JP2010217866A - Liquid crystal aligning agent, liquid crystal display device, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film having an excellent vertical aligning property and long-term stability, suppressed in the lowering of a voltage retention rate when exposed to heat or light for a long time, and excellent afterimage characteristics. <P>SOLUTION: The liquid crystal aligning agent contains: (A) a polyorganosiloxane obtained through hydrolysis and the condensation of a silane compound containing a compound expressed by a formula (1):R<SP>I</SP>Si(OR<SP>II</SP>)<SP>3</SP>wherein R<SP>I</SP>represents a monovalent organic group having a (meth)acryloyl group and R<SP>II</SP>represents a monovalent organic group; and (B) at least one kind of a polymeric compound selected from a group composed of a polyamic acid and a polyimide. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal display element, and a manufacturing method thereof.

Currently, as a liquid crystal display element, a liquid crystal alignment film is formed on the surface of a substrate on which a transparent conductive film is provided to form a substrate for a liquid crystal display element. A so-called TN type (twisted) in which a layer of a nematic liquid crystal having a property is formed into a sandwich cell, and the major axis of liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other. A TN liquid crystal display element having a (Nematic) liquid crystal cell is known. In addition, an STN (Super Twisted Nematic) type liquid crystal display element that can realize a high contrast ratio as compared with a TN type liquid crystal display element, an IPS (In-Plane Switching) type liquid crystal display element that has less viewing angle dependency, and a negative dielectric constant. A VA (Vertical Alignment) type liquid crystal display element using nematic liquid crystal having anisotropy has been developed.
The operating principles of these various liquid crystal display elements are broadly divided into transmission types and reflection types. The transmissive liquid crystal display element performs display by using a change in intensity of transmitted light of a backlight light source from the back of the element when the element is driven. On the other hand, the reflective liquid crystal display element does not use a light source for backlight, and displays the light by using the intensity change of reflected light from the outside such as sunlight when the element is driven. It is considered particularly advantageous for outdoor use because of its low power consumption.
In the transmissive liquid crystal display element, the liquid crystal alignment film provided in the transmissive liquid crystal display element is exposed to light from a backlight light source for a long time. In particular, in liquid crystal projector applications where demand for home theaters has been increasing in recent years in addition to business applications, light sources with extremely high irradiation intensity such as metal halide lamps are used. Further, it is conceivable that the temperature of the liquid crystal display element itself rises during driving due to strong light irradiation. In the case of a reflective liquid crystal display element, there is a high possibility that it will be used outdoors. In this case, sunlight including intense ultraviolet light becomes the light source. In the reflection type, the distance that light passes through the element is longer than the transmission type in principle. Furthermore, both the transmissive liquid crystal display element and the reflective liquid crystal display element tend to be widely used, for example, in a private car, and the temperature of the liquid crystal display element is higher than that conventionally considered as a usage aspect of the liquid crystal display element The usage and installation environment has become a reality.

By the way, in the manufacturing process of a liquid crystal display element, a liquid crystal dropping method, that is, an ODF (One Drop Fill) method, has started to be used from the viewpoint of process shortening and yield improvement. Unlike the conventional method in which liquid crystal is injected into an empty liquid crystal cell that has been assembled in advance using a thermosetting sealant, the ODF method is UV curable at a required location on one side substrate coated with a liquid crystal alignment film. After applying the sealing agent, the liquid crystal is dropped onto a necessary portion and the other substrate is bonded, and then the entire surface is irradiated with ultraviolet light to cure the sealing agent to produce a liquid crystal cell. The ultraviolet light irradiated at this time is usually as strong as several joules per square centimeter. That is, in the liquid crystal display element manufacturing process, the liquid crystal alignment film is exposed to this intense ultraviolet light together with the liquid crystal.
As described above, in the liquid crystal display element, due to its high functionality, versatility, improvement of the manufacturing process, etc., severe light intensity, high-temperature environment, long-time driving, etc. that could not have been considered in the past In such an environment, liquid crystal orientation, electrical characteristics such as voltage holding ratio, or display characteristics that are superior to conventional ones are required. Long life has been demanded.

Conventionally, organic resins such as polyimide, polyamic acid, polyamide, and polyester are known as materials for the liquid crystal alignment film constituting the liquid crystal display element. In particular, polyimide has been used in many liquid crystal display elements because it exhibits excellent physical properties such as heat resistance, affinity with liquid crystal, and mechanical strength among organic resins (Patent Documents 1 to 3). However, in recent liquid crystal display elements, new demands associated with the harsh manufacturing environment and use environment as described above have become stronger, and heat resistance and light resistance to the extent that an organic resin that has been allowed in the past can still be achieved. It became insufficient.
Thus, studies have been made on liquid crystal alignment films having excellent heat resistance and light resistance. For example, Patent Document 4 discloses a vertical alignment type liquid crystal alignment film formed from a polysiloxane solution obtained from a silicon compound having four alkoxyl groups and a silicon compound having three alkoxyl groups. It is described that it has excellent vertical alignment properties, heat resistance and uniformity, and also has excellent stability as a coating solution. However, the liquid crystal alignment film according to the technique of Patent Document 4 does not satisfy the required performance associated with the harsh production environment and use environment, and the storage stability of the coating liquid is insufficient. There is a problem in the convenience of using it.
A liquid crystal aligning agent that can provide a liquid crystal alignment film having sufficient heat resistance and light resistance in extremely severe current production environment and use environment, and excellent in storage stability has not been known yet.

By the way, in order to increase the viewing angle in the VA type liquid crystal panel, there is known an MVA (Multi-Domain Vertical Alignment) type panel in which protrusions are formed in the liquid crystal panel, thereby restricting the tilting direction of the liquid crystal molecules. Yes. However, according to this method, the lack of transmittance and contrast due to the protrusions is unavoidable, and there is a problem that the response speed of the liquid crystal molecules is slow.
Recently, a PSA (Polymer Sustained Alignment) mode has been proposed in order to solve such problems of the MVA type panel. The PSA mode is a polymerizable compound in a gap between a pair of substrates composed of a substrate with a patterned conductive film and a substrate with a conductive film having no pattern, or between a pair of substrates composed of two substrates with a patterned conductive film. An attempt is made to control the alignment direction of the liquid crystal by expressing a pretilt angle characteristic by irradiating ultraviolet rays in a state where a voltage is applied between the conductive films while sandwiching the liquid crystal composition containing the liquid crystal and polymerizing the polymerizable compound. Technology. According to this technology, it is possible to increase the viewing angle and speed up the liquid crystal molecule response by making the conductive film into a specific configuration, and also solve the problem of lack of transmittance and contrast that was inevitable in the MVA type panel. Is done. However, in order to polymerize the polymerizable compound, it is necessary to irradiate a large amount of ultraviolet light, for example, 100,000 J / m ^2. It becomes clear that the reactive compounds remain in the liquid crystal layer, which together cause display unevenness, adversely affect the voltage holding characteristics, or cause problems in the long-term reliability of the panel. Has not reached.
On the other hand, Non-Patent Document 1 proposes a method using a liquid crystal alignment film formed from a polyimide liquid crystal aligning agent containing a reactive mesogen. According to Non-Patent Document 1, a liquid crystal display element including a liquid crystal alignment film formed by such a method is said to respond quickly to liquid crystal molecules. However, Non-Patent Document 1 does not give any guidance on what kind of reactive mesogen should be used, and the amount of necessary ultraviolet irradiation is still large, and there are concerns about display characteristics, particularly voltage holding characteristics. Not wiped out.

JP-A-9-197411 JP 2003-149648 A JP 2003-107486 A JP-A-9-281502 JP-A-6-222366 JP-A-6-281937 JP-A-5-107544

Y. -J. Lee et. al. , SID 09 DIGEST, p666 (2009) T.A. J. et al. Scheffer et. al. J. et al. Appl. Phys. vol. 19, p2013 (1980)

The present invention has been made in view of the circumstances as described above, and its purpose is excellent in vertical alignment and long-term stability and little decrease in voltage holding ratio when exposed to heat and light for a long time. Another object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film having excellent afterimage characteristics.
Still another object of the present invention is to provide a liquid crystal display element that does not deteriorate the display quality even when exposed to heat and light for a long time, and a method for manufacturing the same.
Still other objects and advantages of the present invention will become apparent from the following description.

In accordance with the present invention, the above objects and advantages of the present invention are primarily as follows:
(A) The following formula (1)
R ^I Si (OR ^II ) ₃ (1)
(In Formula (1), R ^I is a monovalent organic group having a (meth) acryloyl group, and R ^II is a monovalent organic group.)
A polyorganosiloxane obtained by hydrolyzing and condensing a silane compound containing a compound represented by formula (B), and (B) a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid and polyimide Achieved.
The above liquid crystal aligning agent 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 a novel liquid crystal display in which the problems of the MVA panel are solved. It can be used to manufacture the device.
Therefore, the above objects and advantages of the present invention are secondly,
Achieved by a liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal alignment agent,
On the conductive film of a pair of substrates having a conductive film, respectively, the liquid crystal aligning agent is applied to form a coating film,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to each other through a layer of liquid crystal molecules,
This is achieved by a method for manufacturing a liquid crystal display element, which includes a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between conductive films of the pair of substrates.

The liquid crystal aligning agent of the present invention can form a liquid crystal aligning film that is excellent in vertical alignment property and long-term stability, has little decrease in voltage holding ratio when exposed to heat and light for a long time, and has excellent afterimage characteristics. Therefore, the liquid crystal display element comprising the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention can be effectively applied to various devices.
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, a high response speed of liquid crystal molecules, good electrical characteristics, and sufficient transmittance and contrast. The display characteristics are excellent and display characteristics are not impaired even when driven continuously for a long time, and the amount of light necessary for irradiation of the liquid crystal display element can be reduced, which contributes to a reduction in manufacturing cost.
The liquid crystal display element can be suitably used for various devices such as a desk calculator, a wristwatch, a clock, a counting display board, a word processor, a personal computer, and a liquid crystal television.

It is 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.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of the present invention is a polyorganosiloxane (hereinafter referred to as “polyorganosiloxane (A)”) obtained by hydrolyzing and condensing a silane compound containing at least (A) the compound represented by the above formula (1). ), And (B) at least one polymer selected from the group consisting of polyamic acid and polyimide (hereinafter referred to as “polymer (B)”).
Containing.
<Polyorganosiloxane (A)>
The polyorganosiloxane (A) in the present invention is a polyorganosiloxane obtained by hydrolyzing and condensing a silane compound containing a compound represented by the above formula (1) (hereinafter referred to as “silane compound (1)”). It is.
As R ^I in the above formula (1), for example, the following formula (R ^I -1)

(In the 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, and d is 0 or 1 and e is an integer from 0 to 3, provided that c, d and e are not 0 at the same time, and when b and d are both 0 and c is not 0, e is 0 is there.)
The group etc. which are represented by these can be mentioned.
Specific examples of such R ^I include, for example, (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-((meta ) Acryloxy) nonyl group, 10-((meth) acryloxy) decyl group, 4- (2-((meth) acryloxy) ethyl) phenyl group, 2-((4- (meth) acryloxy) 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) ethyl group, 2- (2- (2-((meth) acryloxy) ethoxy) ethoxy) ethyl group, 3- (3-((meth) acryloxy) propoxy) propyl group and the like can be mentioned.
As R ^I in the above formula (1), in the above formula (R ^I -1), R is a hydrogen atom or a methyl group, a is an integer of 1 to 10, c is 1, b, d And a group in which each of e is 0 is preferable, more preferably a (meth) acryloxymethyl group, a 2-((meth) acryloxy) ethyl group, a 3-((meth) acryloxy) propyl group, a 4-((meth) An acryloxy) butyl group, a 5-((meth) acryloxy) pentyl group or a 6-((meth) acryloxy) hexyl group, particularly preferably a 3-((meth) acryloxy) propyl group.

R ^II in the above formula (1) is, for example, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylsulfonyl group having an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Examples include alkylsulfonyl groups having an alkyl group,
Specific examples of these include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl and nonyl. A group, a decyl group, an undecyl group, a dodecyl group, etc .;
Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-methoxyphenyl group, and 3,5-dimethoxyphenyl. A group, 2,4,6-trimethoxyphenyl group and the like;
Examples of the arylsulfonyl group having an aryl group having 6 to 12 carbon atoms include a p-toluenesulfonyl group;
Examples of the alkylsulfonyl group having an alkyl group having 1 to 4 carbon atoms include a methylsulfonyl group.
R ^II in the above 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, A methyl group, an ethyl group or a t-butyl group is preferred, and a methyl group is particularly preferred.
Specific examples of the silane compound (1) include (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethyltri-n-propoxysilane, and (meth) acrylic. Loxymethyltri-i-propoxysilane, (meth) acryloxymethyltri-n-butoxysilane, (meth) acryloxymethylpropyltri-sec-butoxysilane,
2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 2- (meth) acryloxyethyltri-n-propoxysilane, 2- (meth) acryloxyethyltri-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) acryloxypropyltri-i -Propoxysilane, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane,
4- (meth) acryloxybutyltrimethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, 4- (meth) acryloxybutyltri-n-propoxysilane, 4- (meth) acryloxybutyltri-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) acryloxypentyltri-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) acryloxyhexyltri-i -Propoxysilane, 6- (meth) acryloxyhexyltri-n-butoxysilane, 6- (meth) acryloxyhexylpropyltri-sec-butoxysilane and the like can be mentioned.

In synthesizing the polyorganosiloxane (A) in the present invention, only the silane compound (1) may be hydrolyzed and condensed, or a mixture of the silane compound (1) and a silane compound other than the silane compound (1). May be hydrolyzed and condensed.
Examples of silane compounds other than the silane compound (1) that can be used here include the following formula (2):
R ^III Si (OR ^IV ) ₃ (2)
(In the formula (1), R ^III is a linear alkyl group having 1 to 18 carbon atoms, a linear fluoroalkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 24 carbon atoms, and R ^IV is 1 Valent organic group.)
(Hereinafter referred to as “silane compound (2)”) and other silane compounds (hereinafter referred to as “silane compound (3)”).
Examples of the linear alkyl group having 1 to 18 carbon atoms of R ^III in the above formula (2) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, Examples include n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-octadecyl group and the like. The linear alkyl group having 1 to 18 carbon atoms of R ^III is preferably a linear alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
Examples of the straight-chain fluoroalkyl group having 1 to 18 carbon atoms of R ^III include trifluoromethyl group, 2- (trifluoromethyl) ethyl group, 3- (trifluoromethyl) propyl group, perfluoro-n-hexyl. Group, perfluoro-n-octyl group, 2- (perfluoro-n-octyl) ethyl group, perfluoro-n-dodecyl group, perfluoro-n-octadecyl group and the like. The straight-chain fluoroalkyl group having 1 to 18 carbon atoms of R ^III is preferably a straight-chain fluoroalkyl group having 1 to 6 carbon atoms, such as a trifluoromethyl group, 2- (trifluoromethyl) ethyl group, 3- A (trifluoromethyl) propyl group or a perfluoro-n-hexyl group is more preferable, and a trifluoromethyl group is particularly preferable.
Examples of the aryl group having 6 to 24 carbon atoms of R ^III include a phenyl group, 4-methylphenyl group, 2-methylphenyl group, 3-methylphenyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-n-hexylphenyl group, 4-n-octylphenyl group, 4-n-dodecylphenyl group, 4-n-octadecylphenyl group, and the like. Among these, A phenyl group, a 4-methylphenyl group, a 3-methylphenyl group or a 2-methylphenyl group is preferable, and a phenyl group is particularly preferable.

The monovalent organic group R ^IV, for example, an alkylsulfonyl group having an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, carbon atoms It may be an arylsulfonyl group having 6 to 8 aryl groups.
Examples of the alkyl group having 1 to 12 carbon atoms of the R ^IV, for example a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl Group etc .;
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a methoxyphenyl group, a dimethoxyphenyl group, and a trimethoxyphenyl group;
Examples of the alkylsulfonyl group having an alkyl group having 1 to 6 carbon atoms include a methylsulfonyl group, an ethylsulfonyl group, an n-hexylsulfonyl group, and the like;
Examples of the arylsulfonyl group having an aryl group having 6 to 8 carbon atoms include a p-toluenesulfonyl group and a 3,5-dimethylphenylsulfonyl group. Among these, R ^IV in the above formula (2) is preferably an alkyl group having 1 to 6 carbon atoms.

Specific examples of the silane compound (2) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxy. Silane, methyltri-n-pentoxysilane, methyltri-sec-butoxysilane, methyltriphenoxysilane, methyltri-p-methylphenoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-i-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-n-pentoxysilane, 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-pentoxysilane, n-propyltri-sec-butoxysilane, n-propyltriphenoxysilane, n-propyltri-p-methylphenoxysilane,
n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-i-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxy Silane, n-butyltri-n-pentoxysilane, n-butyltri-sec-butoxysilane, n-butyltriphenoxysilane, n-butyltri-p-methylphenoxysilane,
n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-pentyltri-n-propoxysilane, n-pentyltri-i-propoxysilane, n-pentyltri-n-butoxysilane, n-pentyltri-sec-butoxy Silane, n-pentyltri-n-pentoxysilane, n-pentyltri-sec-butoxysilane, n-pentyltriphenoxysilane, n-pentyltri-p-methylphenoxysilane,
2- (trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxy Silane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-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, -(Perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluorosilane) Fluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-butoxysilane, 2- ( Perfluoro-n-octyl) ethyltri-sec-butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri -Sec-butoxysilane Rukoto can.

  The silane compound (3) is a silane compound other than the silane compound (1) and the silane compound (2), and specific examples thereof include trichlorosilane, trimethoxysilane, triethoxysilane, tri-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- (per Fluoro- -Octyl) ethyltrichlorosilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane Hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri- n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropylto -Sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n- Butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxy Silane, phenyltrichlorosilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propyl Lopoxysilane, 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-n- Octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i -Propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (Methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercapto Propyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di-n -Butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl ) (Vinyl) di-n-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, Divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n- Lopoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxy Silane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane , (Ethoxy) (methyl) diphenylsilane, bis (3- (meth) acryloxypropyl) dimethoxysilane, bis (3- (meth) acryloxypropyl) diethoxylane, bis (3- (meth) acryloxypropyl) di- i-propoxysilane, bis (3- (meth) acryloxypropyl) di-n-butoxysilane, bis (3- (meth) acryloxypropyl) di-sec-butoxysilane, bis (3- (meth) acryloxy Propyl) diphenoxysilane, tris (3- (meth) acryloxyp Pyr) 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) acryloxypropyl) -i-butoxysilane, tris (3- (meth) acryloxypropyl) 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-hexyldiethoxysilane, 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-propoxysilane, 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-butoxysilane, di-sec-butyl-di-sec-butoxysilane, di-n-pentyl-di-sec-butoxysilane, di-hexyl-di-sec-butoxysilane, trimethylmethoxysilane, triethylmethoxysilane, 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-propoxysilane, tri-i-propyl-n-propoxysilane, tri-n-butyl-n-propoxysilane, tri-sec-butyl-n-propoxysilane, tri-n-hexyl-n-propoxysilane, Tri-n-dodecyl-n-propyl Lopoxysilane, trimethyl-i-propoxysilane, triethyl-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-butyl And the like can be given Kishishiran.
Among these silane compounds (3), tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Triethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane is preferred.

The silane compound used in synthesizing the polyorganosiloxane (A) in the present invention is obtained by changing the silane compound (1) to all silane compounds from the viewpoint of further improving the electrical characteristics of the liquid crystal alignment film to be formed. The content is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and particularly preferably 40 to 60% by weight.
The silane compound used in synthesizing the polyorganosiloxane (A) in the present invention is the silane compound (2) in an amount of 20 to 80 wt. %, More preferably 30 to 70% by weight, and particularly preferably 40 to 60% by weight.
The ratio of the silane compound (3) in the silane compound used for synthesizing the polyorganosiloxane (A) in the present invention is preferably 30% by weight or less, and preferably 10% by weight or less based on the total silane compounds. It is more preferable that Most preferably, the silane compound used in synthesizing the polyorganosiloxane (A) in the present invention does not contain the silane compound (3).
The polyorganosiloxane (A) in the present invention is synthesized by hydrolyzing and condensing the silane compound as described above as a raw material, preferably in an appropriate organic solvent in the presence of water and a catalyst. Can do.
Examples of the organic solvent that can be optionally used when synthesizing the polyorganosiloxane (A) include alcohol compounds, ketone compounds, amide compounds, ester compounds, and other aprotic compounds. These may be used alone or in combination of two or more.

Examples of the alcohol compound include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol , Phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, monoalcohol compounds such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol compounds such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, the partial ethers of polyhydric alcohol compound and dipropylene glycol monopropyl ether, can be mentioned, respectively. These alcohol compounds may be used alone or in combination of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-. Monoketone compounds such as hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fencheon;
Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5 -Methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, etc. The β-diketone compound and the like can be mentioned respectively. These ketone compounds may be used alone or in combination of two or more.
Examples of the amide compound include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-ethyl. Acetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide compounds may be used alone or in combination of two or more.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, acetic acid. i-butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, acetic acid n-nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, vinegar Acid diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples thereof include amyl, diethyl malonate, dimethyl phthalate, and diethyl phthalate. These ester compounds may be used alone or in combination of two or more.
Examples of the other aprotic compounds include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N— Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N -Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone and the like can be mentioned.
Of these solvents, polyhydric alcohol compounds, partial ethers or ester compounds of polyhydric alcohol compounds are particularly preferred.

The proportion of water used in the synthesis of the polyorganosiloxane (A) is preferably 0.5 to 100 mol with respect to 1 mol of the total amount of alkoxyl groups and halogen atoms of the silane compound as a raw material, and more The amount is preferably 1 to 30 mol, and more preferably 1 to 1.5 mol.
Examples of the catalyst that can be used in the synthesis of the polyorganosiloxane (A) include metal chelate compounds, organic acids, inorganic acids, organic bases, ammonia, and alkali metal compounds.
Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Natto) titanium, di-t-butoxy Su (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n -Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri -S c-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis ( Ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy・ Tris (ethyl aceto Acetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Titanium chelate compounds such as acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirc Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetate) Acetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis ( Ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di- sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n- Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) Zirconium, mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium;
Examples thereof include aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum.

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, and gallic acid. Acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.
Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclo. Nonane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.
These catalysts may be used alone or in combination of two or more.
Of these catalysts, metal chelate compounds, organic acids or inorganic acids are preferred, and titanium chelate compounds or organic acids are more preferred.
The amount of the catalyst used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the total silane compound as a raw material.

Water added in the synthesis of the polyorganosiloxane (A) can be added intermittently or continuously in the raw material silane compound or in a solution obtained by dissolving the silane compound in an organic solvent.
The catalyst may be added in advance to a raw material silane compound or a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.
The reaction temperature during the synthesis of the polyorganosiloxane (A) is preferably 0 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.
For the polyorganosiloxane (A), the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 500 to 1,000,000, and preferably 1,000 to 100,000. Is more preferable, and it is more preferable that it is 1,000-50,000.

<Polymer (B)>
The polymer (B) in the liquid crystal aligning agent of the present invention is at least one polymer selected from the group consisting of polyamic acid and polyimide.
The polyamic acid can be obtained by reacting tetracarboxylic dianhydride and diamine, and the polyimide can be obtained by dehydrating and ring-closing the polyamic acid.
[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride that can be used for the synthesis of the polymer (B) include 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-cyclopentanetetra Carboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxy Pentylacetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-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] -o To-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [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-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone The following formulas (TI) and (T-II)

(In the formulas (T-I) and (T-II), R ¹ and R ³ are each a divalent organic group having an aromatic ring, and R ² and R ⁴ are each a hydrogen atom or an alkyl group. And a plurality of R ² and R ⁴ may be the same or different.)
An aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride such as a compound represented by each of the following:
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicar Boxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 , 2 ′, 3,3′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis ( Triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis ( Anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate) Retate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis ( Anhydrotrimellitate), the following formulas (T-1) to (T-4)

An aromatic tetracarboxylic dianhydride such as a compound represented by each of the above can be exemplified. The benzene ring of the aromatic tetracarboxylic dianhydride may be substituted with one or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).
These tetracarboxylic dianhydrides can be used singly or in combination of two or more.
As tetracarboxylic dianhydride used for synthesizing the polymer (B) in the present invention, among the above, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic 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-oxabicyclo [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-dianhydride, 4,9-dioxatricyclo [ .3.1.0 ^2,6] undecane -3,5,8,10- tetraone, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, Of the compounds represented by the above formula (TI), the following formulas (T-5) to (T-7)

And the following formula (T-8) among the compounds represented by formula (T-II):

It is preferable from the viewpoint that it can exhibit good liquid crystal alignment properties including at least one selected from the group consisting of the compounds represented by (hereinafter referred to as “specific tetracarboxylic dianhydride”). .
Specific tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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-oxabicyclo [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, 5,6 tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3, At least one selected from the group consisting of 5,8,10-tetraone, pyromellitic dianhydride and the compound represented by the above formula (T-1) is preferable.
The tetracarboxylic dianhydride used for synthesizing the polymer (B) used in the present invention is a specific tetracarboxylic dianhydride as described above with respect to the total tetracarboxylic dianhydride. It is preferable to contain at least mol%, more preferably at least 40 mol%, particularly preferably at least 45 mol%.

[Diamine]
Examples of the diamine that can be used for the synthesis of the polymer (B) include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 4,4′-diamino. Diphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 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′-amino) Phenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3, '-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-aminophenoxy) 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) Luolene, 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) Bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-3,3′-bis (trifluoromethyl) biphenyl, 4 , 4′-Diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobi Eniru, the following formula (D-1) ~ (D-5)

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5.)
An aromatic diamine such as a compound represented by each of
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, Tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenediethylenediamine, 4,4'-methylenebis (cyclohexylamine) ), 1,3-bis (aminomethyl) cyclohexane, aliphatic diamines such as 1,4-bis (aminomethyl) cyclohexane and alicyclic diamines;
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-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 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-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethyl-benzidine, Formula (DI)

(In the 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, and a1 is an integer of 0 to 3.)
A compound represented by formula (D-II):

(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 a divalent organic group, respectively. A plurality of X ² may be the same or different, each R ⁸ is an alkyl group having 1 to 4 carbon atoms, and a2 is an integer of 0 to 4 respectively. is there.)
A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in the molecule of the compound represented by:
The following formula (D-III)

(In the formula (D-III), R ⁹ represents —O—, —COO— ^* , —OCO— ^* , —NHCO— ^* , —CONH— ^* (in the above, the bond indicated by “*” is R ¹⁰ is bonded to R ¹⁰ ) or —CO—, and R ¹⁰ is a monovalent organic group or carbon having a skeleton or group selected from a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group An alkyl group having 6 to 30 carbon atoms, R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a3 is an integer of 0 to 3.)
Monosubstituted phenylenediamines such as compounds represented by:
The following formula (D-IV)

(In the formula (D-IV), each R ¹² is a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ¹² may be the same or different, and p is each 1 is an integer of 1 to 3, and q is an integer of 1 to 20.)
And diaminoorganosiloxanes such as compounds represented by the formula: 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).
These diamines can be used alone or in combination of two or more.
Among the above, the diamine used for synthesizing the polymer (B) in the present invention includes p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, and 1,5-diamino. Naphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene N) 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, compounds represented by the above formulas (D-1) to (D-5), 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, the following formula (D-6) among the compounds represented by the above formula (DI)

Of the compounds represented by formula (D-II), the following formula (D-7)

Of the compounds represented by formula (D-III), dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy- 2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, the following formula (D-8) ~ (D-15)

And at least one selected from the group consisting of 1,3-bis (3-aminopropyl) -tetramethyldisiloxane among the compounds represented by the formula (D-IV) Hereinafter, it is preferable from the viewpoint of electrical characteristics.
The diamine used for synthesizing the polymer (B) used in the present invention preferably contains 30 mol% or more, and 40 mol% or more of the specific diamine as described above with respect to the total diamine. More preferably, it is particularly preferable to contain 45 mol% or more.

[Synthesis of polyamic acid]
The ratio of the tetracarboxylic dianhydride and the diamine used for the polyamic acid synthesis reaction is 0.2 to 0.2 acid anhydride groups of the tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of the diamine. A ratio of 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 ° C. to 150 ° C., more preferably 0 to 100 ° C., and preferably 0.1 to 24 hours, more preferably 0.00. It takes 5 to 12 hours.
Examples of the organic solvent that can be used in the synthesis of the polyamic acid include an aprotic polar solvent, phenol and derivatives thereof, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, and the like. Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide and the like. ;
Examples of the phenol derivative include m-cresol, xylenol, and halogenated phenol. 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;
Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;

Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, and diethyl malonate. Examples of the ether include 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, 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 and the like;
Examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;
Examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoamylisobutyrate, and diisopentyl ether.
Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and phenol and derivatives thereof (first group organic solvent), or one selected from the first group of organic solvents It is preferable to use a mixture of the above and one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (second group organic solvent). In the latter case, the use ratio of the second group of organic solvents is preferably 50% by weight or less, more preferably 40% by weight or less, with respect to the total of the first group of organic solvents and the second group of organic solvents. Furthermore, it is preferable that it is 30 weight% or less.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized to form polyimide, the reaction solution may be subjected to dehydration and cyclization reaction as it is, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction.
Polyamic acid is isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate and drying the precipitate under reduced pressure, or by distilling off the organic solvent in the reaction solution under reduced pressure using an evaporator. Can be performed. In addition, a method of dissolving this polyamic acid in an organic solvent again and then precipitating with a poor solvent, or a step in which a polyamic acid is again dissolved in an organic solvent, and the solution is washed and then distilled off under reduced pressure with an evaporator. The polyamic acid can be purified by a method performed once or several times.

[Synthesis of polyimide]
The polyimide can be obtained by dehydrating and ring-closing the polyamic acid obtained as described above to imidize.
The polyimide in the present invention may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure that the polyamic acid that is the precursor had, and only a part of the amic acid structure is dehydrated and cyclized. And a partially imidized product in which an imide ring structure coexists.
The imidation ratio of polyimide is preferably 30% or more, more preferably 40 to 90%. This imidation ratio is a numerical value representing the ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of the polyimide 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 performed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring closure catalyst to this solution as necessary. This is done by heating.
The reaction temperature in the method (i) of heating the polyamic acid is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.
On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. Although the usage-amount of a dehydrating agent is based on the desired imidation rate, 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. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. The imidation rate can be increased as the amount of the above dehydrating agent and dehydrating ring-closing agent increases. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

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

[Terminal-modified polymer]
The polymer (B) contained in the liquid crystal aligning agent of the present invention may be a terminal modified type having a controlled molecular weight. By using a terminal-modified polymer, the coating properties of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be obtained by adding a molecular weight modifier to a polymerization reaction system when synthesizing a polyamic acid. Examples of the molecular weight regulator include acid monoanhydride, monoamine compound, monoisocyanate compound and the like.
Examples of the acid monoanhydride include maleic anhydride, 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 and the like;
Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid. .
[Solution viscosity]
The polymer (B) obtained as described above preferably has a solution viscosity of 20 to 800 mPa · s, and a solution viscosity of 30 to 500 mPa · s, when a solution having a concentration of 10% by weight is obtained. It is more preferable that it has.
The solution viscosity (mPa · s) of the above polymer is E for a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using a mold rotational viscometer.
<Use ratio of polyorganosiloxane (A) and polymer (B)>
The ratio of the polyorganosiloxane (A) and the polymer (B) used in the liquid crystal aligning agent of the present invention is the total of the polymers (the total of the polyorganosiloxane (A) and the polymer (B). The same applies hereinafter. The ratio of (A) polyorganosiloxane to.) Is preferably 0.01 to 30% by weight, and more preferably 0.1 to 15% by weight.

<Other additives>
The liquid crystal alignment film of the present invention contains the polyorganosiloxane (A) and the polymer (B) as essential components as described above, but contains other components as necessary unless the effects of the present invention are diminished. It may be. Examples of such other components include (C) a compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound (C)”), (D) a functional silane compound, and the like.
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. In addition to diol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, and the following formula (3)

The compound which has group represented by these can be mentioned.
The epoxy compound (C) in the present invention is preferably a compound having a group represented by the above formula (3), and specific examples thereof include, for 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 and the like can be mentioned.
The blending ratio of these epoxy compounds (C) is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the polymer.

Examples of the (D) functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3 -Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- , 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonyl acetate , 9-triethoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazananoate, methyl 9-triethoxysilyl-3,6-diazananoate, N-benzyl-3- Aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, Glycidoxymethyltriethoxysilane, 2-glycidoxyethylate Silane, 2-glycidoxyethyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, and the like.
The blending ratio of these (D) functional silane-containing compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the total amount of the polymer.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is a liquid in which the polyorganosiloxane (A) and the polymer (B) and other additives optionally blended as necessary are preferably dissolved in an organic solvent. Configured as a composition.
Examples of the organic solvent that can be used in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4. -Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, 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, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. Can be mentioned. These can be used alone or in combination of two or more.

The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably, when heated, a coating film that becomes a liquid crystal aligning film is formed, but the solid content concentration is less than 1 wt%. In this case, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive. Thus, a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating properties.
The particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when the spinner method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. 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 thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10 to 50 degreeC, More preferably, it is 20 to 30 degreeC.

The liquid crystal aligning agent of the present invention obtained as described above can be suitably used for forming a liquid crystal aligning film of a liquid crystal display element having a known structure such as TN type, STN type, IPS type, VA type or the like. In addition, it can be used to manufacture a novel liquid crystal display element in which the problems of the MVA panel are solved.
Hereinafter, a method for forming a liquid crystal alignment film performed using the liquid crystal alignment agent of the present invention, a method for manufacturing a liquid crystal display element including the liquid crystal alignment film, and a novel liquid crystal display element performed using the liquid crystal alignment agent of the present invention A manufacturing method is demonstrated in order.
<Method for forming liquid crystal alignment film>
The liquid crystal alignment film can be formed, for example, by the following steps (1) and (2).
(1) First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, Then, a coating film is formed on a board | substrate by heating an application surface. Here, the substrate to be used differs depending on whether the liquid crystal display element of the present invention is applied to a TN type, STN type, or VA type liquid crystal display element, and the case of application to an IPS type liquid crystal display element.

(1-1) When manufacturing a TN type, STN type, or VA type liquid crystal display element, a pair of two substrates provided with a patterned transparent conductive film is used as a pair on each transparent conductive film formation surface. The liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spin coating method or an ink jet printing method, respectively, and then each coated surface is heated to form a coating film. Here, as the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. In order to obtain a patterned transparent conductive film which can be used, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a mask having a desired pattern when forming a transparent conductive film It is possible to use a method using In applying 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 functional silane compound or functional titanium is formed on the surface of the substrate surface on which the coating film is to be formed. You may give the pretreatment which apply | coats a compound etc. previously.
After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied aligning agent. The pre-bake temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented in order to remove a solvent completely and to thermally imidize the amic acid unit which a polymer (B) has as needed. The firing (post-bake) temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C, and the post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Thus, the film thickness of the formed film 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 liquid crystal display element, the conductive film formation surface of the substrate provided with the comb-shaped transparent conductive film and the counter substrate provided with no conductive film On one surface, the liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spinner method, or an ink jet printing method, and then each coated surface is heated to form a coating film.
The material used for the substrate and the transparent conductive film, the patterning method for the transparent conductive film, the pretreatment of the substrate, and the heating method after applying the liquid crystal aligning agent are the same as in (1-1) above.
The preferable film thickness of the coating film to be formed is the same as (1-1) above.

(2) When the liquid crystal display element manufactured by the method of the present invention is a VA type liquid crystal display element, the coating film formed as described above can be used as it is as a liquid crystal alignment film. If desired, it may be used after the following rubbing treatment.
On the other hand, when manufacturing a liquid crystal display element other than the VA type, a rubbing treatment is performed on the coating film formed as described above to obtain a liquid crystal alignment film.
The rubbing treatment can be performed by rubbing the coating film surface formed as described above with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton in a certain direction. Thereby, the orientation ability of liquid crystal molecules is imparted to the coating film to form a liquid crystal orientation film.
Further, for the liquid crystal alignment film formed as described above, for example, a liquid crystal as disclosed in Patent Document 5 (JP-A-6-222366) and Patent Document 6 (JP-A-6-281937). Treatment for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the alignment film with ultraviolet rays, or liquid crystal alignment as disclosed in Patent Document 7 (Japanese Patent Laid-Open No. 5-107544) Form a resist film on a part of the film surface, and then perform a rubbing process in a direction different from the previous rubbing process, and then remove the resist film so that the liquid crystal alignment film has different liquid crystal alignment capabilities in each region. It is possible to improve the visual field characteristics of the liquid crystal display element obtained by the above.

<Method for Producing Liquid Crystal Display Device Comprising the Liquid Crystal Alignment Film>
A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates opposed to each other. Here, when the rubbing process is performed on the coating film, the two substrates are disposed to face each other so that the rubbing directions in the respective coating films are at 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 arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.
Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase, and then gradually cooled to room temperature, so that the flow alignment during liquid crystal injection is achieved. It is desirable to remove.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
As the liquid crystal, for example, nematic liquid crystal, smectic liquid crystal, or the like can be used, and among these, nematic liquid crystal is preferable. In the case of a VA liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, and phenylcyclohexane liquid crystal are used. It is done. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic type liquid crystal having positive dielectric anisotropy is preferable. For example, biphenyl type liquid crystal, phenyl cyclohexane type liquid crystal, ester type liquid crystal, terphenyl type liquid crystal, biphenyl cyclohexane type A liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like is used. Examples of these liquid crystals include cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names C-15 and CB-15 (Merck); p-decyloxybenzylidene Ferroelectric liquid crystals such as -p-amino-2-methylbutyl cinnamate may be further added and used.
As a polarizing plate bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between protective films of cellulose acetate The polarizing plate which consists of itself can be mentioned.

<Method for manufacturing novel liquid crystal display element>
A method for producing a novel liquid crystal display element performed using the liquid crystal aligning agent of the present invention,
A coating film is formed by applying the liquid crystal aligning agent of the present invention as described above on the conductive film of the pair of substrates having the conductive film,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to each other through a layer of liquid crystal molecules,
A step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates is characterized.
Here, the substrate used is the same as that of the liquid crystal display device including the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention as described above.
As the conductive film, a transparent conductive film is preferably used. For example, a NESA film made of SnO ₂ or an ITO film made of In ₂ O ₃ —SnO ₂ can be used. Each of the conductive films is preferably a patterned conductive film partitioned into a plurality of regions. With such a conductive film configuration, when a voltage is applied between the conductive films (described later), the direction of the pretilt angle of the liquid crystal molecules can be changed for each region by applying a different voltage for each region. This makes it possible to further widen the viewing angle characteristics.
Regarding the method of applying a liquid crystal aligning agent on the conductive film of the substrate, pre-baking and post-baking after coating, and the film thickness of the coating film after post-baking, the liquid crystal aligning film formed from the liquid crystal aligning agent of the present invention described above It is the same as that of the case of the liquid crystal display element which comprises.
The coating film thus formed may be used as it is for the production of a liquid crystal cell in the next step, or may be subjected to a rubbing treatment on the coating surface as necessary prior to the production of the liquid crystal cell. This rubbing treatment can be carried out in the same manner as in the case of a liquid crystal display device comprising a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention.

Next, a liquid crystal cell having a configuration in which the coating film of the pair of substrates on which the coating film is formed is disposed to face each other through a layer of liquid crystal molecules is formed.
The liquid crystal molecules used here are preferably nematic liquid crystals having negative dielectric anisotropy, such as dicyanobenzene liquid crystals, pyridazine liquid crystals, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals. Etc. can be used. The thickness of the liquid crystal molecule layer is preferably 1 to 5 μm.
A method for forming a liquid crystal cell using such a liquid crystal is the same as in the case of a liquid crystal display element having a liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention.
Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.
The voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
As light to irradiate, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light having a wavelength of 300 to 400 nm is preferable. As a light source of irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter, a diffraction grating or the like.
The amount of light irradiation 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 conventionally known PSA mode liquid crystal display element, it was necessary to irradiate light of about 100,000 J / m ^{2. In} the method of the present invention, the amount of light irradiation was set to 50,000 J / M ² or less, and even if it is 10,000 J / m ² or less, a desired liquid crystal display element can be obtained, which contributes to a reduction in manufacturing cost of the liquid crystal display element and is caused by irradiation with strong light. It is possible to avoid deterioration of electrical characteristics and long-term reliability.
And 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 above-mentioned treatment. Examples of the polarizing plate used here include a polarizing plate in which an H film is sandwiched between cellulose acetate protective films, or a polarizing plate made of the H film itself.
The liquid crystal display device manufactured as described above has a wide viewing angle, an extremely fast response speed of liquid crystal molecules, excellent both in display characteristics and long-term reliability, and at a low cost with reduced manufacturing costs. Therefore, it can be suitably applied to various uses.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, the weight average molecular weight of the polyorganosiloxane, the imidization ratio of the polyimide, and the solution viscosity of the polymer were evaluated by the following methods, respectively.
[Weight average molecular weight]
The weight average molecular weight of the polyorganosiloxane was determined as a polystyrene conversion value using monodisperse polystyrene as a standard substance from the results of measurement by gel permeation chromatography under the following conditions using the following apparatus.
Measuring device: Model “8120-GPC” manufactured by Tosoh Corporation
Column: “TSKgelGRCXLII” manufactured by Tosoh Corporation
Solvent: Tetrahydrofuran Sample concentration: 5% by weight
Sample injection volume: 100 μL
Column temperature: 40 ° C
Column pressure: 68 kgf / cm ²
[Imidation rate of polyimide]
The polyimide was sufficiently dried at room temperature under reduced pressure, then dissolved in deuterated dimethyl sulfoxide, and determined from ¹ H-NMR measured at room temperature using tetramethylsilane as a reference substance, and the following formula (1) was obtained.
Imidation rate (%) = (1-A ¹ / A ² × α) × 100 (1)
(In Formula (1), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a polyimide precursor (polyamic acid). The number ratio of other protons to one proton of NH group in
[Solution viscosity]
The solution viscosity (mPa · s) of the polymer was measured at 25 ° C. using an E-type viscometer for a solution having a polymer concentration of 10% by weight using the solvent indicated in each synthesis example.

<Synthesis of polyorganosiloxane (A)>
Synthesis Example A-1
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 50.0 g of 3-methacryloxypropyltrimethoxysilane, 45.0 g of methyltrimethoxysilane, 5.0 g of phenyltrimethoxysilane, methyl isobutyl ketone 500 g and 10.0 g of triethylamine were charged and mixed at room temperature. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the reaction was carried out for 6 hours while mixing under reflux at 80 ° C. After completion of the reaction, the organic layer was taken out, washed with 0.2 wt% ammonium nitrate aqueous solution until the aqueous layer after washing became neutral, and then the solvent and water were distilled off under reduced pressure to remove 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
In Synthetic Example A-1, polyorganosiloxane (A-2) to polyorganosiloxane (A-2) were prepared in the same manner as in Synthetic Example A-1, except that the types and amounts of silane compounds used as raw materials were as shown in Table 1. (A-7) was synthesized respectively.
The yields and weight average molecular weights 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
In the synthesis example A-1, the polyorganosiloxane (a-1) and the polyorganosiloxane (a-1) (A-2) was synthesized respectively.
The yield and weight average molecular weight of these polyorganosiloxanes (a-1) and (a-2) are shown in Table 1, respectively.

Abbreviations of silane compounds in Table 1 have the following meanings.
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 acid dianhydride as tetracarboxylic dianhydride and 43 g (0.40 mol) of p-phenylenediamine and 3 (3,5-diaminobenzoyl) as diamine Oxy) cholestane 52 g (0.10 mol) was dissolved in N-methyl-2-pyrrolidone (NMP) 830 g and reacted at 60 ° C. for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 60 mPa · s.
Next, 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 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new NMP (by removing pyridine and acetic anhydride used in the dehydration cyclization reaction from the system), and the imidation rate was about 50%. About 1,200 g of a solution containing 15% by weight of polyimide (B-1) was obtained.
A small amount of this polyimide solution was taken, and NMP was added thereto to measure the solution viscosity as a solution having a polyimide concentration of 10% by weight, which was 47 mPa · s.
[Synthesis of polyamic acid]
Synthesis Example B-2
1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) and pyromellitic dianhydride 110 g (0.50 mol) as tetracarboxylic dianhydride and 4,4 ′ as diamine -Dissolve 200 g (1.0 mol) of diaminodiphenylmethane in 2,330 g of N-methyl-2-pyrrolidone, react at 40 ° C. for 3 hours, and then add 1,350 g of N-methyl-2-pyrrolidone. As a result, about 3,800 g of a solution containing 10% by weight of polyamic acid (B-2) was obtained.
The solution viscosity of this polyamic acid solution was 135 mPa · s.

Example 1
<Preparation of liquid crystal aligning agent>
As a polymer (B), the solution containing the polyimide (B-1) obtained in Synthesis Example B-1 was converted to polyimide (B-1), and an amount corresponding to 70 parts by weight was taken. 30 parts by weight of polyorganosiloxane (A-1) obtained in Synthesis Example A-1 as siloxane (A) and (C) N, N, N ′, N′-tetraglycidyl-m-xylenediamine 10 as an epoxy compound Part by weight was added, and N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to obtain a solution having a solvent composition of NMP: BC = 55: 45 (weight ratio) and a solid content concentration of 4% by weight. . A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.
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 storage stability]
On the glass substrate, the above-mentioned liquid crystal aligning agent is applied by changing the number of rotations by spin coating, pre-baked at 80 ° C. for 5 minutes, and then post-baked at 200 ° C. for 60 minutes to form a coating film, and after solvent removal The number of rotations at which the film thickness of the film was 1,000 mm was examined.
Next, a part of the liquid crystal aligning agent was taken and stored at −15 ° C. for 5 weeks. The liquid crystal aligning agent after storage was visually observed, and when insoluble precipitates were observed, it was determined that the storage stability was “very poor”.
When insoluble matter was not observed after storage for 5 weeks, the liquid crystal aligning agent after storage was coated on the glass substrate by spin coating with a rotational speed of 1,000 mm before storage, and Pre-baking and post-baking were performed under the same conditions to form a coating film, and the film thickness was measured. When the film thickness deviated from 1,000 mm by 10% or more, the storage stability was judged as “bad”, and when the film thickness deviation was less than 10%, the storage stability was judged as “good”. .
In addition, the measurement of the film thickness of the said coating film was performed using the stylus-type level | step difference film thickness meter made from KLA-Tencor.

<Manufacture and evaluation of vertical alignment type liquid crystal display element>
[Manufacture of vertical alignment type liquid crystal display elements]
The liquid crystal aligning agent prepared above was applied onto the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner, prebaked at 80 ° C. for 5 minutes, and then 200 ° C. in an oven replaced with nitrogen. Was post-baked for 1 hour to form a coating film (liquid crystal alignment film) having a thickness of 0.1 μm. This operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film.
After applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing, the liquid crystal alignment film surfaces of the pair of substrates are rubbed. The adhesive was superposed and pressure-bonded so that the directions were antiparallel, and the adhesive was heat cured at 150 ° C. for 1 hour. Next, a negative liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) is filled in the gap between the liquid crystal inlet and the substrate, and then the liquid crystal inlet is sealed with an epoxy adhesive, and the flow alignment during liquid crystal injection is removed. Therefore, this was heated at 150 ° C. for 10 minutes and then gradually cooled to room temperature.
Further, by vertically bonding the polarizing plates on both sides of the substrate so that the polarization direction forms an angle of 45 ° with the rubbing direction of the liquid crystal alignment film and the polarization directions of the two polarizing plates are orthogonal to each other. Type liquid crystal display device was manufactured.

[Evaluation of vertical alignment liquid crystal display element]
(1) Evaluation of liquid crystal orientation The presence or absence of an abnormal domain in the change in brightness when a voltage of 5 V was turned ON / OFF (applied / released) was observed in the liquid crystal display element manufactured above. In the case of a vertical alignment type liquid crystal display element, light leakage is not observed when the voltage is turned off, and the drive region is displayed white when the voltage is applied, and the light is not leaked from the other regions. When leakage was observed, the liquid crystal orientation was “defective”.
(2) Evaluation of voltage holding ratio After the voltage of 5 V was applied to the liquid crystal display element manufactured above with a 60 microsecond application time and a span of 167 milliseconds, the voltage holding ratio after 167 milliseconds from the application release was obtained. It was measured. As a measuring device, “VHR-1” manufactured by Toyo Corporation was used.
(3) Evaluation of heat resistance The liquid crystal display device produced in the same manner as described above was allowed to stand in an oven at 80 ° C. for 10 hours, and then allowed to stand at room temperature and naturally cooled to room temperature. Next, a voltage of 5 V was applied to the liquid crystal display element with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from the application release was measured. As a measuring device, “VHR-1” manufactured by Toyo Corporation was used.
(4) Evaluation of UV resistance A liquid crystal display device manufactured in the same manner as described above was irradiated with 10 J / cm ² of ultraviolet light using a metal halide lamp with an illuminance of 80 mW / cm ² , and then left at room temperature to stand at room temperature. Naturally cooled until. Subsequently, a voltage of 5 V was applied for 60 microseconds with a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from the application release was measured. As a measuring device, “VHR-1” manufactured by Toyo Corporation was used.
(5) Evaluation of seizure resistance The voltage remaining in the liquid crystal cell immediately after the DC voltage was turned off by applying a voltage of DC 17V to the liquid crystal display element manufactured in the same manner as described above at an environmental temperature of 100 ° C. for 20 hours. (Residual DC voltage) was determined by the flicker-erasing method. When the value of the residual DC voltage was 1,000 mV or less, seizure resistance was “good”, and other cases were regarded as seizure resistance “bad”.

Examples 2-11 and Comparative Examples 1-4
In Example 1, the liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the types and amounts of polyorganosiloxane, polymers (B) and (C) epoxy compounds were as shown in Table 2. Prepared and evaluated in various ways. The evaluation results are shown in Table 2.
In these Examples and Comparative Examples, the polymer (B) was used for the preparation of the liquid crystal aligning agent as the polymer solution obtained in the above synthesis example. The amount of the polymer (B) in Table 2 is a value converted to the amount of the polymer contained in the used polymer solution. In Example 10, the solvent was added so that the solvent composition was NMP: BC: γ-butyrolactone = 50: 40: 10 (weight ratio).

Abbreviations of the epoxy compound (C) in Table 2 have 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 novolac type epoxy resin (product name “Epicoat 157S65” manufactured by Japan Epoxy Resin Co., Ltd.)
“-” In the component column of Table 2 indicates that the component corresponding to the 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) has excellent storage stability and a liquid crystal aligning film formed therefrom. The liquid crystal display element of the present invention has excellent liquid crystal orientation and voltage holding ratio, and is excellent in heat resistance, ultraviolet resistance and seizure resistance.
The liquid crystal display element of the present invention provides a liquid crystal display element that is particularly excellent in seizure resistance as compared with a conventionally known liquid crystal aligning agent mainly composed of polysiloxane.

<Manufacture of liquid crystal cells>
Example 12
Using the liquid crystal aligning agent prepared in Example 1 above, the transparent electrode pattern (two types) and the ultraviolet irradiation amount (three levels) were changed as follows to produce a total of six liquid crystal display elements, evaluated.
[Manufacture of liquid crystal cell having transparent electrode without pattern]
The liquid crystal aligning agent prepared in Example 1 was applied onto a transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.), and 80 ° C. After heating (pre-baking) on the hot plate for 1 minute to remove the solvent, it was heated (post-baking) on a hot plate at 150 ° C. for 10 minutes to form a coating film having an average film thickness of 600 mm.
The coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.1 mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, followed by drying in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a rubbed coating film. This operation was repeated to obtain a pair (two) of substrates having a rubbed coating film.
Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to each outer edge of the pair of substrates having a rubbing-treated film, and then superimposed so that the coating film faces each other. Crimped and cured the adhesive. Next, a liquid crystal cell is manufactured by filling a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port and then sealing the liquid crystal injection port with an acrylic photo-curing adhesive. did.

The above operation was repeated to produce three liquid crystal cells having unpatterned transparent electrodes. One of them was used for the evaluation of the pretilt angle described later. The remaining two liquid crystal cells were irradiated with light in a state where a voltage was applied between the conductive films by the following method, and then subjected to evaluation of a pretilt angle and a voltage holding ratio.
For two of the liquid crystal cells obtained above, an alternating current of 10 Hz is applied between the electrodes, and the liquid crystal is driven, using an ultraviolet gland irradiation device using a metal halide lamp as the light source, UV was irradiated at dose of 10,000 J / ^{m 2} or 100,000J / ^{m 2.} This irradiation amount is a value measured using a light meter that is measured on the basis of a wavelength of 365 nm.

[Evaluation of pretilt angle]
About each liquid crystal cell manufactured above, in accordance with the method described in Non-Patent Document 2 (TJ Scheffer et. Al. J. Appl. Phys. Vol. 19, p2013 (1980)), He- As a result of measuring the pretilt angle by the crystal rotation method using Ne laser light, the pretilt angle of the liquid crystal cell not irradiated with light is 89 °, and the pretilt angle of the liquid crystal cell with the irradiation amount of 10,000 J / m ² is 88 °. The pretilt angle of the liquid crystal cell with an irradiation amount of 100,000 J / m ² was 84 °.

[Manufacture of Liquid Crystal Cell Having Patterned Transparent Electrode]
The liquid crystal aligning agent prepared in Example 1 is patterned into a slit shape as shown in FIG. 1 and aligned on each electrode surface of glass substrates A and B each having ITO electrodes partitioned into a plurality of regions. It is applied using a film printer (Nissha Printing Co., Ltd.), heated on a hot plate at 80 ° C. for 1 minute (prebaked) to remove the solvent, and then heated on a hot plate at 150 ° C. for 10 minutes ( The film was post-baked to form a coating film having an average film thickness of 600 mm. The coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a coating film. This operation was repeated to obtain a pair (two) of substrates having a coating film.
Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to each outer edge having the coating film on the pair of substrates. Cured. Next, a liquid crystal cell is manufactured by filling a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port and then sealing the liquid crystal injection port with an acrylic photo-curing adhesive. did.
The above operation was repeated to produce three liquid crystal cells having patterned transparent electrodes. One of them was used for evaluation of response speed as described later. For the remaining two liquid crystal cells, 10,000 J / m ² or 100,000 J / m with a voltage applied between the conductive films in the same manner as in the production of the liquid crystal cell having the transparent electrode without pattern. After irradiating with light at an irradiation amount of m ² , the response speed was evaluated.
The electrode pattern used here is the same type as the electrode pattern in the PSA mode.

[Evaluation of response speed]
For each liquid crystal cell produced above, first, the luminance of the light transmitted through the liquid crystal cell by irradiating a visible light lamp without applying a voltage was measured with a photomultimeter, and this value was defined as a relative transmittance of 0%. . Next, the transmittance when 60 V AC was applied between the electrodes of the liquid crystal cell for 5 seconds was measured in the same manner as described above, and this value was defined as a relative transmittance of 100%.
At this time, when 60 V AC 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 not irradiated with light is 52 msec, the response speed of the liquid crystal cell with the irradiation amount of 10,000 J / m ² is 48 msec, and the response speed of the liquid crystal cell with the irradiation amount of 100,000 J / m ^2. The speed was 27 msec.

Examples 13 and 14
As the liquid crystal aligning agent, the liquid crystal aligning agent prepared in Example 2 was used in Example 13, and the liquid crystal aligning agent prepared in Example 3 was used in Example 14, respectively. Various liquid crystal cells were manufactured and evaluated.
The evaluation results are shown in Table 3.

From the results of Table 3, in the novel method for producing a liquid crystal display element according to the present invention, the pretilt angle obtained when the ultraviolet ray irradiation amount is 100,000 J / m ² (the value conventionally employed in the PSA mode). It can be seen that an excessive pre-tilt angle is obtained at an irradiation dose of 10,000 J / m ² or less. Moreover, even when the irradiation amount is small, a sufficiently fast response speed is obtained. Further, from the results of Table 2, it is understood that the liquid crystal aligning agent of the present invention has extremely excellent ultraviolet resistance.
Therefore, according to the method for manufacturing a liquid crystal display element of the present invention, the merits of the PSA mode can be realized with a small amount of light irradiation. Without worrying about lack of long-term reliability, a liquid crystal display element having a wide viewing angle, a high response speed of liquid crystal molecules, a high transmittance, and a high contrast can be manufactured.

Claims (9)

(A) The following formula (1)
R ^I Si (OR ^II ) ₃ (1)
(In Formula (1), R ^I is a monovalent organic group having a (meth) acryloyl group, and R ^II is a monovalent organic group.)
It contains at least one polymer selected from the group consisting of polyorganosiloxane obtained by hydrolyzing and condensing a silane compound containing a compound represented by formula (B), and polyamic acid and polyimide. A liquid crystal aligning agent.   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%. In addition to the compound represented by the above formula (1), the silane compound is further represented by the following formula (2)
R ^III Si (OR ^IV ) ₃ (2)
(In the formula (1), R ^III is a linear alkyl group having 1 to 18 carbon atoms, a linear fluoroalkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 24 carbon atoms, and R ^IV is 1 Valent organic group.)
The liquid crystal aligning agent of Claim 1 or 2 which contains the compound represented by these.   Any of Claims 1-3 whose said (A) polyorganosiloxane is a polyorganosiloxane obtained by hydrolyzing and condensing the silane compound which contains the compound represented by said Formula (1) 20 to 80weight%. A liquid crystal aligning agent according to claim 1.   Furthermore, (C) The liquid crystal aligning agent as described in any one of Claims 1-4 which further contains the compound which has at least 1 epoxy group in a molecule | numerator. The compound (C) is represented by the following formula (3)
The liquid crystal aligning agent of Claim 5 which is a compound which has group represented by these.   A liquid crystal alignment film formed from the liquid crystal alignment agent according to claim 1.   A liquid crystal display element comprising the liquid crystal alignment film according to claim 7. A coating film is formed by applying the liquid crystal aligning agent according to any one of claims 1 to 6 on the conductive film of the pair of substrates having the conductive film,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to each other through a layer of liquid crystal molecules,
A method for producing a liquid crystal display element, comprising a step of irradiating the liquid crystal cell with light while applying a voltage between conductive films of the pair of substrates.