group etc. are mentioned, respectively.

R ^II in Chemical Formula 1 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a t-butyl group, still more preferably a methyl group, an ethyl group or It is a t-butyl group, Especially preferably, it is a methyl group.

As a specific example of such a silane compound (1), for example, (meth) acryloxymethyl trimethoxysilane, (meth) acryloxymethyl triethoxysilane, (meth) acryloxymethyl tri-n-propoxysilane, ( (Meth) acryloxymethyl tri-i-propoxysilane, (meth) acryloxymethyl tri-n-butoxysilane, (meth) acryloxymethylpropyl tri-sec-butoxysilane,

2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 2- (meth) acryloxyethyltri-n-propoxysilane, 2- (meth) acryloxyethyl Tri-i-propoxysilane, 2- (meth) acryloxyethyltri-n-butoxysilane, 2- (meth) acryloxyethylpropyltri-sec-butoxysilane,

3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyl Tri-i-propoxysilane, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane,

4- (meth) acryloxybutyl trimethoxysilane, 4- (meth) acryloxybutyl triethoxysilane, 4- (meth) acryloxybutyl tri-n-propoxysilane, 4- (meth) acryloxybutyl Tri-i-propoxysilane, 4- (meth) acryloxybutyltri-n-butoxysilane, 4- (meth) acryloxybutylpropyltri-sec-butoxysilane,

5- (meth) acryloxypentyltrimethoxysilane, 5- (meth) acryloxypentyltriethoxysilane, 5- (meth) acryloxypentyltri-n-propoxysilane, 5- (meth) acryloxy Pentyltri-i-propoxysilane, 5- (meth) acryloxypentyltri-n-butoxysilane, 5- (meth) acryloxypentylpropyltri-sec-butoxysilane,

6- (meth) acryloxyhexyltrimethoxysilane, 6- (meth) acryloxyhexyltriethoxysilane, 6- (meth) acryloxyhexyltri-n-propoxysilane, 6- (meth) acryloxyhexyl Tri-i-propoxysilane, 6- (meth) acryloxyhexyltri-n-butoxysilane, 6- (meth) acryloxyhexylpropyl tri-sec-butoxysilane, and the like.

When synthesize | combining the polyorganosiloxane (A) in this invention, only the silane compound (1) may be hydrolyzed and condensed, or the mixture of a silane compound (1) and silane compounds other than a silane compound (1) may be hydrolyzed. You can also dissolve and condense.

As silane compounds other than the silane compound (1) which can be used here, the compound represented by following formula (2) (henceforth "silane compound (2)"), and other silane compounds (henceforth "silane compound (3) ) ").

(In Formula 2, R ^III is a straight chain 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 linear alkyl group having 1 to 18 carbon atoms of R ^III in Formula 2 include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl, n-octadecyl group, etc. are mentioned. The alkyl group of R ^III having 1 to 18 carbon atoms of straight-chain, the straight-chain alkyl groups having 1 to 6 carbon atoms are preferred, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

Examples of the linear fluoroalkyl group having 1 to 18 carbon atoms of R ^III include trifluoromethyl group, 2- (trifluoromethyl) ethyl group, 3- (trifluoromethyl) propyl group, and perfluoro-n-. A hexyl group, a perfluoro-n-octyl group, a 2- (perfluoro-n-octyl) ethyl group, a perfluoro-n-dodecyl group, a perfluoro-n-octadecyl group, and the like. Examples of R ^III fluoroalkyl having 1 to 18 carbon atoms in the straight-chain alkyl group, the alkyl group preferably a linear fluoroalkyl group having 1 to 6 carbon atoms, and a trifluoromethyl group, a ethyl group, 3- (trifluoro-2- (trifluoromethyl) Methyl) propyl group or perfluoro-n-hexyl group is more preferable, and trifluoromethyl group is particularly preferable.

Examples of the aryl group having 6 to 24 carbon atoms for R ^III include phenyl group, 4-methylphenyl group, 2-methylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, and 4-n-propylphenyl group. , 4-n-hexylphenyl group, 4-n-octylphenyl group, 4-n-dodecylphenyl group, 4-n-octadecylphenyl group, etc. are mentioned, Among these, a phenyl group, 4-methylphenyl group, 3-methylphenyl group, 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, or an alkylsulfonyl group having an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 8 carbon atoms. Sulfonyl groups and the like.

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

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

As an alkylsulfonyl group which has a C1-C6 alkyl group, For example, methylsulfonyl group, ethylsulfonyl group, n-hexylsulfonyl group, etc .;

Examples of the arylsulfonyl group having an aryl group having 6 to 8 carbon atoms include p-toluenesulfonyl group, 3,5-dimethylphenylsulfonyl group, and the like. In these, as R <^IV> in said General formula (2), it is preferable that it is a C1-C6 alkyl group.

As a specific example of such a silane compound (2), for example, methyl trimethoxysilane, methyl triethoxysilane, methyl tri-n-propoxy silane, methyl tri-i-propoxy silane, methyl tri-n-butoxy Silane, methyltri-sec-butoxysilane, methyltri-n-pentasilane, methyltri-sec-butoxysilane, methyltriphenoxysilane, methyltri-p-methylphenoxysilane,

Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-i-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltree -n-pentasilane, ethyltri-sec-butoxysilane, ethyltriphenoxysilane, ethyltri-p-methylphenoxysilane,

n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-i-propoxysilane, n-propyltri-n-butoxysilane, n -Propyltri-sec-butoxysilane, n-propyltri-n-pentasilane, n-propyltri-sec-butoxysilane, n-propyltriphenoxysilane, n-propyltri-p-methylphenoxy Silane,

n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-i-propoxysilane, n-butyltri-n-butoxysilane, n -Butyl tri-sec-butoxysilane, n-butyl tri-n-pentasilane, n-butyl tri-sec-butoxysilane, n-butyl triphenoxysilane, n-butyl tri-p-methylphenoxy Silane,

n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-pentyltri-n-propoxysilane, n-pentyltri-i-propoxysilane, n-pentyltri-n-butoxy Silane, n-pentyltri-sec-butoxysilane, n-pentyltri-n-pentasilane, n-pentyltri-sec-butoxysilane, n-pentyltriphenoxysilane, n-pen Tiltri-p-methylphenoxysilane,

2- (trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoro Rhomethyl) ethyltri-i-propoxysilane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (purple Fluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl ) Ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro -n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyl Li-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyl Tri-i-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, for example, trichlorosilane, trimethoxysilane, triethoxysilane and tri-n- Propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n -Propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyl Trimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-prop Sisilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyl Trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n- Butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltrier Methoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane , Phenyltrichlorosilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysilane, methyldi- sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi- sec-butoxysilane,

(Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro R-n-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-i-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) die Methoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di -n-butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) Diethoxysilane, (methyl) (vinyl) di-n-prop Foxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, Divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxy Silane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, di Phenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-pro Foxtrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethyl Column, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl) Diphenylsilane, bis (3- (meth) acryloxypropyl) dimethoxysilane, bis (3- (meth) acryloxypropyl) diethoxysilane, bis (3- (meth) acryloxypropyl) di-i-pro Foxysilane, bis (3- (meth) acryloxypropyl) di-n-butoxysilane, bis (3- (meth) acryloxypropyl) di-sec- butoxysilane, bis (3- (meth) acryloxy Propyl) diphenoxysilane, tris (3- (meth) acryloxypropyl) methoxysilane, tris (3- (meth) acryloxypropyl) ethoxysilane, tris (3- (meth) acryloxypropyl) -n -Propoxysilane, tris (3- (meth) acryloxypropyl) -i-propoxysilane, tris (3- (meth) acryloxypropyl) -n-butoxysilane, tris (3- (meth) acryloxy Propyl) -i-butoxysilane, tris (3- (meth) acrylicoxy Phenoxysilane,

Dimethyldimethoxysilane, Diethyldimethoxysilane, Di-n-propyldimethoxysilane, Di-i-propyldimethoxysilane, Di-n-butyldimethoxysilane, Di-sec-butyldimethoxysilane, Di-n -Pentyldimethoxysilane, di-hexyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, di-n-propyldiethoxysilane, di-i-propyldiethoxysilane, di-n-butyldiethoxysilane , Di-sec-butyldiethoxysilane, di-n-pentyldiethoxysilane, di-hexyl diethoxysilane, dimethyl-di-i-propoxysilane, diethyl-di-i-propoxysilane, di-n -Propyl-di-i-propoxysilane, di-i-propyl-di-i-propoxysilane, di-n-butyl-di-i-propoxysilane, di-sec-butyl-di-i-prop Foxysilane, di-n-pentyl-di-i-propoxysilane, di-hexyl-di-i-propoxysilane, dimethyl-di-sec-butoxysilane, diethyl-di-sec-butoxysilane, Di-n-propyl-di-sec-butoxysilane, di-i-propyl-di-sec-butoxysilane, di-n-butyl-di-sec-part Methoxysilane, di-sec-butyl-di-sec-butoxysilane, di-n-pentyl-di-sec-butoxysilane, di-hexyl-di-sec-butoxysilane, trimethylmethoxysilane, triethyl Methoxysilane, tri-n-propylmethoxysilane, tri-i-propylmethoxysilane, tri-n-butylmethoxysilane, tri-sec-butylmethoxysilane, tri-n-hexylmethoxysilane, tri -n-dodecylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, tri-n-propylethoxysilane, tri-i-propylethoxysilane, tri-n-butylethoxysilane, tri-sec- Butylethoxysilane, tri-n-hexylethoxysilane, tri-n-dodecylethoxysilane, trimethyl-n-propoxysilane, triethyl-n-propoxysilane, tri-n-propyl-n-prop Foxysilane, tri-i-propyl-n-propoxysilane, tri-n-butyl-n-propoxysilane, tri-sec-butyl-n-propoxysilane, tri-n-hexyl-n-propoxysilane , Tri-n-dodecyl-n-propoxysilane, trimethyl-i-propoxysilane, tree Ethyl-i-propoxysilane, tri-n-propyl-i-propoxysilane, tri-i-propyl-i-propoxysilane, tri-n-butyl-i-propoxysilane, tri-sec-butyl- i-propoxysilane, tri-n-hexyl-i-propoxysilane, tri-n-dodecyl-i-propoxysilane, trimethyl-sec-butoxysilane, triethyl-sec-butoxysilane, tri- n-propyl-sec-butoxysilane, tri-i-propyl-sec-butoxysilane, tri-n-butyl-sec-butoxysilane, tri-sec-butyl-sec-butoxysilane, tri-n- Hexyl-sec-butoxysilane, tri-n-dodecyl-sec-butoxysilane, and the like.

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

The silane compound used when synthesizing the polyorganosiloxane (A) in the present invention is 20 to 80% by weight of the silane compound (1) based on the total silane compounds from the viewpoint of further improving the electrical properties of the liquid crystal alignment film formed. It is preferable to contain%, It is more preferable to contain 30 to 70 weight%, It is preferable to contain 40 to 60 weight% especially.

The silane compound used when synthesizing the polyorganosiloxane (A) in the present invention contains from 20 to 80% by weight of the silane compound (2) based on the total silane compounds from the viewpoint of improving the reliability by appropriate degree of crosslinking. It is more preferable to contain 30 to 70 weight%, and it is especially preferable to contain 40 to 60 weight%.

As a ratio of the silane compound (3) in the silane compound used when synthesize | combining the polyorganosiloxane (A) in this invention, it is preferable that it is 30 weight% or less with respect to all the silane compounds, and it is more preferable that it is 10 weight% or less. Do. As for the silane compound used when synthesize | combining the polyorganosiloxane (A) in this invention, it is most preferable not to contain a silane compound (3).

The polyorganosiloxane (A) in this invention can be synthesize | combined by using the above-mentioned silane compound as a raw material, and hydrolyzing and condensing it in presence of water and a catalyst preferably in a suitable organic solvent.

As an organic solvent which can be arbitrarily used when synthesize | combining a polyorganosiloxane (A), an alcohol compound, a ketone compound, an amide compound or an ester compound, or other aprotic compound is mentioned, for example. These can be used individually or in combination of 2 or more types.

Examples of the alcohol compound include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol and 2-methylbutanol , sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n- Octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, mono alcohol 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-2,4, 2 Polyhydric alcohol compounds such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl 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 can also be used 1 type or in combination of 2 or more types.

As said ketone compound, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n- Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone, phenchon Mono ketone compounds such as these;

Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonane Dione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4 (Beta) -diketone compounds, such as -heptane dione, etc. are mentioned, respectively. These ketone compounds can also be used 1 type or in combination of 2 or more types.

As said amide compound, for example, formamide, N-methylformamide, 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 can also be used 1 type or in combination of 2 or more types.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate and i-acetic acid. Propyl, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, Benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetic acid, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene acetate Glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetate glycol, methoxytriglycol acetate, ethyl propionate N-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate and diethyl phthalate. Can be mentioned. These ester compounds can also be used 1 type or in combination of 2 or more types.

Examples of the other aprotic compounds include acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-pi Peridone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone Etc. can be mentioned.

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

As a ratio of the water used at the time of the synthesis | combination of a polyorganosiloxane (A), Preferably it is 0.5-100 mol with respect to 1 mol of the total amount of the alkoxyl group and halogen atoms which the silane compound which is a raw material has, More preferably, it is 1- It is more preferable that it is 30 mol and it is a ratio which becomes 1-1.5 mol.

As a catalyst which can be used at the time of synthesis | combination of a polyorganosiloxane (A), a metal chelate compound, an organic acid, an inorganic acid, an organic base, ammonia, an alkali metal compound, etc. are mentioned, for example.

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, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis (Acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di-n-butoxy bis (acetylacetonate) Titanium, di-sec-butoxy bis (acetylacetonate) titanium, di-t-butoxy bis (acetylacetonate) titanium, monoethoxy tris (acetylacetonate) titanium, mono-n-propoxy Tris (acetylacetonate) titanium, mono-i-propoxy tris (acetyl Setonate) titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, Tetrakis (acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium , Tri-n-butoxy mono (ethylacetoacetate) 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 (ethylacetoacetate) titanium, di-n-butoxy bis (ethylacetoacetate) Titanium, di-sec-butoxy bis (ethylacetoacetate T) titanium, di-t-butoxy bis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i- Propoxy tris (ethylacetoacetate) titanium, mono-n-butoxytris (ethylacetoacetate) titanium, mono-sec-butoxytris (ethylacetoacetate) titanium, mono-t-butoxytris ( Ethyl acetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono Titanium chelate compounds such as (ethylacetoacetate) titanium;

Triethoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri-i-propoxy mono (acetylacetonate) zirconium, tri-n-butoxy mono (Acetylacetonate) zirconium, tri-sec-butoxy mono (acetylacetonate) zirconium, tri-t-butoxy mono (acetylacetonate) zirconium, diethoxy bis (acetylacetonate) zirconium, di- n-propoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di-n-butoxy bis (acetylacetonate) zirconium, di-sec-butoxy Bis (acetylacetonate) zirconium, di-t-butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonate) zirconium, Mono-i-propoxy Tris (acetylacetonate) zirconium, mono-n-butoxytris (acetylacetonate) zirconium, mono-sec-butoxytris (acetylacetonate) zirconium, mono-t-butoxytris (acetylacetonate Zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (ethylaceto Acetate) zirconium, tri-n-butoxy mono (ethylacetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, tri-t-butoxy mono (ethylacetoacetate) zirconium, die Toxy bis (ethylacetoacetate) zirconium, di-n-propoxy bis (ethylacetoacetate) zirconium, di-i-propoxy bis (ethylacetoacetate) zirconium, di-n-part C. bis (ethylacetoacetate) zirconium, di-sec-butoxy bis (ethylacetoacetate) zirconium, di-t-butoxy bis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) Zirconium, mono-n-propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxytris (ethylacetoacetate) zirconium, mono-sec -Butoxy tris (ethylacetoacetate) zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, Zirconia such as bis (acetylacetonate) bis (ethylacetoacetate) zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium Zirconium chelate compounds;

And aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum.

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, and gallic acid. , Butyric acid, melit acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid And trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.

As said inorganic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, etc. are mentioned, for example.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine and monomethyl diethanol. Amine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicyclo undecene, tetramethylammonium hydroxide, etc. are mentioned.

As said alkali metal compound, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. are mentioned, for example.

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

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

The usage-amount of a catalyst becomes like this. Preferably it is 0.001-10 weight part with respect to a total of 100 weight part of the silane compound which is a raw material, More preferably, it is 0.001-1 weight part.

Water added during 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 the 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 the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.

As reaction temperature at the time of synthesis | combination of a polyorganosiloxane (A), Preferably it is 0-100 degreeC, More preferably, it is 15-80 degreeC. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) with respect to the polyorganosiloxane (A) is 500-1,000,000, It is more preferable that it is 1,000-100,000, It is 1,000-50,000 More preferred.

<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 said polyamic acid can be obtained by making tetracarboxylic dianhydride and diamine react, and the said polyimide can be obtained by dehydrating and closing this polyamic acid.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride which can be used for the synthesis | combination of a polymer (B), for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4 -Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3 , 5-tricarboxycyclopentylacetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahi Dro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4, 5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1, 3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-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 [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-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 [1,2-c] -furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5, 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetra Drofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3 , 5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5, Aliphatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides such as 8,10-tetraone, a compound represented by the following formulas (TI) and (T-II);

(In formula (TI) and (T-II), R <^1> and R <^3> is a divalent organic group which has an aromatic ring, respectively, R <^2> and R <^4> is a hydrogen atom or an alkyl group, respectively, and ^two or more R <^2> and R exists ⁴ may each be the same or different)

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Acid dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydrides, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride , p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (tri Phenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimelitate), propylene glycol-bis (anhydrotrimelitate), 1,4-butanediol-bis (anhydrotri Mellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimelitate), 2,2-bis (4-hydroxyphenyl) propane- Aromatic tetracarboxylic dianhydrides, such as a compound represented by bis (anhydro trimellitate) and the following general formula (T-1)-(T-4), are mentioned. The benzene ring of the aromatic tetracarboxylic dianhydride may be substituted with one or two or more alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms.

These tetracarboxylic dianhydrides can be used individually by 1 type or in combination of 2 or more types.

As tetracarboxylic dianhydride used for synthesize | combining the polymer (B) in this invention, butane tetracarboxylic dianhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride among the above-mentioned things. , 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclo Pentylacetic dianhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6- dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8 -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 [1,2-c] furan-1,3-dione, bicyclo [2.2 .2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicycle [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl ) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-anhydride, 4 , 9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic Acid dianhydrides, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8 -Among the compounds represented by the following formulas (T-5) to (T-7) and the compounds represented by the formula (T-II) among naphthalene tetracarboxylic dianhydrides and the compounds represented by the general formula (TI) It contains at least one selected from the group consisting of compounds represented by the following formula (T-8) (hereinafter referred to as "specific tetracarboxylic dianhydride") It is preferable from a viewpoint that it can express favorable liquid crystal alignability.

Specific tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5, 9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabi Cyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-fura Yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-anhydride, Group consisting of 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride and a compound represented by the above formula (T-1) At least 1 sort (s) chosen from is preferable.

The tetracarboxylic dianhydride used for synthesizing the polymer (B) used in the present invention contains at least 30 mol% of the specific tetracarboxylic dianhydride as described above with respect to the total tetracarboxylic dianhydride. It is preferable, it is more preferable to contain 40 mol% or more, and it is especially preferable to contain 45 mol% or more.

[Diamine]

As diamine which can be used for the synthesis | combination of a polymer (B), it is p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenylethane, for example, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl)- 1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenylether, 3,3'-diamino Benzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-ami Phenoxy) biphenyl, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene , 2,7-diaminofluorene, 9,9-dimethyl-2,7-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, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bis Aniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'-bis (trifluoro Methyl) biphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -Octafluorobiphenyl, a compound represented by each of the following formulas (D-1) to (D-5) Aromatic diamines such as;

(Y in Formula (D-4) is an integer of 2-12, z in Formula (D-5) is an integer of 1-5)

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, Isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, 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, 1,4-bis (aminomethyl) cyclohexane;

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5, 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-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-diaminoacridine, N, N'-bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3, 6-diamino Carbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethyl-benzidine, a compound represented by the following formula (DI), Diamine which has two primary amino groups and nitrogen atoms other than the said primary amino group in molecule | numerators, such as a compound represented by following General formula (D-II);

(In Formula (DI), R ⁵ is a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine, and X ¹ is a divalent organic group. , R ⁶ is an alkyl group having 1 to 4 carbon atoms, a1 is an integer of 0 to 3)

(In Formula (D-II), R ⁷ is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine, and X ² is each divalent. An organic group, and a plurality of X ^{2 's} may be the same or different, and each R ⁸ is an alkyl group having 1 to 4 carbon atoms, and a2 each represents an integer of 0 to 4).

Mono-substituted phenylenediamines such as compounds represented by the following general formula (D-III);

(In formula (D-III), R <^9> is -O-, -COO- *, -OCO- *, -NHCO- *, -CONH- * (However, in the above, the bond which attached "*" is R.) ¹⁰ ) or -CO-, and R ¹⁰ is a monovalent organic group having 6 to 30 carbon atoms or a skeleton having a skeleton or group selected from a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group and a fluorophenyl group. R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a3 is an integer of 0 to 3)

Diamino organosiloxane, such as a compound represented by the following general formula (D-IV), etc. are mentioned. The benzene ring of the aromatic diamine may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).

(In formula (D-IV), R <^12> is a C1-C12 hydrocarbon group, respectively, two or more R <^12> may be same or different, p is an integer of 1-3, respectively, q is 1- Is an integer of 20)

These diamines can be used individually or in combination of 2 or more types.

Examples of the diamine used to synthesize the polymer (B) in the present invention include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2, 7-diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene , 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediiso Propylidene) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) Biphenyl, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, formulas (D-1) to (D-5) Compounds represented by each, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N -Methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -Benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, among the compounds represented by the formula (DI), the compound represented by the following formula (D-6), the formula (D Among the compounds represented by the following formula (D-7) among the compounds represented by -II), among the compounds represented by the above formula (D-III), dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2, 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5- Diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminoben And 1,3-bis (3-aminopropyl) -tetramethyldisiloxane among the compounds represented by the following formulas (D-8) to (D-15) and the compounds represented by the formula (D-IV) It is preferable from the viewpoint of electrical properties to include at least one selected from the group (hereinafter referred to as "specific diamine").

It is preferable that the diamine used in order to synthesize | combine the polymer (B) used by this invention contains 30 mol% or more of said specific diamine with respect to all the diamine, It is more preferable to contain 40 mol% or more, It is preferable to contain 45 mol% or more especially.

[Synthesis of Polyamic Acid]

The use ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is preferably a ratio in which the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group of the diamine. Preferably it is the ratio used as 0.3 to 1.2 equivalent.

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

As an organic solvent which can be used at the time of synthesis | combination of a polyamic acid, an aprotic polar solvent, a phenol and its derivatives, alcohol, a ketone, ester, an ether, a halogenated hydrocarbon, a hydrocarbon, etc. are mentioned, for example. Examples of the aprotic polar solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone and tetramethylurea. , Hexamethylphosphortriamide and the like;

As said phenol derivative, m-cresol, xylenol, a halogenated phenol, etc. are mentioned, for example. Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and the like;

As said ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .;

As said ester, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate is mentioned, for example. Examples of the ether include 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, and ethylene glycol ethyl ether. Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc. ;

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

As said hydrocarbon, hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, etc. are mentioned, for example.

Among these organic solvents, at least one selected from the group consisting of aprotic polar solvents and phenols and derivatives thereof (first group of organic solvents), or at least one type selected from the first group of organic solvents, and alcohols Preference is given to using at least one mixture selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, and more preferably 40% by weight or less, based on the total of the organic solvent of the first group and the organic solvent of the second group. It is more preferable that it is 30 weight% or less.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, may be used for the production of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or after the isolated polyamic acid is purified to prepare a liquid crystal aligning agent. Can also be used for In the case where the polyamic acid is dehydrated and closed to form a polyimide, the reaction solution may be used as it is for the dehydration ring closing reaction, or after isolating the polyamic acid contained in the reaction solution and then used for the dehydration ring closing reaction, or the isolated polyamic acid. It can also be used for the dehydration ring closure reaction after purification.

Isolation of a polyamic acid can be performed by pouring the said reaction solution in a large amount of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure, or distilling off the organic solvent in a reaction solution by evaporation under reduced pressure. Further, this polyamic acid is dissolved in an organic solvent again, and then precipitated with a poor solvent, or a solution in which polyamic acid is dissolved in an organic solvent again, and the solution is washed and then distilled off under reduced pressure with an evaporator once. Or polyamic acid can be refine | purified by the method of performing several times.

Synthesis of Polyimide

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

The polyimide in this invention may be the complete imide which dehydrated and closed all the amic acid structures which the polyamic acid which is a precursor has, and only a part of the amic acid structure is dehydrated and closed, and the amic acid structure and the imide ring structure coexist. The partial imide may be sufficient.

The imidation ratio of polyimide becomes like this. Preferably it is 30% or more, More preferably, it is 40 to 90%. This imidation ratio is a numerical value which showed the ratio which the number of the imide ring structure occupies with respect to the sum of the number of the amic acid structure of the said polyimide, and the number of imide ring structures as a percentage. At this time, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably heated by (i) a method of heating the polyamic acid, or (ii) the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added to the solution, if necessary. It is done by the method.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide obtained may fall. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.

On the other hand, as a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said polyamic acid of said (ii). Although the usage-amount of a dehydrating agent changes with a desired imidation ratio, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic-acid structure of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. The imidation ratio can be increased as the usage-amount of the above-mentioned dehydrating agent and dehydrating ring closure agent increases. As an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. 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 by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or may be used for manufacture of a liquid crystal aligning agent after refine | purifying the polyimide obtained. On the other hand, in the said method (ii), the reaction solution containing a polyimide is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, or may be used for the production of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution, or after the polyimide is isolated to be used for the preparation of the liquid crystal aligning agent. You may use it for the manufacture of a liquid crystal aligning agent after refine | purifying an isolated polyimide. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of a polyimide can be performed by performing the same operation as mentioned above as a method of isolation and purification of a polyamic acid.

[Terminal Modified Polymer]

The polymer (B) contained in the liquid crystal aligning agent of this invention may be terminal modified form in which molecular weight was adjusted. By using the polymer of the terminal modification type, the coating characteristic of a liquid crystal aligning agent, etc. can be further improved, without impairing the effect of this invention. Such a terminal-modified polymer can be performed by adding a molecular weight modifier to the polymerization reaction system when synthesizing the polyamic acid. As a molecular weight modifier, an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example.

As said acid anhydride, maleic anhydride, a phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc .;

Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n- Eicosylamine, etc .;

As said monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, respectively.

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 of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid.

[Solution viscosity]

It is preferable to have a solution viscosity of 20-800 mPa * s, and, as for the polymer (B) obtained as mentioned above to have a solution of 10 weight% of concentration, it is more preferable to have a solution viscosity of 30-500 mPa * s. .

The solution viscosity (mPa · s) of the polymer is a polymer solution having a concentration of 10% by weight using a good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using an E-type rotational viscometer.

<Use ratio of polyorganosiloxane (A) and a polymer (B)>

As a usage ratio of the polyorganosiloxane (A) and the polymer (B) in the liquid crystal aligning agent of this invention, the sum total of a polymer (it says the sum total of a polyorganosiloxane (A) and a polymer (B), and is the same below). It is preferable that it is 0.01-30 weight% as a ratio of (A) polyorganosiloxane with respect to, and it is more preferable that it is 0.1-15 weight%.

<Other additives>

Although the liquid crystal aligning film of this invention contains the above-mentioned polyorganosiloxane (A) and polymer (B) as an essential component, it may contain other components as needed, unless the effect of this invention is attenuated. Examples of such other components include compounds having one or more epoxy groups (hereinafter referred to as "epoxy compound (C)"), (D) functional silane compounds, and the like in the (C) molecule.

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, Neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl Not only ether, etc. can be mentioned, The compound which has a group represented by following formula (3) is mentioned.

As an epoxy compound (C) in this invention, the compound which has group represented by the said General formula (3) is preferable, As a specific example, N, N, N ', N'- tetraglycidyl-m-xylenediamine , 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N -Diglycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane, N, N- diglycidyl-cyclohexylamine, etc. are mentioned.

The compounding ratio of these epoxy compounds (C) becomes like this. Preferably it is 40 weight part or less with respect to a total of 100 weight part of polymers, More preferably, it is 0.1-30 weight part.

As said (D) functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyl Triethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N -Trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxy Silyl-3,6-diazanyl acetate, 9-trimethoxysilyl-3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, 9- Rimethoxysilyl-3,6-methyl diazanonanate, 9-triethoxysilyl-3,6-methyl diazanonanate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyl Triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2 -Glycidoxy ethyl trimethoxy silane, 2-glycidoxy ethyl triethoxy silane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxy silane, etc. are mentioned.

The compounding ratio of these (D) functional silane containing compounds becomes like this. Preferably it is 2 weight part or less with respect to a total of 100 weight part of polymers, More preferably, it is 0.02-0.2 weight part.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is comprised as a liquid composition in which a polyorganosiloxane (A) and a polymer (B) and the other additive arbitrarily mix | blended as needed are melt-containing in an organic solvent preferably.

As an organic solvent which can be used for the liquid crystal aligning agent of this invention, for example, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N -Dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-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 independently, or may mix and use 2 or more types.

Although solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is selected suitably in consideration of viscosity, volatility, etc., Preferably it is 1- It is the range of 10 weight%. That is, the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate as mentioned later, Preferably, the coating film used as a liquid crystal aligning film is formed by heating, However, when solid content concentration is less than 1 weight%, the film thickness of this coating film is too much. When it becomes small and a favorable liquid crystal aligning film is unable to be obtained, and solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes large too much and a favorable liquid crystal aligning film cannot be obtained, the viscosity of a liquid crystal aligning agent increases and application | coating characteristic falls. Will be.

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, the range of 1.5 to 4.5 weight% of solid content concentration is especially preferable by the spinner method. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10 degreeC-50 degreeC, More preferably, it is 20 degreeC-30 degreeC.

The liquid crystal aligning agent of this invention obtained as mentioned above can be preferably used, in order to form the liquid crystal aligning film of the liquid crystal display element of well-known structures, such as TN type, STN type, IPS type, VA type, and MVA. It can be used to manufacture a novel liquid crystal display device in which the problem of the panel is eliminated.

Hereinafter, in the formation method of the liquid crystal aligning film performed using the liquid crystal aligning agent of this invention, the manufacturing method of the liquid crystal display element provided with the said liquid crystal aligning film, and the manufacturing method of the novel liquid crystal display element performed using the liquid crystal aligning agent of this invention. This will be described in order.

<Formation Method of Liquid Crystal Alignment Film>

In order to form a liquid crystal aligning film, it can carry out by the process of the following (1) and (2), for example.

(1) First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and then a coating film is formed on a board | substrate by heating a coating surface. Here, the board | substrate used when applying the liquid crystal display element of this invention to a TN type, STN type or VA type liquid crystal display element, and when applying to an IPS type liquid crystal display element differs.

(1-1) When manufacturing a TN type, STN type, or VA type liquid crystal display element, two board | substrates with which the patterned transparent conductive film is provided are made into a pair, and the liquid crystal of this invention on each transparent conductive film formation surface. An aligning agent is apply | coated preferably by the offset printing method, the spin coating method, or the inkjet printing method, respectively, and then a coating film is formed by heating each application surface. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, poly (alicyclic olefin) and the like can be used. Examples of the transparent conductive film provided on one side of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). In order to obtain a patterned transparent conductive film, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, for example, using a mask having a desired pattern when forming a transparent conductive film The method can be performed. At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a pretreatment for applying a functional silane compound, a functional titanium compound, or the like to the surface on which the coating film should be formed on the substrate surface in advance. May be performed.

After apply | coating a liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of liquid drop prevention of the apply | coated aligning agent, etc. Preliminary baking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. The preliminary baking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, the solvent is completely removed, and a firing (post-baking) step is performed for the purpose of thermally imidizing the amic acid unit possessed by the polymer (B). This firing (post-baking) temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. 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 µm, more preferably 0.005 to 0.5 µm.

(1-2) On the other hand, when manufacturing an IPS type | mold liquid crystal display element, it looked at the electrically conductive film formation surface of the board | substrate with which the transparent conductive film patterned by the comb-tooth-shaped pattern is seen, and the one side of the opposing board | substrate with which the conductive film is not provided. The liquid crystal aligning agent of this invention is apply | coated preferably by the offset printing method, the spinner method, or the inkjet printing method, respectively, and then a coating film is formed by heating each application surface.

About the material of the board | substrate and a transparent conductive film used at this time, the patterning method of a transparent conductive film, the pretreatment of a board | substrate, and the heating method after apply | coating a liquid crystal aligning agent, it is the same as said (1-1).

The preferable film thickness of the coating film formed is the same as said (1-1).

(2) When the liquid crystal display element manufactured by the method of this invention is a VA type liquid crystal display element, the coating film formed as mentioned above can be used as a liquid crystal aligning film as it is, but the rubbing process mentioned later according to the objective was performed. You can also use it later.

On the other hand, when manufacturing liquid crystal display elements other than VA type, a rubbing process is given to the coating film formed as mentioned above, and it is set as a liquid crystal aligning film.

The rubbing treatment can be performed by rubbing in a predetermined direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton or the like on the coating film surface formed as described above. Thereby, the orientation ability of liquid crystal molecules is provided to a coating film, and it becomes a liquid crystal aligning film.

Moreover, about the liquid crystal aligning film formed as mentioned above, for example, in patent document 5 (Unexamined-Japanese-Patent No. 6-222366) and patent document 6 (Japanese Unexamined-Japanese-Patent No. 6-281937). A process of changing the pretilt angle of a portion of the liquid crystal alignment film by irradiating a portion of the liquid crystal alignment film as described, and Patent Document 7 (Japanese Patent Laid-Open No. 5-107544). A liquid crystal display device obtained by forming a resist film on a part of the surface of the same liquid crystal alignment film, then performing a rubbing treatment in a direction different from the previously performed rubbing treatment, and then removing the resist film, and allowing the liquid crystal alignment film to have different liquid crystal alignment capabilities for each region. It is possible to improve the field of view characteristics.

<The manufacturing method of the liquid crystal display element provided with the said liquid crystal aligning film>

The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as above-mentioned, and arrange | positioning a liquid crystal between two board | substrates which oppose. Here, when the rubbing process is performed with respect to a coating film, two board | substrates are mutually arrange | positioned so that the rubbing direction in each coating film may mutually become a predetermined angle, for example, orthogonal or antiparallel.

In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method. First, two substrates are disposed to face each other so as to face each liquid crystal alignment film, and the peripheral portions of the two substrates are bonded together using a sealant, and the cell partitioned by the substrate surface and the sealant. After the injection filling of the liquid crystal within the interval, the liquid crystal cell can be produced by sealing the injection hole.

The second method is a method called an ODF (One Drop Fill) method. An ultraviolet-ray curable sealing material is apply | coated to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, after dropping a liquid crystal on the liquid crystal aligning film surface, the other board | substrate is bonded so that a liquid crystal aligning film may oppose. Then, a liquid crystal cell can be manufactured by irradiating ultraviolet light to the whole surface of a board | substrate, and hardening a sealing agent.

Also by any method, it is preferable to remove the orientation of the liquid crystal at the time of liquid crystal injection by heating it to the temperature which the liquid crystal used with respect to the liquid crystal cell manufactured as mentioned above takes an isotropic phase, and then gradually cooling to room temperature.

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

Here, as a sealing agent, the epoxy resin etc. which contain the hardening agent and the aluminum oxide sphere as a spacer can be used, for example.

As said liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. can be used, for example, A nematic liquid crystal is preferable among these. In the case of a VA type liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable, and for example, a dicyano benzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, a cfamily clock liquid crystal, a biphenyl liquid crystal And phenylcyclohexane-based liquid crystals are used. 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, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a non A phenylcyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. are used. To these liquid crystals, For example, cholesteric liquid crystals, such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate; Chiral agent sold as brand names C-15 and CB-15 (made by Merck); Ferroelectric liquid crystals such as p-disiloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.

As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol, and between the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

<Method for Manufacturing New Liquid Crystal Display Element>

The manufacturing method of the novel liquid crystal display element performed using the liquid crystal aligning agent of this invention,

On the said conductive film of a pair of board | substrates which have a conductive film, the liquid crystal aligning agent of this invention as mentioned above is apply | coated, respectively, and a coating film is formed,

Forming a liquid crystal cell of a structure in which the coating films of the pair of substrates on which the coating films are formed face each other through a layer of liquid crystal molecules,

And a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates.

Here, as a board | substrate used, it is the same as the case of the liquid crystal display element provided with the liquid crystal aligning film formed from the above-mentioned liquid crystal aligning agent of this invention.

As the conductive film, it is preferable to use a transparent conductive film, and for example, an NESA film containing SnO ₂ , an ITO film containing In ₂ O ₃ -SnO ₂ , and the like can be used. It is preferable that this conductive film is a patterned conductive film divided into a plurality of regions, respectively. With such a conductive film configuration, when a voltage is applied between the conductive films (to be described later), by applying a different voltage for each region, the direction of the pretilt angle of the liquid crystal molecules can be changed for each region. It becomes possible to widen.

About the method of apply | coating a liquid crystal aligning agent on the said conductive film of such a board | substrate, and the film thickness of the coating film after prebaking, post-baking, and post-baking after application | coating, the liquid crystal display provided with the liquid crystal aligning film formed from the liquid crystal aligning agent of the said invention. Same as the case of the device.

The coating film formed in this way may be used for manufacture of the liquid crystal cell of a subsequent process as it is, or you may perform a rubbing process with respect to a coating film surface as needed before manufacture of a liquid crystal cell. This rubbing process can be performed similarly to the case of the liquid crystal display element provided with the liquid crystal aligning film formed from the liquid crystal aligning agent of the said invention.

 Subsequently, the coating films of the pair of substrates on which the coating films are formed face each other through a layer of liquid crystal molecules to form a liquid crystal cell having a configuration in which the coating films are arranged oppositely.

As the liquid crystal molecules used herein, nematic liquid crystals having negative dielectric anisotropy are preferable, and for example, dicyanobenzene-based liquid crystals, pyridazine-based liquid crystals, Schiff-based liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, and phenylcyclohexane System liquid crystal etc. can be used. It is preferable that the thickness of the layer of liquid crystal molecules shall be 1-5 micrometers.

The method of forming a liquid crystal cell using such a liquid crystal is the same as that of the liquid crystal display element provided with the liquid crystal aligning film formed from the liquid crystal aligning agent of the said 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 voltage applied here can be, for example, 5 to 50 V DC or alternating current.

As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used, for example. Ultraviolet rays in the preferred wavelength region can be obtained by means of using the light source together with a filter, a diffraction grating, or the like, for example.

The irradiation amount of light is preferably 1,000 J / m 2 or more and less than 100,000 J / m 2, more preferably 1,000 to 50,000 J / m 2. In the manufacture of a liquid crystal display device of PSA mode known in the prior art, it is necessary to irradiate light of about 100,000 J / m 2, but in the method of the present invention, the light irradiation amount is set to 50,000 J / m 2 or less, and further, 10,000 J / m 2 or less. Also, a desired liquid crystal display element can be obtained, which is effective for reducing the manufacturing cost of the liquid crystal display element, and can also prevent the decrease in the electrical properties due to the strong light irradiation and the decrease in the long-term reliability.

Moreover, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after performing the process as mentioned above. As a polarizing plate used here, the polarizing plate which sandwiched the H film | membrane between cellulose acetate protective films, or the polarizing plate which consists of H films themselves is mentioned.

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

[Example]

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples. Below, the weight average molecular weight of polyorganosiloxane, the imidation ratio of polyimide, and the solution viscosity of a polymer were evaluated by the following method, respectively.

[Weight Average Molecular Weight]

The weight average molecular weight of the polyorganosiloxane was calculated | required as polystyrene conversion value using monodisperse polystyrene as a standard substance from the result measured by the gel permeation chromatography on the following conditions using the following apparatus.

Measuring device: manufactured by Tosoh Corporation, model "8120-GPC"

Column: Toso Corporation, "TSKgelGRCXLII"

Solvent: Tetrahydrofuran

Sample concentration: 5% by weight

Sample injection volume: 100 μL

Column temperature: 40 ℃

Column pressure: 68 kgf / ㎠

[Imidation Rate of Polyimide]

The polyimide was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, and obtained by the following equation (1) from ¹ H-NMR measured at room temperature using tetramethylsilane as a reference substance.

[Equation 1]

Imidation ratio (%) = (1-A ¹ / A ² × α) × 100

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

[Solution viscosity]

The solution viscosity (mPa * s) of a polymer was measured at 25 degreeC using the E-type rotational viscometer with respect to the solution of 10 weight% of polymer concentration using the solvent described in each synthesis example.

<Synthesis of Polyorganosiloxane (A)>

Synthesis Example A-1

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

Synthesis Examples A-2 to A-7

Polyorganosiloxanes (A-2) to (A) in the same manner as in Synthesis Example A-1, except that the type and amount of the silane compound used as the raw material in Synthesis Example A-1 was as described in Table 1, respectively. A-7) was synthesized respectively.

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

<Comparative Synthesis Example of Polyorganosiloxane>

Comparative Synthesis Examples a-1 and a-2

Polyorganosiloxanes (a-1) and (a) in the same manner as in Synthesis Example A-1 except that the type and amount of the silane compound used as the raw material in Synthesis Example A-1 was as described in Table 1, respectively. -2) were synthesized respectively.

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

The abbreviation of the silane compound in Table 1 has the following meanings, respectively.

MPTMS: 3-methacryloxypropyltrimethoxysilane

APTMS: 3-acryloxypropyltrimethoxysilane

MTMS: Methyltrimethoxysilane

PTMS: Phenyltrimethoxysilane

MTES: Methyltriethoxysilane

ETMS: ethyltrimethoxysilane

TMS: tetramethoxysilane

DMPDMS: bis (3-methacryloxypropyl) dimethoxysilane

<Synthesis example of polymer (B)>

Synthesis of Polyimide

Synthesis Example B-1

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 43 g (0.40 mol) of p-phenylenediamine and 3 (3,5-diaminobenzoyl) as diamine 52 g (0.10 mol) of oxy) cholestane was dissolved in 830 g of N-methyl-2-pyrrolidone (NMP), and reacted at 60 ° C. for 6 hours to obtain a solution containing polyamic acid. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of NMP, and the solution of 10 weight% of polyamic-acid concentration was 60 mPa * s.

Subsequently, 1,900 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was substituted with fresh NMP (pyridine and acetic anhydride used for the dehydration ring closure reaction were removed to the outside of the system by this operation) to thereby remove polyimide (B-1) having an imidization ratio of about 50%. About 1,200g of solutions containing 15 weight% were obtained.

The solution viscosity measured as a small amount of this polyimide solution, the addition of NMP, and the solution of 10 weight% of polyimide concentrations was 47 mPa * s.

[Synthesis of Polyamic Acid]

Synthesis Example B-2

1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) as tetracarboxylic dianhydride and 110 g (0.50 mol) pyromellitic dianhydride, 4,4'-dia as diamine 200 g (1.0 mole) of minodiphenylmethane was dissolved in 2,330 g of N-methyl-2-pyrrolidone, and reacted at 40 ° C. for 3 hours, and then 1,350 g of N-methyl-2-pyrrolidone was added. By this, about 3,800 g of solutions containing 10 weight% of polyamic acid (B-2) were obtained.

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

Example 1

<Production of Liquid Crystal Alignment Agent>

A solution containing the polyimide (B-1) obtained in Synthesis Example B-1 as a polymer (B) in terms of polyimide (B-1) was taken in an amount equivalent to 70 parts by weight, and this was polyorgano. 30 parts by weight of the polyorganosiloxane (A-1) obtained in Synthesis Example A-1 as siloxane (A) and (C) N, N, N ', N'-tetraglycidyl-m-xylene as an epoxy compound 10 parts by weight of diamine was added, and additionally N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added so that the solvent composition was NMP: BC = 55: 45 (weight ratio) and solid content 4 weight. It was set as the solution which is%. The liquid crystal aligning agent was manufactured by filtering this solution using the filter of 1 micrometer of pore diameters.

Various evaluation was performed as follows using this liquid crystal aligning agent. The evaluation results are shown in Table 1.

<Evaluation of liquid crystal aligning agent>

[Evaluation of Preservation Stability]

The liquid crystal aligning agent was apply | coated on the glass substrate by the spin-coating method by variable amount, and it baked preliminarily at 80 degreeC for 5 minutes, and then formed a coating film by post-baking at 200 degreeC for 60 minutes, and the coating film after solvent removal The rotation speed of the film thickness of 1,000 kPa was investigated.

Subsequently, a part of the said liquid crystal aligning agent was taken and this was preserve | saved at -15 degreeC for 5 weeks. The liquid crystal aligning agent after storage was observed visually, and when precipitation of an insoluble matter was observed, it was determined as storage stability "extreme defect".

If insoluble matters are not observed after 5 weeks of storage, the liquid crystal aligning agent after storage is applied onto the glass substrate by spin coating at a rotational speed of 1,000 kPa with a film thickness before storage, and prebaking under the same conditions as described above. And post-baking was performed, the coating film was formed and the film thickness was measured. When this film thickness has a 10% or more deviation from 1,000 kPa, it was determined as storage stability "poor", and when the film thickness deviation was less than 10%, it was determined as storage stability "good".

In addition, the measurement of the film thickness of the said coating film was performed using the needle contact type | mold difference thickness meter made by KLA-Tencor.

<Production and Evaluation of Vertically Oriented Liquid Crystal Display Elements>

[Production of Vertically Oriented Liquid Crystal Display Device]

The above-mentioned liquid crystal aligning agent was apply | coated using the spinner on the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO film, prebaked at 80 degreeC for 5 minutes, and then 1 hour at 200 degreeC in the oven substituted with nitrogen. After baking, a coating film (liquid crystal aligning film) having a thickness of 0.1 탆 was formed. This operation was repeated and a pair (two sheets) of board | substrates which have a liquid crystal aligning film were manufactured.

After screen-printing the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer on the outer peripheral part of the surface which has one liquid crystal aligning film among the said board | substrates, so that the rubbing direction may become anti-parallel to the liquid crystal aligning film surface of a pair of board | substrates. They were pressed to face each other, pressed, and heated at 150 ° C. for 1 hour to thermally cure the adhesive. Subsequently, the negative liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) was filled in the gap between the substrates from the liquid crystal injection hole, and then the liquid crystal injection hole was sealed with an epoxy adhesive, and this was removed at 150 ° C. in order to remove the flow orientation during liquid crystal injection. After heating for 10 minutes, it was cooled slowly to room temperature.

Moreover, the vertical alignment type liquid crystal display element was manufactured by bonding a polarizing plate to the outer both surfaces of a board | substrate so that the polarization direction may make an angle of 45 degrees with the rubbing direction of a liquid crystal aligning film, and so that the polarization directions of two polarizing plates may orthogonally cross.

[Evaluation of Vertically Oriented Liquid Crystal Display Element]

(1) Evaluation of liquid crystal alignment

The presence or absence of an abnormal domain in the change in contrast when the voltage of 5 V was turned ON and OFF (applied and released) was observed in the liquid crystal display device manufactured as described above. In the case of the vertically-aligned liquid crystal display element, no light leakage is observed when the voltage is OFF, and when the driving region is white display and there is no light leakage from the other region when the voltage is applied, the liquid crystal alignment property is "good." The case where leakage was observed was made into the liquid-crystal orientation "badness."

(2) Evaluation of voltage retention

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 then the voltage retention after 167 milliseconds from the release of the application was measured. As a measuring apparatus, "VHR-1" by Toyo Technica Co., Ltd. was used.

(3) evaluation of heat resistance

After standing for 10 hours in an oven at 80 ° C. in the liquid crystal display device manufactured in the same manner as above, the resultant was allowed to stand at room temperature and naturally cooled to room temperature. Subsequently, a voltage of 5 V was applied to this liquid crystal display element at an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention after 167 milliseconds from the release of the application was measured. As a measuring apparatus, "VHR-1" by Toyo Technica Co., Ltd. was used.

(4) evaluation of UV resistance

After irradiating the ultraviolet light of 10 J / cm <2> with the metal halide lamp of illumination intensity of 80 mW / cm <2> to the liquid crystal display element manufactured in the same manner to the above, it was left to stand at room temperature and naturally cooled to room temperature. Subsequently, after applying a voltage of 5 V in an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention after 167 milliseconds from the release of the application was measured. As a measuring apparatus, "VHR-1" by Toyo Technica Co., Ltd. was used.

(5) Evaluation of fire resistance

A voltage of 17 V DC was applied to the liquid crystal display device manufactured in the same manner as described above for 20 hours at an environment temperature of 100 ° C., and the voltage (residual DC voltage) remaining in the liquid crystal cell immediately after breaking the DC voltage was subjected to the flicker elimination method. Obtained by The case where the value of this residual DC voltage was 1,000 mV or less was made into the baking resistance "good", and the other case was made into the baking resistance "bad".

Examples 2-11 and Comparative Examples 1-4

A liquid crystal aligning agent was prepared in the same manner as in Example 1, except that the types and amounts of the polyorganosiloxane, polymer (B) and (C) epoxy compounds in Example 1 were as described in Table 2, respectively, Various evaluations were performed. The evaluation results are shown in Table 2.

In addition, in these Examples and the comparative examples, the polymer (B) was used for manufacture of the liquid crystal aligning agent as the polymer solution obtained by the said synthesis example. The quantity of the polymer (B) in Table 2 is the value converted into the quantity of the polymer contained in the used polymer solution. Moreover, in Example 10, the solvent was added so that a solvent composition might become NMP: BC: (gamma) -butyrolactone = 50: 40: 10 (weight ratio).

The abbreviation of the epoxy compound (C) in Table 2 has the following meanings, respectively.

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 (Japan Epoxy Resin Co., Ltd. make, brand name "Epicoat 157S65")

"-" In the component column of Table 2 shows that the component corresponded to the said column was not used.

As is clear 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 aligning film formed therefrom. A display element shows the outstanding liquid crystal aligning property and voltage retention, and is excellent also in heat resistance, ultraviolet-ray resistance, and baking resistance.

The liquid crystal display element of this invention provides the liquid crystal display element especially excellent in the baking part characteristic especially compared with the liquid crystal aligning agent which has the conventionally known polysiloxane as a main component.

<Production of Liquid Crystal Cells>

Example 12

Using the liquid crystal aligning agent manufactured in the said Example 1, the pattern (two types) and ultraviolet irradiation amount (three levels) of the transparent electrode were changed as follows, and six liquid crystal display elements in total were manufactured and evaluated.

[Production of Liquid Crystal Cell with Transparent Electrode Without Pattern]

The liquid crystal aligning agent manufactured in the said Example 1 was apply | coated on the transparent electrode surface of the glass substrate which has a transparent electrode containing an ITO film using a liquid crystal aligning film printing machine (made by Nippon Shashin Insatsu Co., Ltd.), and 80 degreeC hotplate The solvent was removed by heating (pre-baking) for 1 minute above, followed by heating (post-baking) for 10 minutes on a hot plate at 150 ° C to form a coating film having an average film thickness of 600 kPa.

About this coating film, the rubbing process was performed by the rubbing machine which has the roll which wound up the rayon spring at roll rotation speed 400rpm, stage movement speed of 3 cm / sec, and hairpin indentation length of 0.1 mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes to obtain a substrate having a rubbing treated coating film. This operation was repeated and a pair (two sheets) of the board | substrate which has a rubbing process coating film was obtained.

Subsequently, after the pair of substrates were coated with an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 µm on each outer edge of the coated film, which was subjected to a rubbing treatment, the coated film was overlapped to face each other and pressed to cure the adhesive. Subsequently, after filling a nematic liquid crystal (MLC-6608, Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection hole, the liquid crystal cell was manufactured by sealing a liquid crystal injection hole with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a transparent electrode without a pattern. One of them was used for evaluation of the pretilt angle mentioned later as it is. The remaining two liquid crystal cells were irradiated in a state where a voltage was applied between the conductive films by the following method, respectively, and then used for evaluation of the pretilt angle and voltage retention.

To two of the liquid crystal cells obtained above, an alternating current of 10 Hz at a frequency of 60 Hz was applied between the electrodes, respectively, and ultraviolet rays were 10,000 using an ultraviolet irradiation device using a metal halide lamp as the light source while the liquid crystal was being driven. Irradiation was carried out at a dose of J / m 2 or 100,000 J / m 2. In addition, this irradiation amount is the value measured using the photometer measured with the wavelength of 365 nm reference | standard.

[Evaluation of Pretilt Angle]

For each of the liquid crystal cells produced above, He- based on the method described in Non-Patent Document 2 (TJ Scheffer et. Al. J. Appl. Phys. Vol. 19, p. 2013 (1980)), respectively. 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 which was not irradiated with light was 89 °, and the pretilt angle of the liquid crystal cell with an irradiation amount of 10,000 J / m2 was 88 °, The pretilt angle of the liquid crystal cell of irradiation amount 100,000 J / m <2> was 84 degrees.

[Production of Liquid Crystal Cell with Patterned Transparent Electrode]

The liquid crystal aligning agent prepared in Example 1 was patterned in the slit shape as shown in FIG. 1, and the liquid crystal on each electrode surface of the glass substrates (A) and (B) which respectively has the ITO electrode divided into the some area | region. Apply using an alignment film printing machine (manufactured by Nippon Shashin Insatsu Co., Ltd.), remove the solvent by heating (pre-baking) on a hot plate at 80 ° C for 1 minute, and then heat the plate for 10 minutes on a hot plate at 150 ° C (post-baking). ) To form a coating film having an average film thickness of 600 kPa. The coating film was subjected to ultrasonic cleaning in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a coating film. This operation was repeated and the pair (2 sheets) of the board | substrate which has a coating film was obtained.

Subsequently, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 µm was applied to each of the outer edge portions having the coating films of the pair of substrates, and then overlapped and pressed so that the coating film surfaces faced, and the adhesive was cured. Subsequently, after filling a nematic liquid crystal (MLC-6608, Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection hole, the liquid crystal cell was manufactured by sealing a liquid crystal injection hole with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a patterned transparent electrode. One of them was used for evaluation of the response speed mentioned later as it is. With respect to the remaining two liquid crystal cells, at a irradiation amount of 10,000 J / m 2 or 100,000 J / m 2 with a voltage applied between the conductive films by the same method as in the manufacture of the liquid crystal cell having the transparent electrode without the above pattern. It was used for evaluation of response speed after light irradiation.

In addition, the pattern of the electrode used here is a pattern similar to the electrode pattern in PSA mode.

[Evaluation of response speed]

About each liquid crystal cell produced above, the brightness of the light which permeate | transmitted the liquid crystal cell by irradiating a visible light lamp first without applying a voltage was measured with the photomultimeter, and this value was made into 0% of the relative transmittance. Next, the transmittance | permeability when AC 60V was applied for 5 second between the electrodes of a liquid crystal cell was measured similarly to the above, and this value was made into 100% of the relative transmittance | permeability.

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

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

Examples 13 and 14

As the liquid crystal aligning agent, various liquid crystals were carried out in the same manner as in Example 12 except that the liquid crystal aligning agent prepared in Example 13 was used in Example 13, and the liquid crystal aligning agent prepared in Example 3 was used in Example 14, respectively. Cells were prepared and evaluated.

The evaluation results are shown in Table 3.

From the result of Table 3, in the manufacturing method of the novel liquid crystal display element in this invention, when the ultraviolet irradiation amount is set to 100,000 J / m <2> (the value used conventionally in PSA mode), the degree of the pretilt angle obtained will become excess, and 10,000 It turned out that it becomes an appropriate pretilt angle at the irradiation amount of J / m <2> or less. Moreover, even when the irradiation amount was small, a sufficiently fast response speed was obtained. Moreover, from the result of Table 2, it turned out that the liquid crystal aligning agent of this invention has the very outstanding ultraviolet resistance.

Therefore, according to the manufacturing method of the liquid crystal display element of this invention, since the advantage of PSA mode can be realized even with a small amount of light irradiation, the generation of display nonuniformity resulting from a high light irradiation amount, the fall of voltage holding | maintenance characteristic, and long-term reliability lack of A liquid crystal display device having a wide viewing angle, a fast response speed of liquid crystal molecules, a high transmittance, and a high contrast can be manufactured without concern.

Claims (9)

(A) a polyorganosiloxane obtained by hydrolyzing and condensing a silane compound comprising a compound represented by the following formula (1), and
(B) at least one polymer selected from the group consisting of polyamic acid and polyimide
It contains, The liquid crystal aligning agent characterized by the above-mentioned.
<Formula 1>

(In Formula 1, R ^I is a monovalent organic group having a (meth) acryloyl group, and R ^II is a monovalent organic group.) The liquid crystal aligning agent of Claim 1 whose ratio of (A) polyorganosiloxane with respect to the sum total of said (A) polyorganosiloxane and (B) polymer is 0.01-30 weight%. The liquid crystal aligning agent according to claim 1 or 2, wherein the silane compound further includes a compound represented by the following Formula 2 in addition to the compound represented by the Formula 1.
<Formula 2>

(In Formula 2, R ^III is a straight chain 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 liquid crystal alignment 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 wt% of the compound represented by the formula (1). My. The liquid crystal aligning agent of Claim 1 or 2 which further contains the compound which has 1 or more epoxy groups in a molecule | numerator. The liquid crystal aligning agent of Claim 5 whose said (C) compound is a compound which has group represented by following formula (3).
<Formula 3>

It formed with the liquid crystal aligning agent of Claim 1 or 2, The liquid crystal aligning film characterized by the above-mentioned. The liquid crystal aligning film of Claim 7 is provided, The liquid crystal display element characterized by the above-mentioned. On the said conductive film of a pair of board | substrates which have a conductive film, the liquid crystal aligning agent of Claim 1 or 2 is apply | coated, respectively, and a coating film is formed,
Forming a liquid crystal cell of a structure in which the coating films of the pair of substrates on which the coating films are formed face each other through a layer of liquid crystal molecules,
And a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates.

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