JP2010256857A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent which can form a liquid crystal alignment layer excellent in liquid crystal aligning properties, high in heat resistance and light resistance and excellent in electric characteristics, and has high storage stability. <P>SOLUTION: The liquid crystal aligning agent includes a polyorganosiloxane (A) having an Si-X' bond (X' is a group including a structure having liquid crystal aligning ability) and an Si-X<SP>I</SP>bond (X<SP>I</SP>is a group including an epoxy structure) and a compound (B) which has, within a molecule, two or more of at least one of structure selected from a group comprising acetal ester structures of carboxylic acids, ketal ester structures of carboxylic acids, 1-alkyl cycloalkyl ester structures of carboxylic acids, and t-butyl ester structures of carboxylic acids. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

Currently, as a liquid crystal display element, a liquid crystal alignment film made of an organic resin or the like is formed on the surface of a substrate on which a transparent conductive film is provided to form a liquid crystal display element substrate. A nematic liquid crystal layer having a dielectric anisotropy of is formed into a sandwich cell, and the major axis of the liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other. A TN type liquid crystal display element having a so-called TN type (Twisted 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 (Patent Documents 1 to 5).
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. Reflective liquid crystal display elements do not use a backlight light source, but display using the intensity change of reflected light from outside such as sunlight when the element is driven. It is considered to be particularly advantageous for outdoor use because of its small number.
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 addition to business applications, in liquid crystal projector applications where demand for home theaters is increasing in recent years, 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 system itself rises during driving due to intense light irradiation.
Reflective liquid crystal display elements are highly likely to be used outdoors, and in this case, sunlight including strong ultraviolet light is the light source. In the reflective type, the distance that light passes through the element is longer than that in the transmissive 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 an automobile for private use, and at a higher temperature than a mode conventionally considered as a mode of use 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 the intense ultraviolet light together with the liquid crystal.
In this way, in liquid crystal display elements, due to their high functionality, versatility, improved manufacturing processes, etc., harsh environments that could not be considered before, such as high-intensity light irradiation, high-temperature environments, and long-time driving, etc. In such an environment, the liquid crystal display device is required to have better electrical characteristics such as liquid crystal orientation, voltage holding ratio, and display characteristics, and the liquid crystal display element has a longer 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 6 to 8).
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 9 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 the liquid crystal alignment film is excellent in vertical alignment, heat resistance and uniformity, and also excellent in stability as a coating solution. However, the liquid crystal alignment film based on this technology does not satisfy the required performance due to the harsh production and use environment, and the storage stability of the coating solution is still insufficient, so it is used industrially. There is a problem in convenience in doing.
Furthermore, as a liquid crystal display element, there is still a strong demand for developing a liquid crystal aligning agent that does not cause a problem of afterimage, that is, has excellent electrical characteristics.
On the other hand, if the liquid crystal alignment film is formed by rubbing, dust and static electricity are likely to be generated in the process, which causes problems such as dust adhering to the alignment film surface and causing display defects. There is known a photo-alignment method for imparting liquid crystal alignment ability by irradiating a photosensitive thin film such as polyvinyl cinnamate, polyimide, or azobenzene derivative formed on the surface with polarized or non-polarized radiation (Patent Documents 10 to 12). ). According to these methods, uniform liquid crystal alignment can be realized without generating static electricity or dust. However, even if the liquid crystal alignment film formed by these techniques exhibits a good pretilt angle at the beginning of formation, a phenomenon in which the pretilt angle develops over time occurs and the temporal stability of the pretilt angle is lacking. It has been pointed out.

As described above, it is possible to provide a liquid crystal alignment film having sufficient heat resistance and light resistance in extremely harsh current production environment and use environment, and excellent storage stability and a liquid crystal display element. Liquid crystal aligning agents that sometimes exhibit excellent electrical properties are not yet known. In addition, a liquid crystal aligning agent that exhibits sufficient pretilt angle stability over time when formed by a photo-alignment method is not yet known.
In order to solve these problems, the inventors of the present invention recently developed a liquid crystal alignment polyorganosiloxane obtained by introducing a structure having liquid crystal alignment ability utilizing the reactivity of polyorganosiloxane having an epoxy group. It reported about the liquid crystal aligning agent to contain (patent documents 13-16).
However, the harsh use environment described above tends to become more and more severe, and further improvement in the heat resistance of the liquid crystal alignment film is required.

JP-A-4-153622 JP 60-107020 A JP 56-91277 A US Pat. No. 5,928,733 Japanese Patent Laid-Open No. 11-258605 JP-A-9-197411 JP 2003-149648 A JP 2003-107486 A JP-A-9-281502 JP-A-6-287453 JP 2003-307736 A JP 2004-163646 A Japanese Patent Application No. 2008-19346 International Publication No. 09/25385 Pamphlet WO09 / 25386 pamphlet WO09 / 25388 pamphlet JP-A 63-291922 JP-A-6-222366 JP-A-6-281937 JP-A-5-107544

“Science of sol-gel method”, Agne Jofusha Co., Ltd., 1988, pp. 155-161 T.A. J. et al. Scheffer et. al. J. et al. Appl. Phys. vo. 19, p2013 (1980))

The present invention has been made in view of the circumstances as described above, and its purpose is excellent in liquid crystal orientation, high heat resistance and light resistance, and in particular, voltage holding even under high-intensity light irradiation in a high temperature environment. It is an object of the present invention to provide a liquid crystal aligning agent that can form a liquid crystal aligning film that is excellent in electrical characteristics and has a good storage stability.
Another object of the present invention is to provide a liquid crystal display device that has excellent heat resistance, light resistance and electrical characteristics, and excellent stability over time of the pretilt angle when the photo-alignment method is adopted in forming the liquid crystal alignment film. There is to do.
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 polyorganosiloxane having a Si—X ′ bond (where X ′ is a group containing a structure having liquid crystal alignment ability) and a Si— ^XI bond (where X ^I is a group containing an epoxy structure) (A And at least one structure selected from the group consisting of an acetal ester structure of carboxylic acid, a ketal ester structure of carboxylic acid, a 1-alkylcycloalkyl ester structure of carboxylic acid, and a t-butyl ester structure of carboxylic acid in the molecule. Compound (B) having two or more
It is achieved by a liquid crystal aligning agent containing
The above objects and advantages of the present invention are, secondly,
This is achieved by a liquid crystal display device comprising a liquid crystal alignment film formed from the liquid crystal alignment agent.

The liquid crystal aligning agent of the present invention has a liquid crystal aligning film that has excellent liquid crystal alignment properties, high heat resistance and light resistance, and has a low voltage holding ratio even when irradiated with high-intensity light, particularly in a high temperature environment, and has excellent electrical characteristics. It can be formed and has excellent storage stability.
The liquid crystal display element of the present invention comprising the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention is excellent in heat resistance, light resistance and electrical characteristics, and when a photo-alignment method is adopted in forming the liquid crystal alignment film. Even if it exists, it is excellent in the temporal stability of the pretilt angle.

The liquid crystal aligning agent of this invention contains the above polyorganosiloxane (A) and a compound (B) at least.
<Polyorganosiloxane (A)>
The polyorganosiloxane (A) in the present invention has a Si—X ′ bond (where X ′ is a group containing a structure having liquid crystal alignment ability) and a Si—X ^I bond (where X ^I is a group containing an epoxy structure). A polyorganosiloxane.
Examples of the structure having liquid crystal alignment ability in the group X ′ include, for example, a group having 17 to 51 carbon atoms having a steroid skeleton, an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, At least selected from an alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms, a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, and a fluoroalkoxycyclohexyl group having a fluoroalkoxyl group having 1 to 20 carbon atoms. A structure including one kind is preferable.
The group having 17 to 51 carbon atoms having the steroid skeleton is preferably one having 17 to 30 carbon atoms. Specific examples thereof include, for example, cholestane-3-yl group, cholesta-5-en-3-yl group, cholesta-24-en-3-yl group, cholesta-5,24-dien-3-yl group, lanostane A -3-yl group etc. can be mentioned.
Examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, and n-decyl group. N-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-stearyl group, n-eicosyl group and the like. it can. The alkyl group preferably has 4 to 20 carbon atoms.
Examples of the fluoroalkyl group having 1 to 20 carbon atoms include trifluoromethyl group, perfluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 4,4,4, A 5,5,5-pentafluoropentyl group, 3,3,4,4,5,5,5-heptafluoropentyl group and the like can be mentioned.
Examples of the alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms include n-propylcyclohexyl group, n-butylcyclohexyl group, n-pentylcyclohexyl group, n-hexylcyclohexyl group, n-heptylcyclohexyl group, n- An octyl cyclohexyl group can be exemplified.
Examples of the fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms include a trifluoromethylcyclohexyl group;
Examples of the fluoroalkoxycyclohexyl group having a fluoroalkoxy group having 1 to 20 carbon atoms include 4,4,4-trifluorobutoxycyclohexyl group and 4,4,5,5,5-pentafluoropentoxycyclohexyl group. , Can be mentioned respectively.
The structure having liquid crystal alignment ability is a group having 17 to 51 carbon atoms having a steroid skeleton, an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, or an alkyl having 1 to 20 carbon atoms. In addition to at least one selected from the group consisting of an alkylcyclohexyl group having a group and a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, the following formula (X′-1)

(In formula (X′-1), m is an integer of 0 to 4.)
The liquid crystal aligning agent obtained can be made into a liquid crystal alignment film by a photo-alignment method. As m in the formula (X′-1), 0 or 1 is preferable, and 0 is more preferable.
The "epoxy structure" in the above group X ^I means a 1,2-epoxy structure.
Examples of the group X ^I include the following formula (X ^I -1 ′) or (X ^I −2 ′)

(In the formulas ( ^XI- 1 ') and ( ^XI- 2'), s is an integer of 0-3, t is an integer of 1-6, u is an integer of 0-2, v Is an integer of 0 to 6, and “*” indicates a bond.
A group represented by
Particularly preferably, the following formula ( ^XI- 1) or ( ^XI- 2)

(Wherein ^(X I -1) and ^(X I -2), "*", respectively, indicating that a bond.)
It is group represented by these.
'The percentage of group X' polyorganosiloxane (A) in the group X in the present invention based on the sum of and groups ^{X I,} preferably 10 to 90 mol%, 20 to 80 mol% It is preferable that it is 25-75 mol% especially.
For the polyorganosiloxane (A) in the present invention, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 to 10,000,000, more preferably 5,000. ~ 100,000, more preferably 7,000 to 50,000.
Such polyorganosiloxane (A), for example, Si-X ^I binding (although X ^I has the same meaning as X ^I in the polyorganosiloxane (A).) Polyorganosiloxane (hereinafter having, having an "epoxy group Polyorganosiloxane "),
It can be a reaction product with at least one group selected from the group consisting of a carboxyl group and a hydroxyl group and a compound having a structure having liquid crystal alignment ability (hereinafter also referred to as “compound a”).

The polyorganosiloxane having an epoxy structure preferably has a polystyrene-equivalent weight average molecular weight of 500 to 100,000, more preferably 1,000 to 10,000, as measured by gel permeation chromatography (GPC). It is preferably 1,000 to 5,000.
The group X ^I is particularly preferably a group represented by the formula (X ^I -1) or (X ^I -2), like the group X ^I in the polyorganosiloxane (A).
Such polyorganosiloxane having an epoxy group is preferably a silane compound having an epoxy group, or a mixture of a silane compound having an epoxy group and another silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst. Can be synthesized by hydrolysis or hydrolysis / condensation.
Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropylmethyldiethoxy. Silane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy Silane etc. can be mentioned, It is preferable to use 1 or more types selected from these.

  Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, 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, methyltrimethoxysilane, Rutriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) ) Ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (tri Fluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltri Methoxy Lan, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2 -(Perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluorosilane Fluoro-n-octyl) ethyltri-i-propoxysilane, 2- (Perful Oro-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane,

Hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec- Butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 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-butoxy Silane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercapto Propyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxy Silane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane Allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri- n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi -I-propoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl Tildi-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 In addition to silane compounds having one silicon atom such as (ethoxy) (methyl) diphenylsilane,

Product names such as KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X -21-5848, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22 -176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672 , X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-10 3, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, manufactured by Shin-Etsu Chemical Co., Ltd.);
Glass resin (manufactured by Showa Denko KK); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray Dow Corning Co., Ltd.); FZ3711, FZ3722 (The above is made by Nippon Unicar Co., Ltd.);
DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (manufactured by Chisso Corporation);
Methyl silicate MS51, Methyl silicate MS56 (above, manufactured by Mitsubishi Chemical Corporation);
Examples thereof include partial condensates such as ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.); GR100, GR650, GR908, GR950 (manufactured by Showa Denko Co., Ltd.).

Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltri One or more selected from the group consisting of methoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane are preferred.
The polyorganosiloxane having an epoxy group preferably has an epoxy equivalent of 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol. Therefore, when synthesizing a polyorganosiloxane having an epoxy group, the proportion of the silane compound having an epoxy group and another silane compound is adjusted so that the epoxy equivalent of the resulting polyorganosiloxane is within the above range. Is preferably set.

Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane having an epoxy group include hydrocarbons, ketones, esters, ethers, alcohols, and the like.
Examples of the hydrocarbon include toluene and xylene;
Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone;
Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate;
Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;
Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl. Examples include ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like. Of these, it is preferable to use a water-insoluble organic solvent.
These organic solvents can be used alone or in admixture of two or more.
The amount of the organic solvent used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total silane compounds.
The amount of water used in producing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 times mol, more preferably 1 to 30 times mol, based on all silane compounds.

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. can be used, for example.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
Examples thereof include quaternary organic amines such as tetramethylammonium hydroxide. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine;
Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

As a catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or organic base as a catalyst, the desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing side reactions such as ring opening of the epoxy group. This is preferable. In addition, the liquid crystal aligning agent of the present invention containing a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a cinnamic acid derivative is extremely excellent in storage stability, which is advantageous. It is. The reason for this is that, as pointed out in Non-Patent Document 1 ("Science of Sol-Gel Method", Agne Sefu Co., Ltd., 1988, pp. 154-161), it is used as a catalyst in hydrolysis and condensation reactions. If an alkali metal compound or an organic base is used, it is presumed that a three-dimensional structure such as a random structure or a cage structure is formed and a polyorganosiloxane having a low silanol group content is obtained. When the content ratio of the silanol group is small, the condensation reaction between the silanol groups is suppressed, and when the liquid crystal aligning agent of the present invention contains another polymer described later, the silanol group and the other polymer Since the condensation reaction is suppressed, it is assumed that the storage stability is excellent.
As the catalyst, an organic base is particularly preferable. The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate. For example, the amount is preferably 0.01 to 3 moles relative to the total silane compound, More preferably, it is 0.05-1 times mole.

The hydrolysis or hydrolysis / condensation reaction in producing the polyorganosiloxane having an epoxy group is carried out by dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, and dissolving the solution in an organic base. It is preferable to carry out by mixing with water and heating with, for example, an oil bath.
During the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux.
After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by weight is preferable because the washing operation becomes easy. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the solvent is removed to achieve the target. A polyorganosiloxane having an epoxy group can be obtained.
In the present invention, a commercially available polyorganosiloxane having an epoxy group may be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (manufactured by Chisso Corporation).

The compound a is a compound having a structure having at least one group selected from the group consisting of a carboxyl group and a hydroxyl group and liquid crystal alignment ability. The “hydroxyl group” in the compound a is a concept including a phenolic hydroxyl group in addition to an alcoholic hydroxyl group.
The compound a is preferably the following formula (a-1)
R-Z (a-1)
(In formula (a-1), R is a group including a structure having liquid crystal alignment ability, and Z is a carboxyl group or a hydroxyl group.)
It is a compound represented by these.
Compound a, group Z in a compound a is a compound that leads to a group X 'in the polyorganosiloxane (A) by forming a linking group by reacting with groups X ^I of the polyorganosiloxane having an epoxy structure Therefore, the contents of the structure having R liquid crystal alignment ability can be understood in the same manner as the contents of the structure having liquid crystal alignment ability in the group X ′ of the polyorganosiloxane (A). Moreover, the group R, the ones in which the groups Z and group X ^I plus binding group formed by the reaction underlying X 'will be obvious to those skilled in the art.
Z in the formula (a-1) is preferably a carboxyl group.
Hereinafter, preferred embodiments of the compound a will be described.
A group having 17 to 51 carbon atoms, an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, and an alkyl group having 1 to 20 carbon atoms, wherein R (and hence X ′) has a steroid skeleton. In addition to the alkylcyclohexyl group having the above formula or the fluoroalkylcyclohexyl group having a C1-C20 fluoroalkyl group, the compound a having a structure represented by the above formula (X′-1) includes, for example, the following formula Compounds represented by each of (A-1) to (A-8) are preferred.

(In the formula (A-1), R ^I is a group having 17 to 51 carbon atoms having a steroid skeleton, an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or a cyclohexyl group, or An alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms or a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms,
X ¹ is a single bond, an oxygen atom, a sulfur atom, a phenylene group, a cyclohexylene group, —COO—, —NHCO—, —CONH— or —CO—, and X ² is a single bond or the following formula (X ² −1 ) To (X ² -6)

(In the above formulas, "*" indicates a bond marked with this is X ¹ side.)
A group represented by any one of
X ³ is a single bond, a phenylene group, ^* —O— (CH ₂ ) _a —, ^* —O— (CH ₂ ) _a —CO—,

Or ^* — (CH ₂ ) _a —OCO— (CH ₂ ) _a — (wherein, a is each independently an integer of 1 to 6, and “*” represents a bond to which —CH═ It is a group represented by the CH-CO- side.)
Z is synonymous with Z in the above formula (a-1),
However, when two adjacent bonds are both single bonds, they are collectively considered as one single bond. )

(In the formula (A-2), ^{R I} and Z each has the same meaning as ^{R I} and Z in the above formula (A-1),
X ⁴ is a single bond, oxygen atom, sulfur atom, ^* —COO—, ^* —OCO—, ^* —NHCO—, ^* —CONH— or ^* —CO— (in the above, “*” is a bond attached thereto) Is on the R ^I side.)
X ⁵ is a single bond or a phenylene group,
X ⁶ is a single bond or the following formula (X ⁶ -1)

(In formula (X ⁶ -1), “*” indicates that the bond with this is on the X ⁷ side.)
A group represented by
X ⁷ is a single bond, ^* —CO—, ^* —OCO— (CH ₂ ) _a —, ^* —OCO— (CH ₂ ) _a —CO—, ^* —O— (CH ₂ ) _a —, or

(In the above, a is an integer from 1 to 6, and "*". Indicating that bond marked with this is X ⁶ side) is, however, neither of two adjacent coupling single bond In this case, it is assumed that these are combined into a single bond. )

(In the formula (A-3), ^{R I} and Z each has the same meaning as ^{R I} and Z in the above formula (A-1), ^{X 8} is a single bond or ^* -O- _{(CH 2) a} - (However, a is an integer of 1-6, "*" indicates that the bond with this is on the -CH = CH-CO- side), and m is an integer of 0-4. is there.)

(In the formula (A-4) ~ (A -6), R I and Z each has the same meaning as ^{R I} and Z in the above formula (A-1), ^{X 9} are each a single bond, an oxygen atom it, a sulfur ^atom, * ^-COO-, * ^-OCO-, * ^-NHCO-, in * -CONH- or ^* -CO- (or, "*" is a bond marked with this is ^{R I} side X ¹⁰ is a single bond, an oxygen atom, a sulfur atom, or —O— (CH ₂ ) _a — ^* (where a is an integer of 1 to 6, and “*” represents this ) Indicates that the bond marked with is on the Z side.)

(In the formula (A-7) and (A-8), ^{R I} and Z each has the same meaning as ^{R I} and Z in the above formula ^{(A-1), X 11} are each a single ^{bond, *} — (CH ₂ ) _a —COO—, ^* —COO— (CH ₂ ) _a — or ^* —O— (CH ₂ ) _a —O— (where a is an integer from 1 to 6, and “*” This indicates that the bond with this is on the Z side.)
However, in the above formulas (A-1) to (A-8), combinations of substituents that can form an O—O bond or an α, β-diketo structure are not allowed.
The alkyl group having 2 to 20 carbon atoms ^{R I} in the above, for example ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- octyl group, n- decyl group, Examples thereof include an n-dodecyl group, an n-hexadecyl group, an n-octadecyl group, and an n-eicosyl group. The alkyl group preferably has 4 to 20 carbon atoms.
Examples of the fluoroalkyl group having 1 to 20 carbon atoms in R ^I include trifluoromethyl group, perfluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 4, Examples include 4,5,5,5-pentafluoropentyl group and 4,4,5,5,6,6,6-heptafluorohexyl group.
The monovalent organic group ^{R I} having a steroid skeleton in R ^I, preferably from 17 to 30 carbon atoms. Specific examples of R ¹ having a steroid skeleton include, for example, cholestane-3-yl group, cholesta-5-en-3-yl group, cholesta-24-en-3-yl group, cholesta-5,24-diene- A 3-yl group, a lanostane-3-yl group, etc. can be mentioned.

As a more preferable example of the compound a, when Z in the formula (a-1) is —COOH, the compound represented by the formula (A-1) is, for example, the following formula (A-1-C1): A compound represented by each of (A-1-C22);
Examples of the compound represented by the formula (A-2) include compounds represented by the following formulas (A-2-C1) to (A-2-C5);
Examples of the compound represented by the formula (A-3) include a compound represented by the following formula (A-3-C1) or (A-3-C2);
Examples of the compound represented by the formula (A-4) include compounds represented by the following formulas (A-4-C1) to (A-4-C3);
Examples of the compound represented by the formula (A-5) include a compound represented by the following formula (A-5-C1);
Examples of the compound represented by the formula (A-6) include a compound represented by the following formula (A-6-C1) or (A-6-C2);
Examples of the compound represented by the formula (A-7) include a compound represented by the following formula (A-7-C1);
Examples of the compound represented by the above formula (A-8) include compounds represented by the following formula (A-8-C1) or (A-8-C2).

(In the above, R ^I has the same meaning as in the above formulas (A-1) to (A-8), and a is an integer of 1 to 6, respectively.)
As another preferable example of the compound a in the case where R is a group including a structure represented by the formula (X′-1), when Z is —OH, the compound a is represented by the formula (A-1). Examples of the compound include, for example, compounds represented by the following formulas (A-1-O1) to (A-1-O7);
Examples of the compound represented by the formula (A-2) include compounds represented by the following formulas (A-2-O1) to (A-2-O3);
Examples of the compound represented by the above formula (A-8) include a compound represented by the following formula (A-8-O1).

(In the above, R ^I has the same meaning as in the above formulas (A-1), (A-2) and (A-8)).
On the other hand, R in the formula (a-1) is a group having 17 to 51 carbon atoms having a steroid skeleton, an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, 1 to 1 carbon atoms. In the case of having an alkylcyclohexyl group having 20 alkyl groups or a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, but not including the structure represented by the above formula (X′-1) As the compound a, for example, compounds represented by the following formulas (A-9) to (A-11) are preferable.

(R ^I and Z in the above formula are respectively synonymous with R ^I and Z in the above formula (A-1),
X ¹² in the formulas (A-10) and (A-11) is a single bond, an oxygen atom, ^* -COO- or ^* -OCO- (in the above, "*" is a bond with an R ^{It is the I} side.)
P in the formula (A-11) is 1 or 2. )
Examples of the compound represented by the above formula (A-9) in which Z is —COOH include, for example, n-butanoic acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n -Nonanoic acid, n-decanoic acid, n-lauric acid, n-dodecanoic acid, n-tridecanoic acid, n-tetradecanoic acid, n-pentadecanoic acid, n-hexadecanoic acid, n-heptadecanoic acid, n-stearic acid, n -Nonadecanoic acid, n-eicosanoic acid, tetrahydroabietic acid, monocholestanyl succinate, monocholestanyl glutarate, the following formula (A-9-1)
_{C h F2 h + 1 -C i} H 2i -COOH (A-9-1)
(In formula (A-9-1), h is an integer of 1 to 3, and i is an integer of 3 to 18.)
A compound represented by:
Examples of the compound represented by the above formula (A-10) in which Z is —COOH include, for example, 4-methylbenzoic acid, 4-ethylbenzoic acid, 4- (n-propyl) benzoic acid, 4- (n -Butyl) benzoic acid, 4- (n-pentyl) benzoic acid, 4- (n-hexyl) benzoic acid, 4- (n-heptyl) benzoic acid, 4- (n-octyl) benzoic acid, 4- (n -Nonyl) benzoic acid, 4- (n-decyl) benzoic acid, 4- (n-dodecyl) benzoic acid, 4- (n-octadecyl) benzoic acid, 4- (n-methoxy) benzoic acid, 4- (n -Ethoxy) benzoic acid, 4- (n-propoxy) benzoic acid, 4- (n-butoxy) benzoic acid, 4- (n-pentyloxy) benzoic acid, 4- (n-hexyloxy) benzoic acid, 4- (N-Heptyloxy) benzoic acid, 4- (n-octyloxy) Benzoic acid, 4- (n-nonyloxy) benzoic acid, 4- (n-decyloxy) benzoic acid, 4- (n-dodecyloxy) benzoic acid, 4- (n-octadecyloxy) benzoic acid, the following formula (A- 9-2) to (A-9-4)

(In the above formula, j is an integer of 5 to 20, k is an integer of 1 to 3, m is an integer of 0 to 18, and n is an integer of 1 to 18.)
A compound represented by each of the above;
Specific examples of the compound represented by the above formula (A-11) in which Z is —COOH include, for example, 4- (n-butyl) cyclohexylcarboxylic acid, 4- (n-pentyl) cyclohexylcarboxylic acid, 4- ( Examples thereof include n-butyl) bicyclohexylcarboxylic acid and 4- (n-pentyl) bicyclohexylcarboxylic acid.
Furthermore, examples of the compound represented by the above formula (A-9) in which Z is —OH include, for example, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol and 1-decanol. 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol And so on.

The compounds represented by the above formulas (A-1) to (A-11) can be obtained as commercial products, respectively, or can be synthesized by appropriately combining organic chemistry methods. Hereinafter, the R ^I is described as primarily an example of a compound is an alkyl group, in the same manner as also for the compounds other than R ^I is an alkyl group, or can be synthesized by methods analogous thereto is readily apparent to those skilled in the art Will be understood.
For example, the compound represented by the above formula (A-1-C1) is prepared by heating hydroxycinnamic acid and an alkyl halide having an alkyl group corresponding to R ^I in the presence of a suitable base such as potassium carbonate. After the reaction, it can be obtained by hydrolysis with an appropriate aqueous alkali solution such as sodium hydroxide.
The compound represented by formula (A-1-C2), for example hydroxycinnamic acid and R ^I suitable, such as potassium carbonate and alkyl carboxylic acid chlorides having a corresponding alkyl group that in the presence of a base 0 ° C. ~ room temperature It can obtain by making it react at the temperature of.
In the compound represented by the above formula (A-1-C4), for example, methyl hydroxybenzoate and an alkyl halide having an alkyl group corresponding to R ¹ or tosylated alkyl are present in the presence of a suitable base such as potassium carbonate. After reacting at a temperature of room temperature to 100 ° C., it is hydrolyzed with an appropriate aqueous alkali solution such as sodium hydroxide, and further converted into an acid chloride with thionyl chloride, and then this is reacted in the presence of an appropriate base such as potassium carbonate. Can be obtained by reacting with hydroxycinnamic acid at a temperature of 0 ° C. to room temperature.
The compound represented by the above formula (A-1-C5) is obtained by reacting, for example, hydroxybenzoic acid and an alkyl carboxylic acid chloride having an alkyl group corresponding to R ^I in the presence of a suitable base such as triethylamine at 0 ° C. to room temperature. After reacting at a temperature, an acid chloride is obtained with thionyl chloride, which can be obtained by reacting with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at a temperature of 0 ° C. to room temperature.

The compound represented by the above formula (A-1-C6) is, for example, 4-alkylbenzoic acid converted to acid chloride with thionyl chloride, and this is treated with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate. It can be obtained by reacting at room temperature.
The formula (A-1-C7) a compound represented by, for example 4-hydroxycyclohexyl carboxylate and a suitable alkali such as sodium or metallic sodium hydride and an alkyl halide having an alkyl group corresponding to R ^I In the presence of water, it is converted to ether, hydrolyzed with an aqueous alkali solution such as sodium hydroxide, further converted to acid chloride with thionyl chloride, and then this is treated with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate. And 0 ° C. to room temperature.
The compound represented by the above formula (A-1-C8) is obtained by converting, for example, 4-alkylcyclohexylcarboxylic acid having an alkyl group corresponding to R ^I into an acid chloride with thionyl chloride, an appropriate base such as potassium carbonate. It can be obtained by reacting with hydroxycinnamic acid in the presence at a temperature of 0 ° C. to room temperature.
The formula (A-1-C9) a compound represented by, after forming the alkyl halide and hydroxybenzaldehyde are reacted in the presence of a base such as potassium carbonate ether bond having an alkyl group corresponding to R ^I, 4-acetylbenzoic acid can be obtained by aldol condensation in the presence of sodium hydroxide. Compounds represented by each of the above formulas (A-1-C10) to (A-1-C15) can also be obtained by a method analogous thereto.

The compound represented by the above formula (A-2-C1) is obtained by reacting, for example, 4-iodophenol with an alkyl acrylate having an alkyl group corresponding to R ^I using palladium and an amine as a catalyst (generally “Heck reaction”). The desired cyclic acid anhydride such as succinic anhydride or glutaric anhydride can be obtained by ring-opening addition to the reaction product.
The compound represented by the above formula (A-2-C2) can be obtained by aldol condensation of 4-alkylacetophenone having an alkyl group corresponding to R ^I and 4-formylbenzoic acid in the presence of sodium hydroxide. . The compound represented by the above formula (A-2-C3) can also be obtained by a method analogous thereto.
The compound represented by the above formula (A-2-C4) can be obtained by aldol condensation of 4-alkylacetophenone having an alkyl group corresponding to R ^I and 4-hydroxybenzaldehyde in the presence of sodium hydroxide. The compound represented by the above formula (A-2-C5) can also be obtained by a method analogous thereto.
The compound represented by the above formula (A-3-C1) is obtained by a method of obtaining an acrylic ester having an alkyl group corresponding to R ^I and 4-bromocinnamic acid using a palladium catalyst (generally referred to as Heck reaction). be able to. A compound represented by the above formula (A-3-C2) can also be obtained by a method analogous thereto.
For example, in the case where R ^I is an alkyl group, the compound represented by the above formula (A-4-C1) includes an alkyl succinic anhydride having an alkyl group corresponding to R ^I and 4-aminocinnamic acid. Can be obtained by reacting under reflux in acetic acid or under reflux in toluene or xylene in the presence of a suitable base catalyst such as triethylamine,
When R ^I is a fluoroalkyl group, maleic anhydride is protected with a suitable protecting group such as p-toluidine, and then coupled with a Grignard reaction with a fluoroalkyl iodide having a fluoroalkyl group corresponding to R ^I. It can be obtained by a method of deprotection by hydrolysis after ringing, dehydration ring closure, and reaction with 4-aminocinnamic acid.

The compound represented by the above formula (A-4-C2) can be synthesized, for example, by one of the following two routes.
As a first route, after maleic anhydride is protected with a suitable protecting group such as p-toluidine, an alcohol having an alkyl group corresponding to R ^I is added with Michael in the presence of a suitable base with potassium carbonate. Deprotection by hydrolysis, dehydration and ring closure, and reacting the product with 4-aminocinnamic acid in the same manner as in the synthesis of the compound represented by the above formula (A-4-C1). Can be mentioned.
As a second route, after ether is reacted in the presence of a halogenated alkyl, such as silver oxide having an alkyl group corresponding to methyl malic acid and R ^I, hydrolyzing performs dehydration ring closure, the A method of reacting the product with 4-aminocinnamic acid in the same manner as in the synthesis of the compound represented by the above formula (A-4-C1) can be mentioned.
The formula (A-4-C3) a compound represented by, for example, instead of an alcohol having an alkyl group corresponding to R ^I addition to using a thiol having an alkyl group corresponding to R ^I is above formula (A- It can be obtained in the same manner as in the first route in the synthesis of the compound represented by 4-C2).
The compound represented by the above formula (A-5-C1) is, for example, 1,2,4-tricarboxycyclohexane anhydride converted to acid chloride with thionyl chloride, and then an alcohol having an alkyl group corresponding to R ^I and triethylamine. Reaction in the presence of a suitable base such as the above, and the product is reacted with 4-aminocinnamic acid in the same manner as in the synthesis of the compound represented by the above formula (A-4-C1). Can be obtained.

The compound represented by the above formula (A-6-C1) is obtained by, for example, reacting a compound R ^I —OH corresponding to a desired compound with trimellitic anhydride to synthesize an ester compound as an intermediate, It can be synthesized by reacting this ester compound with 4-aminocinnamic acid. The synthesis of the intermediate ester compound is preferably carried out in the presence of a basic compound in a suitable solvent. Examples of the solvent that can be used here include tetrahydrofuran, and examples of the basic compound include triethylamine. Can do. The reaction between the ester compound and 4-aminocinnamic acid is, for example, a method in which both are refluxed in acetic acid, both in toluene or xylene in the presence of a suitable catalyst (for example, an acid catalyst such as sulfuric acid or a base catalyst such as triethylamine). And a method of refluxing.
The compound represented by the above formula (A-6-C2) is obtained by refluxing 5-hydroxyphthalic acid in, for example, diethylbenzene, dehydrating and cyclizing to make an acid anhydride, and then using 4-aminocinnamic acid and the same method as described above. Is synthesized by reacting the imide compound with a compound R ^I- X corresponding to the desired compound (where X is a halogen atom). can do. At this time, it is preferably carried out in a suitable solvent in the presence of a basic compound. Examples of the solvent that can be used here include amide compounds such as N, N-dimethylacetamide, and examples of the basic compound include potassium carbonate.
The formula (A-7-C1) a compound represented by, for example 4-nitro cinnamic acid, is reacted with an alkyl halide having an alkyl group corresponding to R ^I with an ester in the presence of potassium carbonate, the The nitro group can be obtained by reacting the product with 1,2,4-tricarboxycyclohexylcyclohexane anhydride after reducing the nitro group with, for example, tin chloride to an amino group. The latter reaction can be carried out, for example, by refluxing the starting compound in acetic acid or refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine. A compound represented by the above formula (A-8-C1) can also be synthesized by a method analogous thereto.
In the synthesis of the compound represented by the above formula (A-7-C1), the compound represented by the above formula (A-8-C2) is a hydroxy group instead of 1,2,4-tricarboxycyclohexylcyclohexane anhydride. After synthesizing a cinnamic acid derivative having an imide ring using phthalic acid, it can be obtained by reacting with succinic anhydride or glutaric anhydride.

The compound represented by the above formula (A-1-O1) reacts an alkyl halide having an alkyl group corresponding to R ^I with 4-hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond. After formation, 4-hydroxyacetophenone can be obtained by aldol condensation in the presence of sodium hydroxide. The compounds represented by the above formulas (A-1-O2) to (A-1-O7) can also be obtained by a method according to the above.
The compound represented by the above formula (A-2-O1) is obtained by reacting, for example, 4-iodophenol and an alkyl acrylate having an alkyl group corresponding to R ^I using palladium and an amine as a catalyst (generally “Heck reaction”). Can be obtained.
The compound represented by the above formula (A-2-O2) can be obtained by aldol condensation of 4-alkylacetophenone having an alkyl group corresponding to R ^I and 4-hydroxybenzaldehyde in the presence of sodium hydroxide. it can. The compound represented by the above formula (A-2-O3) can also be obtained by a method according to the above.
The compound represented by the above formula (A-8-O1) is obtained by, for example, converting 4-nitrocinnamic acid into an acid chloride with thionyl chloride, and then reacting with an alcohol having an alkyl group corresponding to R ^I to form an ester. The nitro group can be obtained by, for example, reducing the nitro group with tin chloride to form an amino group, and then reacting the product with hydroxyphthalic anhydride. The latter reaction can be carried out, for example, by refluxing the starting compound in acetic acid or refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine.

Of these compounds a, preferably
R in the formula (a-1) has the structure represented by the formula (X′-1), and the formulas (A-1-C1), (A-1-C3), (A-1- C4), (A-1-C6) to (A-1-C8), (A-1-C16), (A-1-C19), (A-1-C21), (A-4-C1) , (A-4-C2), (A-5-C1) and (A-7-C1),
R does not have the structure represented by the above formula (X′-1) as n-butanoic acid, n-hexanoic acid, n-octanoic acid, n-lauric acid, n-stearic acid, 4-n- Octadecylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-octylbenzoic acid, 4-n-hexylbenzoic acid, 4-n-octadecyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n- Octyloxybenzoic acid, 4-n-hexyloxybenzoic acid, 1-hexanethiol, 1-heptanethiol, 1-octanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol, 1-dodecanethiol, 1 -Tetradecanethiol, 1-hexadecanethiol, 1-octadecanethiol, morecholestanyl succinate and the following formulas (A-9-3-1) to ( A-9-3-3)

It is a compound represented by each of these.
In the present specification, the compound a in which R does not have the structure represented by the formula (X′-1) is hereinafter referred to as “another pretilt angle developing compound”.
The polyorganosiloxane (A) in the present invention requires that a part of the Si- ^XI bond derived from the polyorganosiloxane having an epoxy structure remains. Therefore, when carrying out the reaction of both, it is preferable to use a compound a less number of moles than the number of moles of group X ^I having the polyorganosiloxane having an epoxy structure.
The ratio of compound a in the synthesis of the polyorganosiloxane (A) in the present invention, relative to 1 mol of the group X ^I having the polyorganosiloxane having an epoxy structure, and 0.1 to 0.9 moles Is more preferable, 0.2 to 0.8 mol is more preferable, and 0.25 to 0.75 is more preferable.
The reaction between the polyorganosiloxane having an epoxy structure and the compound a is preferably performed in the presence of a catalyst. As such a catalyst, for example, an organic base or a compound known as a so-called curing accelerator that accelerates the reaction between an epoxy compound and an acid anhydride can be used.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
A quaternary organic amine such as tetramethylammonium hydroxide can be used. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide preferable.
Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine;
2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- ( 2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s -Triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2′-methyl] An imidazole compound such as an isocyanuric acid adduct of loumidazolyl- (1 ′)] ethyl-s-triazine;

Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;
Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, Tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate Such as over preparative quaternary phosphonium salts;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;
Boron compounds such as boron trifluoride and triphenyl borate;
Metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as amine addition accelerators such as dicyandiamide and adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator in which the surface of a curing accelerator such as the imidazole compound, organophosphorus compound or quaternary phosphonium salt is coated with a polymer;
An amine salt type latent curing agent accelerator;
Examples include latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.
These catalysts are preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane having an epoxy structure. used.
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
The synthesis reaction of the polyorganosiloxane (A) can be performed in the presence of an organic solvent, if necessary. Examples of such organic solvents include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like. Of these, ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products and ease of purification of the products. The solvent has a solid content concentration (ratio in which the total weight of components other than the solvent in the reaction solution occupies the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 50% by weight. used.
The polyorganosiloxane (A) reacts a polyorganosiloxane having an epoxy structure with the compound a and introduces a group having liquid crystal alignment into the polyorganosiloxane by utilizing ring-opening addition of an epoxy group. is there. This production method is simple and is a very suitable method in that the introduction rate of the structure having liquid crystal alignment ability can be increased.
In the above, compound a may be used alone or in combination of two or more compounds a. In this case, when the ratio of the compound a having a group represented by the formula (X′-1) is preferably 50 mol% or more with respect to the total amount of the compound a, the polyorganosiloxane (A) is The liquid crystal aligning agent to contain can form the liquid crystal aligning film which shows favorable liquid crystal aligning property by the photo-alignment method.
In the above, when the group Z of the compound a is —COOH, the reaction may be performed by replacing part of the compound a with another carboxylic acid. In this case, the use ratio of the other carboxylic acid is preferably 50 mol% or less with respect to the total of the compound a and the other carboxylic acid.

<Compound (B)>
The compound (B) in the present invention is selected from the group consisting of an acetal ester structure of carboxylic acid, a ketal ester structure of carboxylic acid, a 1-alkylcycloalkyl ester structure of carboxylic acid and a t-butyl ester structure of carboxylic acid in the molecule. And a compound having two or more of at least one structure. The compound (B) may be a compound having two or more of the same kind of structures among these structures, or may be a compound having two or more of the different kinds of structures out of these structures. Good.
Examples of the group that forms the acetal ester structure of the carboxylic acid include the following formulas (B-1) and (B-2).

(In Formula (B-1), R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 carbon atoms. -10 aralkyl groups,
In formula (B-2), n1 is an integer of 2-10. )
And groups represented by each of the above. Here, the alkyl group of R ¹ in the above formula (B-1) is a methyl group;
The alicyclic group is a cyclohexyl group;
The aryl group is a phenyl group;
As the aralkyl group, a benzyl group is preferable,
As the alkyl group for R ² , an alkyl group having 1 to 6 carbon atoms;
As the alicyclic group, an alicyclic group having 6 to 10 carbon atoms;
The aryl group is a phenyl group;
As the aralkyl group, a benzyl group or a 2-phenylethyl group is preferable,
N1 in Formula (B-2) is preferably 3 or 4.

Examples of the group represented by the formula (B-1) include 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-i-propoxyethoxycarbonyl group, 1- n-butoxyethoxycarbonyl group, 1-i-butoxyethoxycarbonyl group, 1-sec-butoxyethoxycarbonyl group, 1-t-butoxyethoxycarbonyl group, 1-cyclopentyloxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 1-norbornyloxyethoxycarbonyl group, 1-bornyloxyethoxycarbonyl group, 1-phenoxyethoxycarbonyl group, 1- (1-naphthyloxy) ethoxycarbonyl group, 1-benzyloxyethoxycarbonyl group, 1-phenethyloxy Ethoxycarbonyl group, (cyclohexyl) (methoxy) methoxycarbonyl group, (cyclohexyl) (ethoxy) methoxycarbonyl group, (cyclohexyl) (n-propoxy) methoxycarbonyl group, (cyclohexyl) (i-propoxy) methoxycarbonyl group, (cyclohexyl) ) (Cyclohexyloxy) methoxycarbonyl group, (cyclohexyl) (phenoxy) methoxycarbonyl group, (cyclohexyl) (benzyloxy) methoxycarbonyl group, (phenyl) (methoxy) methoxycarbonyl group, (phenyl) (ethoxy) methoxycarbonyl group, (Phenyl) (n-propoxy) methoxycarbonyl group, (phenyl) (i-propoxy) methoxycarbonyl group, (phenyl) (cyclohexyloxy) methoxycarbo Group, (phenyl) (phenoxy) methoxycarbonyl group, (phenyl) (benzyloxy) methoxycarbonyl group, (benzyl) (methoxy) methoxycarbonyl group, (benzyl) (ethoxy) methoxycarbonyl group, (benzyl) (n- (Propoxy) methoxycarbonyl group, (benzyl) (i-propoxy) methoxycarbonyl group, (benzyl) (cyclohexyloxy) methoxycarbonyl group, (benzyl) (phenoxy) methoxycarbonyl group, (benzyl) (benzyloxy) methoxycarbonyl group, etc. ;
Examples of the group represented by the formula (B-2) include a 2-tetrahydrofuranyloxycarbonyl group and a 2-tetrahydropyranyloxycarbonyl group. Of these, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group and the like are preferable.
Examples of the group that forms the ketal ester structure of the carboxylic acid include the following formulas (B-3) to (B-5):

(In Formula (B-3), R ³ is an alkyl group having 1 to 12 carbon atoms, and R ⁴ and R ⁵ are an alkyl group having 1 to 12 carbon atoms and an alicyclic group having 3 to 20 carbon atoms, respectively. A group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms,
In formula (B-4), R ⁶ is an alkyl group having 1 to 12 carbon atoms, n2 is an integer of 2 to 8,
In formula (B-5), R ⁷ is an alkyl group having 1 to 12 carbon atoms, and n3 is an integer of 2 to 8. )
And groups represented by each of the above. Here, the alkyl group of R ³ in the above formula (B-3) is preferably a methyl group,
The alkyl group for R ⁴ is a methyl group;
The alicyclic group is a cyclohexyl group and the aryl group is a phenyl group;
As the aralkyl group, a benzyl group is preferable,
The alkyl group for R ^{5 is} an alkyl group having 1 to 6 carbon atoms;
As the alicyclic group, an alicyclic group having 6 to 10 carbon atoms;
The aryl group is a phenyl group;
As the aralkyl group, a benzyl group or a 2-phenylethyl group is preferable,
The alkyl group for R ⁶ in formula (B-4) is a methyl group;
n2 is preferably 3 or 4, respectively.
The alkyl group for R ⁷ in formula (B-5) is a methyl group;
n3 is preferably 3 or 4, respectively.

  Examples of the group represented by the formula (B-3) include a 1-methyl-1-methoxyethoxycarbonyl group, a 1-methyl-1-ethoxyethoxycarbonyl group, and a 1-methyl-1-n-propoxyethoxycarbonyl group. 1-methyl-1-i-propoxyethoxycarbonyl group, 1-methyl-1-n-butoxyethoxycarbonyl group, 1-methyl-1-i-butoxyethoxycarbonyl group, 1-methyl-1-sec-butoxyethoxy Carbonyl group, 1-methyl-1-t-butoxyethoxycarbonyl group, 1-methyl-1-cyclopentyloxyethoxycarbonyl group, 1-methyl-1-cyclohexyloxyethoxycarbonyl group, 1-methyl-1-norbornyloxy Ethoxycarbonyl group, 1-methyl-1-bornyloxyethoxycarbonyl group 1-methyl-1-phenoxyethoxycarbonyl group, 1-methyl-1- (1-naphthyloxy) ethoxycarbonyl group, 1-methyl-1-benzyloxyethoxycarbonyl group, 1-methyl-1-phenethyloxyethoxycarbonyl group 1-cyclohexyl-1-methoxyethoxycarbonyl group, 1-cyclohexyl-1-ethoxyethoxycarbonyl group, 1-cyclohexyl-1-n-propoxyethoxycarbonyl group, 1-cyclohexyl-1-i-propoxyethoxycarbonyl group, 1 -Cyclohexyl-1-cyclohexyloxyethoxycarbonyl group, 1-cyclohexyl-1-phenoxyethoxycarbonyl group, 1-cyclohexyl-1-benzyloxyethoxycarbonyl group, 1-phenyl-1-methoxyethoxycarbo Group, 1-phenyl-1-ethoxyethoxycarbonyl group, 1-phenyl-1-n-propoxyethoxycarbonyl group, 1-phenyl-1-i-propoxyethoxycarbonyl group, 1-phenyl-1-cyclohexyloxyethoxycarbonyl Group, 1-phenyl-1-phenoxyethoxycarbonyl group, 1-phenyl-1-benzyloxyethoxycarbonyl group, 1-benzyl-1-methoxyethoxycarbonyl group, 1-benzyl-1-ethoxyethoxycarbonyl group, 1-benzyl -1-n-propoxyethoxycarbonyl group, 1-benzyl-1-i-propoxyethoxycarbonyl group, 1-benzyl-1-cyclohexyloxyethoxycarbonyl group, 1-benzyl-1-phenoxyethoxycarbonyl group, 1-benzyl- 1-benzyl An oxyethoxycarbonyl group, etc .;

Examples of the group represented by the formula (B-4) include a 2- (2-methyltetrahydrofuranyl) oxycarbonyl group, a 2- (2-methyltetrahydropyranyl) oxycarbonyl group, and the like;
Examples of the group represented by the formula (B-5) include a 1-methoxycyclopentyloxycarbonyl group and a 1-methoxycyclohexyloxycarbonyl group. Of these, a 1-methyl-1-methoxyethoxycarbonyl group, a 1-methyl-1-cyclohexyloxyethoxycarbonyl group, and the like are preferable.
Examples of the group that forms the 1-alkylcycloalkyl ester structure of the carboxylic acid include the following formula (B-6):

(In formula (B-6), R ⁸ is an alkyl group having 1 to 12 carbon atoms, and n4 is an integer of 1 to 8)
The group represented by these can be mentioned. Here, the alkyl group of R ⁸ in the above formula (B-6) is preferably an alkyl group having 1 to 10 carbon atoms.

  Examples of the group represented by the above formula (B-6) include 1-methylcyclopropoxycarbonyl group, 1-methylcyclobutoxycarbonyl group, 1-methylcyclopentoxycarbonyl group, 1-methylcyclohexyloxycarbonyl group, 1-methylcycloheptyloxycarbonyl group, 1-methylcyclooctyloxycarbonyl group, 1-methylcyclononyloxycarbonyl group, 1-methylcyclodecyloxycarbonyl group, 1-ethylcyclopropoxycarbonyl group, 1-ethylcyclobutoxy Carbonyl group, 1-ethylcyclopentoxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1-ethylcycloheptyloxycarbonyl group, 1-ethylcyclooctyloxycarbonyl group, 1-ethylcyclononyloxycarbonyl group, 1- Echi Cyclodecyloxycarbonyl group, 1- (iso) propylcyclopropoxycarbonyl group, 1- (iso) propylcyclobutoxycarbonyl group, 1- (iso) propylcyclopentoxycarbonyl group, 1- (iso) propylcyclohexyloxycarbonyl group 1- (iso) propylcycloheptyloxycarbonyl group, 1- (iso) propylcyclooctyloxycarbonyl group, 1- (iso) propylcyclononyloxycarbonyl group, 1- (iso) propylcyclodecyloxycarbonyl group, 1- (iso) butylcyclopropoxycarbonyl group, 1- (iso) butylcyclobutoxycarbonyl group, 1- (iso) butylcyclopentoxycarbonyl group, 1- (iso) butylcyclohexyloxycarbonyl group, 1- (iso) Butylcycloheptyloxy Rubonyl group, 1- (iso) butylcyclooctyloxycarbonyl group, 1- (iso) butylcyclononyloxycarbonyl group, 1- (iso) butylcyclodecyloxycarbonyl group, 1- (iso) pentylcyclopropoxycarbonyl group, 1- (iso) pentylcyclobutoxycarbonyl group, 1- (iso) pentylcyclopentoxycarbonyl group, 1- (iso) pentylcyclohexyloxycarbonyl group, 1- (iso) pentylcycloheptyloxycarbonyl group, 1- ( Iso) pentylcyclooctyloxycarbonyl group, 1- (iso) pentylcyclononyloxycarbonyl group, 1- (iso) pentylcyclodecyloxycarbonyl group,

1- (iso) hexylcyclopropoxycarbonyl group, 1- (iso) hexylcyclobutoxycarbonyl group, 1- (iso) hexylcyclopentoxycarbonyl group, 1- (iso) hexylcyclohexyloxycarbonyl group, 1- (iso) Hexylcycloheptyloxycarbonyl group, 1- (iso) hexylcyclooctyloxycarbonyl group, 1- (iso) hexylcyclononyloxycarbonyl group, 1- (iso) hexylcyclodecyloxycarbonyl group, 1- (iso) heptyl Cyclopropoxycarbonyl group, 1- (iso) heptylcyclobutoxycarbonyl group, 1- (iso) heptylcyclopentoxycarbonyl group, 1- (iso) heptylcyclohexyloxycarbonyl group, 1- (iso) heptylcycloheptyloxycarbonyl 1- (I ) Heptylcyclooctyloxycarbonyl group, 1- (iso) heptylcyclononyloxycarbonyl group, 1- (iso) heptylcyclodecyloxycarbonyl group, 1- (iso) octylcyclopropoxycarbonyl group, 1- (iso) octylcyclo Butoxycarbonyl group, 1- (iso) octylcyclopentoxycarbonyl group, 1- (iso) octylcyclohexyloxycarbonyl group, 1- (iso) octylcycloheptyloxycarbonyl group, 1- (iso) octylcyclooctyloxycarbonyl A 1- (iso) octylcyclononyloxycarbonyl group, a 1- (iso) octylcyclodecyloxycarbonyl group, and the like.
The group forming the t-butyl ester structure of the carboxylic acid is a t-butoxycarbonyl group.

As the compound (B) in the present invention, the following formula (B)
B _n R (B)
(In the formula (B), B is a group represented by any one of the above formulas (B-1) to (B-5) or a t-butoxycarbonyl group, n is 2, and R is a single bond. Or a group obtained by removing n-valent hydrogen from a heterocyclic compound having 3 to 10 carbon atoms and n is an integer of 2 to 10 or an n-valent hydrocarbon group having 1 to 18 carbon atoms .)
The compound represented by these is preferable. n is preferably 2 or 3.
As specific examples of R in the above formula (B), when n is 2, a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, a 1,2-phenylene group, a 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthalenyl group, 5-sodium sulfo-1,3-phenylene group, 5-tetrabutylphosphonium sulfo-1,3-phenylene group and the like;
In the case where n is 3, the following formula

And a group represented by the formula: benzene-1,3,5-triyl group. As said alkylene group, a linear thing is preferable.
The compound (B) represented by the above formula (B) can be synthesized by an organic chemistry standard method or by appropriately combining organic chemistry standard methods.
For example, a compound in which the group B in the above formula (B) is a group represented by the above formula (B-1) (except when R ¹ is a phenyl group) is preferably in the presence of a phosphoric acid catalyst. And compound R— (COOH) _n (wherein R and n are as defined above in formula (B)) and compound R ² —O—CH═R ¹ ′ (wherein R ² is as defined above) And synthesizing by adding R ¹ ′, which is a group obtained by removing a hydrogen atom from the 1-position carbon of the group R ¹ in the above formula (B). Can do.
The compound in which the group B in the formula (B) is a group represented by the formula (B-2) is preferably a compound R- (COOH) _n (wherein R and R in the presence of a p-toluenesulfonic acid catalyst). n is as defined in the above formula (B).) and the following formula

(In the above formula, n1 has the same meaning as in the above formula (B-2).)
It can synthesize | combine by adding the compound represented by these.
The ratio of the compound (B) used in the liquid crystal aligning agent of the present invention includes the acetal ester structure of the carboxylic acid, the ketal ester structure of the carboxylic acid, the 1-alkylcycloalkyl ester structure of the carboxylic acid, and the carboxylic acid. ratio of the total number of moles of the at least one structure, with respect to Si-X ^I bond 1 mol having a polyorganosiloxane (a), a 0.1 to 10 mol selected from the group consisting of Roh t- butyl ester structure The ratio is preferably 0.4 to 4 mol, more preferably 1.5 to 2 mol. Therefore, when the compound represented by the above formula (B) is used as the compound (B), the usage ratio of the compound (B) is based on 1 mol of Si- ^XI bond of the polyorganosiloxane (A). 0.1 / n to 10 / n mole, preferably 0.4 / n to 4 / n mole, and more preferably 1.5 / n to 2 / n mole. It will be. However, in the above, n has the same meaning as in the above formula (B).
By containing such a compound (B), the liquid crystal aligning agent of the present invention is preferable because it can form a liquid crystal aligning film excellent in heat resistance and light resistance and is excellent in storage stability.

<Other ingredients>
The liquid crystal aligning agent of this invention contains the above polyorganosiloxane (A) and a compound (B) as an essential component.

  In addition to the polyorganosiloxane (A) and the compound (B) as described above, the liquid crystal aligning agent of the present invention may further contain other components as long as the effects of the present invention are not impaired. Examples of such other components include a polymer (C) other than the polyorganosiloxane (A) (hereinafter referred to as “other polymer (C)”), a compound having at least one epoxy group in the molecule. (However, the thing corresponding to the said polyorganosiloxane (A) is remove | excluded. Hereafter, it is called an "epoxy compound."), A functional silane compound, a hardening | curing agent, a hardening catalyst, surfactant, etc. can be mentioned.

  Said other polymer (C) can be used in order to improve the solution characteristic of the liquid crystal aligning agent of this invention, and the electrical property of the liquid crystal aligning film obtained. Examples of such other polymers include at least one polymer (C1) selected from the group consisting of polyamic acid and polyimide, and polyorganosiloxanes (C2) other than the polyorganosiloxane (A) (hereinafter referred to as “other polymers”). Polyorganosiloxane (C2) "), polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like.

{Polyamic acid}
The polyamic acid can be obtained by reacting tetracarboxylic dianhydride and diamine.
Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid in the present invention include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, and the like. Can be mentioned. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride 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- No 1,2-dicarboxylic acid 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2 : 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and the like;
As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride can be mentioned, respectively,
The tetracarboxylic dianhydride described in Japanese Patent Application No. 2009-84462 can be used.

Among these, the tetracarboxylic dianhydride used for synthesizing the polyamic acid preferably includes an alicyclic tetracarboxylic dianhydride, and 2,3,5-tricarboxycyclopentyl. It is preferable to contain at least one selected from the group consisting of acetic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride, in particular 2,3,5-tricarboxycyclopentyl acetic acid dianhydride It is preferable that a thing is included.
The tetracarboxylic dianhydride used to synthesize the polyamic acid is composed of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride. It is preferable that at least one selected from the group contains 10 mol% or more, more preferably 20 mol% or more, more preferably 2,3,5-tricarboxyl, based on the total tetracarboxylic dianhydride. Most preferably, it is composed of at least one selected from the group consisting of cyclopentylacetic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

Examples of the diamine used for synthesizing the polyamic acid include aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane, and the like. Specific examples thereof include aliphatic diamines such as 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenyle Diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 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, 1,4-bis- (4-aminophenyl)- Piperazine, 3,5-diaminobenzoic acid, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diamino Benzene, Pentadekanokishi 2,4-diaminobenzene, Hekisadekanokishi 2,4-diaminobenzene, Okutadekanokishi 2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, Tetoradekanokishi 2,5-diaminobenzene,

Pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, choles Tanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3, 6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- ( 4'-trifluoromethylbenzoiro C) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl ) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-Heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -piperidine and the following formula (D-1)

(In the formula (D-1), ^{X I} is an alkyl group having 1 to 3 carbon ^atoms, * ^-O-, * -COO- or ^* -OCO- (where bond marked with "*" is diaminophenyl group And x is 0 or 1, y is an integer from 0 to 2, and z is an integer from 1 to 20.)
A compound represented by:
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, respectively.
The diamine described in Japanese Patent Application No. 2009-84462 can be used.
The ^{X I} in the above formula (D-1) an alkyl group having 1 to 3 carbon ^atoms, * -O- or ^* -COO- (provided that a bond marked with "*" is bonded to the diamino phenyl group.) In Preferably there is. Specific examples of the group C _z H _{2z + 1} — include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n -An eicosyl group etc. can be mentioned. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.
Specific examples of the compound represented by the formula (D-1) include, for example, the following formulas (D-1-1) to (D-1-4):

And the like, and the like.
In the above formula (D-1), x and y are preferably not 0 at the same time.
These diamines can be used alone or in combination of two or more.
The proportion of tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is 0.2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group contained in the diamine compound. The ratio which becomes -2 equivalent is preferable, More preferably, it is the ratio which becomes 0.3-1.2 equivalent.
The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 to 150 ° C., more preferably at a temperature of 0 to 100 ° C., preferably 0.5 to 24 hours, more preferably 2 to 10 Done for hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide;
Mention may be made of phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount (a) of the organic solvent used is such that the total amount (b) of tetracarboxylic dianhydride and diamine compound is preferably 0.1 to 50% by weight, more preferably 5 to 5%, based on the total amount (a + b) of the reaction solution. The amount is 30% by weight.

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 into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, 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.
The 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. Etc. Alternatively, the method of dissolving this polyamic acid in an organic solvent again and then precipitating with a poor solvent, or washing the solution after re-dissolution with water and then distilling the organic solvent in the solution under reduced pressure with an evaporator once or The polyamic acid can be purified by a method of several times.

[Polyimide]
The polyimide can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid obtained as described above. At this time, all of the amic acid structure may be dehydrated and closed to completely imidize, or only a part of the amic acid structure may be dehydrated and closed to form a partially imidized product in which the amic acid structure and the imide structure coexist. Also good.
The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) 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 imidized polymer obtained may decrease. The reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 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, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the polyamic acid structural unit. 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 closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. 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., and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 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 dehydrating ring-closing 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.

[Other polyorganosiloxane (C2)]
As the other polyorganosiloxane (C2), for example, at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter also referred to as “raw material silane compound”) is preferable. It can be synthesized by hydrolysis or hydrolysis / condensation in the presence of water and a catalyst in an organic solvent.
Examples of the raw material silane compound that can be used here include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert- Butoxysilane, tetrachlorosilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane , Methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxy Lan, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; dimethyldimethoxysilane, dimethyldiethoxysilane, Examples include dimethyldichlorosilane; trimethylmethoxysilane, trimethylethoxysilane, and trimethylchlorosilane. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane are preferred.

Examples of organic solvents that can optionally be used in the synthesis of other polyorganosiloxanes 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 ethyl hexanediol-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, partial ethers of a polyhydric alcohol compounds such as dipropylene glycol monopropyl ether, etc., can be exemplified 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. Each of the β-diketone compounds and the like can be mentioned. 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, 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, diethylene ether 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 other polyorganosiloxane is preferably 0.5 to 100 moles, more preferably 1 to 1 mole of the total amount of alkoxyl groups and halogen atoms in the raw material silane compound. It is preferably ˜30 mol, and more preferably 1 to 1.5 mol.
Examples of catalysts that can be used in the synthesis of other polyorganosiloxanes include metal chelate compounds, organic acids, inorganic acids, organic bases, ammonia, and alkali metal compounds.

  Examples of the metal chelate compound include 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, 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 thereof include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.
Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclo. Nonane, diazabicycloundecene, tetramethylammonium hydroxide, and the like can be given.
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 with respect to 100 parts by weight of the raw material silane compound.
Water added during the synthesis of other polyorganosiloxane (C2) can be added intermittently or continuously in the raw material silane compound or in a solution of the silane compound dissolved 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 in the synthesis of the other polyorganosiloxane (C2) 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.

[Use ratio of other polymer (C)]
When the liquid crystal aligning agent of this invention contains another polymer (C) with the above-mentioned polyorganosiloxane (A), as a content rate of another polymer, polyorganosiloxane (A) 100 weight The amount is preferably 10,000 parts by weight or less based on parts. The more preferable content ratio of the other polymer (C) varies depending on the type of the other polymer.
More preferable use ratio of both in the case where the liquid crystal aligning agent of the present invention contains at least one polymer (C1) selected from the group consisting of polyorganosiloxane (A) and polyamic acid and polyimide, The total amount of polyamic acid and polyimide with respect to 100 parts by weight of the polyorganosiloxane (A) is 200 to 5,000 parts by weight.
On the other hand, when the liquid crystal aligning agent of the present invention contains a polyorganosiloxane (A) and another polyorganosiloxane (C2), the more preferable use ratio of both is 100 parts by weight of the polyorganosiloxane (A). The amount of the other polyorganosiloxane (C2) is 100 to 2,000 parts by weight.
When the liquid crystal aligning agent of this invention contains another polymer (C) with a polyorganosiloxane (A), as a kind of other polymer (C), it is from the group which consists of a polyamic acid and a polyimide. It is preferably at least one polymer (C1) selected, or other polyorganosiloxane (C2). The other polymer (C) is particularly preferably at least one polymer (C1) selected from the group consisting of polyamic acid and polyimide.

[Epoxy compound]
The said epoxy compound can be contained in the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness with respect to the substrate surface of the liquid crystal aligning film formed. Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′— Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-dia Bruno diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - such as aminomethyl cyclohexane may be mentioned as preferred. The blending ratio of these epoxy compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the total of the polymers (the total of the polyorganosiloxane (A) and the other polymer (C); the same shall apply hereinafter). More preferably, it is 0.1-30 weight part. When the liquid crystal aligning agent of the present invention contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of efficiently causing an epoxy group crosslinking reaction.

[Functional silane compounds]
The said functional silane compound can be used in order to improve the adhesiveness with the board | substrate of the liquid crystal aligning film obtained. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3. -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltri Methoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7 Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And patents Document 17 is described in (JP 63-291922 JP), and the like reaction product of a silane compound having a tetracarboxylic dianhydride and an amino group.
When the liquid crystal aligning agent of the present invention contains a functional silane compound, the content ratio is preferably 50 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the total polymer. is there.

[Curing agent, curing catalyst]
The curing agent and the curing catalyst can be contained in the liquid crystal aligning agent of the present invention for the purpose of strengthening the cross-linking of the polyorganosiloxane (A) and increasing the strength of the liquid crystal alignment film, respectively. When the liquid crystal aligning agent of this invention contains a hardening | curing agent, you may use a hardening accelerator together.
As the curing agent, a curing agent generally used for curing an epoxy group can be used. As such a curing agent, for example, a polyvalent amine, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid can be used. Specific examples of the polyvalent carboxylic acid anhydride include cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid and the like. Examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1 , 2,3-tricarboxylic acid-2,3-acid anhydride, 4-methyltetrahydrophthalic acid anhydride, methyl nadic acid anhydride, dodecenyl succinic acid anhydride, as well as conjugated double bonds such as α-terpinene and alloocimene Used in the synthesis of Diamic-Alder reaction products of alicyclic compounds with maleic anhydride and their hydrogenated products, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, and polyamic acid Examples of the tetracarboxylic dianhydride include the compounds exemplified above.
Examples of the curing accelerator include diazabicycloalkenes such as imidazole compounds, quaternary phosphorus compounds, quaternary amine compounds, 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and stannic chloride,
High melting point dispersion type latent curing accelerators such as amine addition accelerators such as dicyandiamide and adducts of amine and epoxy resin;
Microcapsule-type latent curing accelerator in which the surface of a curing accelerator such as quaternary phosphonium salt is coated with a polymer; amine salt-type latent curing accelerator; high-temperature dissociation type such as Lewis acid salt and Bronsted acid salt And a latent curing accelerator such as a thermal cationic polymerization type latent curing accelerator.
Examples of the curing catalyst that can be used include an antimony hexafluoride compound, a phosphorus hexafluoride compound, and aluminum trisacetylacetonate.
[Surfactant]
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. it can.
When the liquid crystal aligning agent of this invention contains surfactant, as the content rate, Preferably it is 10 weight part or less with respect to 100 weight part of the whole liquid crystal aligning agent, More preferably, it is 1 weight part or less. is there.

<Liquid crystal aligning agent>
As described above, the liquid crystal aligning agent of the present invention contains the polyorganosiloxane (A) and the compound (B) as essential components, and additionally contains other components as necessary. It is prepared as a solution composition in which the components are dissolved in an organic solvent.
As an organic solvent that can be used to prepare the liquid crystal aligning agent of the present invention, polyorganosiloxane (A) and compound (B) and other optional components are dissolved and do not react with these. Those are preferred.
The preferable organic solvent that can be preferably used in the liquid crystal aligning agent of the present invention varies depending on the type of the other polymer (C) that is optionally added.
As a preferable organic solvent in the case where the liquid crystal aligning agent of the present invention contains at least one polymer (C1) selected from the group consisting of polyorganosiloxane (A) and polyamic acid and polyimide, The organic solvent illustrated above can be mentioned as what is used for a synthesis | combination. These organic solvents can be used alone or in combination of two or more.
On the other hand, the liquid crystal aligning agent of the present invention contains only polyorganosiloxane (A) as a polymer, or contains polyorganosiloxane (A) and other polyorganosiloxane (C2). Examples of preferred organic solvents include 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, and dipropylene glycol ethyl. Ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Recall monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, Propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, acetic acid Methylpentyl, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate , Amyl acetate, acetic acid isoamyl, and the like. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate and the like can be mentioned.

A preferred solvent used in the preparation of the liquid crystal aligning agent of the present invention is obtained by combining one or more of the above-mentioned organic solvents according to the presence or absence of other polymers and their types, Each component contained in the liquid crystal aligning agent does not precipitate at a preferable solid content concentration, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mN / m.
The solid content concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, Preferably it is the range of 1-10 weight%. The liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the film thickness of this coating film becomes too small. In some cases, it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal alignment agent increases, resulting in insufficient coating characteristics. There is a case. The particularly preferable range of the solid content concentration varies depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by weight is particularly preferable. 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 for preparing the liquid crystal aligning agent of the present invention is preferably 0 ° C. to 200 ° C., more preferably 10 ° C. to 60 ° C.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention as described above.
The method of forming a liquid crystal alignment film using the liquid crystal aligning agent of the present invention has the structure having the liquid crystal aligning ability of the compound a used for the synthesis of the liquid crystal aligning polyorganosiloxane in the present invention (therefore, polyorganosiloxane). It differs depending on whether or not the structure having the liquid crystal alignment ability in the group X ′ in (A) has the structure represented by the above formula (X′-1).
When the polyorganosiloxane (A) does not have the structure represented by the above formula (X′-1), the liquid crystal aligning agent of the present invention is applied on the substrate to form a coating film. By performing rubbing treatment accordingly, a liquid crystal alignment film can be obtained.
On the other hand, when the polyorganosiloxane (A) has a structure represented by the above formula (X′-1), the liquid crystal aligning agent of the present invention is applied onto the substrate to form a coating film. Then, a liquid crystal alignment film can be obtained by irradiating the coating film with radiation.

[When the polyorganosiloxane (A) does not have a structure represented by the above formula (X′-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. As a pair of two substrates provided with a patterned transparent conductive film, the liquid crystal aligning agent of the present invention, preferably a roll coater method, a spinner method, a printing method, an inkjet, is formed on each transparent conductive film forming surface. Apply each method. Then, the coated surface is preheated (prebaked) and then baked (postbaked) to form a coating film. The pre-bake conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-bake conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
Examples of the substrate include glass such as float glass and soda glass; and a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and alicyclic polyolefin.

As the 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. Can be used. To obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when forming a transparent conductive film, etc. be able to. When 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.
When the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film for a vertical alignment type liquid crystal display element, the coating film formed as described above is used as it is for a liquid crystal alignment film for a vertical alignment type liquid crystal display element. However, rubbing treatment may optionally be performed on the coating surface. On the other hand, when the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film for a horizontal alignment type liquid crystal display element, the coating film formed as described above is subjected to rubbing treatment to obtain a liquid crystal alignment film can do.
The rubbing treatment can be performed, for example, by rubbing in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton. In this case, as shown in, for example, Patent Document 18 (JP-A-6-222366), Patent Document 19 (JP-A-6-281937), etc. The surface of the liquid crystal alignment film may be subjected to a treatment for changing the pretilt angle by irradiating a part of the film with ultraviolet rays, or as shown in Patent Document 20 (Japanese Patent Laid-Open No. 5-107544). A resist film is formed on a part of the film, and then the rubbing process is performed in a direction different from the previous rubbing process, and then the resist film is removed, so that the liquid crystal alignment film has a different liquid crystal alignment ability for each region. Thus, the visual field characteristics of the obtained horizontal liquid crystal display element may be improved.

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. 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.
In any case, it is desirable to remove the flow alignment at the time of injection by heating the liquid crystal cell to a temperature at which the liquid crystal used has an isotropic phase and then slowly cooling it to room temperature.
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.

As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.
As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. When manufacturing a liquid crystal display element having a TN liquid crystal cell or an STN liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy (positive liquid crystal) is preferable, for example, a biphenyl liquid crystal or a phenylcyclohexane system. Liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal and the like are used. For example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names C-15 and CB-15 (manufactured by Merck); A ferroelectric liquid crystal such as p-amino-2-methylbutyl cinnamate may be further added and used.
On the other hand, in the case of a vertical alignment type liquid crystal cell, a nematic type liquid crystal having negative dielectric anisotropy (negative type liquid crystal) is preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal Type liquid crystal, biphenyl type liquid crystal, phenylcyclohexane type liquid crystal and the like are used.
The polarizing plate used outside the liquid crystal cell is composed of a polarizing film called a “H film” in which iodine is absorbed while stretching and orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate etc. can be mentioned.

[When the polyorganosiloxane (A) has a structure represented by the above formula (X′-1)]
In this case, in the method for producing a liquid crystal alignment film when the polyorganosiloxane (A) does not have the structure represented by the formula (X′-1), a radiation irradiation treatment is performed instead of the rubbing treatment. Thus, a liquid crystal display element can be manufactured.
As the radiation used for the radiation irradiation treatment, linearly polarized light, partially polarized radiation, or non-polarized radiation can be used. For example, ultraviolet rays or visible rays including light having a wavelength of 150 to 800 nm are used. However, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination thereof. May be. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction.
As a light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, 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 or a diffraction grating.
The irradiation dose of radiation, preferably less than 1 J / ^{m 2} or more 10,000 J / ^{m 2,} more preferably from 10~3,000J / ^{m 2.} In addition, when providing the liquid crystal aligning ability by the photo-alignment method to the coating film formed from the conventionally known liquid crystal aligning agent, the irradiation dose of 10,000 J / m < ² > or more was required. However, using the liquid crystal aligning agent of the present invention, the radiation dose at the time of photo-alignment method is 3,000 J / ^{m 2} or less, further 1,000 J / ^{m 2} or less, excellent even in particular 500 J / ^{m 2} or less Liquid crystal orientation can be imparted, which contributes to a reduction in manufacturing cost of the liquid crystal display element.

The liquid crystal display element of the present invention is preferably a vertical alignment type liquid crystal display element.
The liquid crystal display element of the present invention thus produced is excellent in heat resistance, light resistance and electrical characteristics, and excellent in stability over time of the pretilt angle even when the photo-alignment method is adopted in the formation of the liquid crystal alignment film. It is.

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 examples, the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Corporation, TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
The epoxy equivalent was measured according to the “hydrochloric acid-methyl ethyl ketone method” of JIS C2105.
The following synthesis examples were repeated at the following synthesis scale as necessary to secure the necessary amount of product to be used in the following synthesis examples and examples.

<Synthesis of polyorganosiloxane having epoxy structure>
Synthesis example 1
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine at room temperature. Mixed with. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure, whereby polyorganosiloxane EPS-1 Was obtained as a viscous transparent liquid.
When this polyorganosiloxane EPS-1 was subjected to ¹ H-NMR analysis, a peak based on the oxiranyl group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no reaction occurred.
This polyorganosiloxane EPS-1 had an Mw of 2,200 and an epoxy equivalent of 186.
<Synthesis of Compound a>
Synthesis example a-1
Scheme 1 below

According to the above, compound (A-1-C1-1) was synthesized.
A 1 L eggplant-shaped flask was charged with 82 g of p-hydroxycinnamic acid, 304 g of potassium carbonate and 400 mL of N-methyl-2-pyrrolidone, stirred at room temperature for 1 hour, and then added with 166 g of 1-bromopentane at 100 ° C. Stir for 5 hours. Thereafter, the solvent was distilled off under reduced pressure. To this, 48 g of sodium hydroxide and 400 mL of water were added and refluxed for 3 hours to conduct a hydrolysis reaction. After completion of the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was collected and recrystallized with ethanol to obtain 80 g of white crystals of the compound (A-1-C1-1).
Synthesis example a-2
Scheme 2 below

According to the above, compound (A-1-C4-1) was synthesized.
A 1 L eggplant-shaped flask was charged with 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate, and 320 mL of N-methyl-2-pyrrolidone, stirred at room temperature for 1 hour, and then charged with 99. 1-bromopentane. 7 g was added and reacted at 100 ° C. for 5 hours with stirring. After completion of the reaction, reprecipitation was performed with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate and refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 104 g of white crystals of the compound (A-1-C4-1A).
104 g of this compound (A-1-C4-1A) was placed in a reaction vessel, 1 L of thionyl chloride and 770 μL of N, N-dimethylformamide were added thereto, and the mixture was stirred at 80 ° C. for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with an aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, concentrated, and then tetrahydrofuran was added to form a solution.
Next, 74 g of 4-hydroxycinnamic acid, 138 g of potassium carbonate, 4.8 g of tetrabutylammonium, 500 mL of tetrahydrofuran, and 1 L of water were charged into a 5 L three-necked flask different from the above. This aqueous solution was ice-cooled, and a tetrahydrofuran solution containing a reaction product of the above compound (A-1-C4-1A) and thionyl chloride was slowly added dropwise, and the reaction was further performed with stirring for 2 hours. After completion of the reaction, the reaction mixture was neutralized by adding hydrochloric acid, extracted with ethyl acetate, the extract was dried over magnesium sulfate, concentrated, and recrystallized with ethanol to give compound (A-1 90 g of white crystals of -C4-1) were obtained.
Synthesis example a-3
Scheme 3 below

According to the above, compound (A-1-C4-2) was synthesized.
A 1 L eggplant-shaped flask was charged with 82 g of methyl 4-hydroxybenzoate, 166 g of potassium carbonate, and 400 mL of N, N-dimethylacetamide, stirred at room temperature for 1 hour, and then 4,4,4-trifluoro-1-iodobutane. 95 g was added, and the reaction was carried out at room temperature with stirring for 5 hours. After completion of the reaction, reprecipitation was performed with water. Next, 32 g of sodium hydroxide and 400 mL of water were added to the precipitate and refluxed for 4 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 80 g of white crystals of the compound (A-1-C4-2A).
46.4 g of this compound (A-1-C4-2A) was placed in a reaction vessel, and 200 mL of thionyl chloride and 0.2 mL of N, N-dimethylformamide were added thereto, followed by stirring at 80 ° C. for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with an aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, concentrated, and then tetrahydrofuran was added to form a solution.
Next, 36 g of 4-hydroxycinnamic acid, 55 g of potassium carbonate, 2.4 g of tetrabutylammonium, 200 mL of tetrahydrofuran and 400 mL of water were charged into a 2 L three-necked flask different from the above. This aqueous solution was ice-cooled, a tetrahydrofuran solution containing a reaction product of the above compound (A-1-C4-2A) and thionyl chloride was slowly added dropwise, and the reaction was further performed with stirring for 2 hours. After completion of the reaction, the reaction mixture was neutralized by adding hydrochloric acid, extracted with ethyl acetate, the extract was dried over magnesium sulfate, concentrated, and recrystallized with ethanol to give compound (A-1 39 g of white crystals of -C4-2) were obtained.
Synthesis example a-4
Scheme 4 below

Thus, compound (A-1-C8-1) was synthesized.
That is, in the above synthesis example a-2, except that 9.91 g of 4-pentyl-transcyclohexylcarboxylic acid was used instead of the compound (A-1-C4-1A), By carrying out similarly to the synthesis | combination of 1-C4-1), 13g of white crystals of the compound (A-1-C8-1) were obtained.
Synthesis example a-5
Scheme 5 below

According to the above, compound (A-1-C16-1) was synthesized.
In a 500 mL three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, 31 g of compound (A-1-C16-1A), 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine, 56 mL of triethylamine, Acrylic acid 8.2mL and N, N- dimethylacetamide 200mL were prepared, and it reacted with stirring at 120 degreeC for 3 hours. After completion of the reaction, the organic layer obtained by adding 1 L of ethyl acetate to the filtrate obtained by filtering the reaction solution was separated and washed successively with dilute hydrochloric acid twice and water three times. Thereafter, the organic layer was dried over magnesium sulfate, concentrated and dried, and then recrystallized with a mixed solvent of ethyl acetate and tetrahydrofuran to obtain 15 g of crystals of the compound (A-1-C16-1).
Synthesis example a-6
Scheme 6 below

According to the above, compound (A-1-C17-1) was synthesized.
That is, by carrying out in the same manner as in Synthesis Example a-5 except that 36 g of compound (A-1-C17-1A) was used instead of compound (A-1-C16-1A), compound (A- 16 g of 1-C17-1) was obtained.
Synthesis Example a-7
Scheme 7 below

Thus, compound (A-4-C1-1) was synthesized.
A 200 mL eggplant flask equipped with a reflux tube was charged with 12 g of decyl succinic anhydride, 8.2 g of 4-aminocinnamic acid and 100 mL of acetic acid, and reacted under reflux for 2 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, the organic layer was washed with water, dried over magnesium sulfate, purified on a silica column, and recrystallized with a mixed solvent of ethanol and tetrahydrofuran. 10 g of white crystals (purity 98.0%) of compound (A-4-C1-1) was obtained.
Synthesis Example a-8
In the synthesis example a-5, the same procedure as in the synthesis example a-5 except that 28 g of the compound (A-1-C16-2A) represented by the following formula was used instead of the compound (A-1-C16-1A). As a result, 14 g of a crystal of the compound (A-1-C16-2) represented by the following formula was obtained.

Synthesis Example a-9
Scheme 8 below

Thus, compound (A-9-4-1) was synthesized.
A 500 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube was charged with 39 g of β-cholestanol, 20 g of succinic anhydride, 1.5 g of N, N-dimethylaminopyridine, 200 mL of ethyl acetate and 17 mL of triethylamine and refluxed for 8 hours. The reaction was performed below. After completion of the reaction, the organic layer obtained by adding 200 mL of tetrahydrofuran to the reaction mixture was washed successively with 1N aqueous hydrochloric acid twice and with water three times, dried over magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained solid was recrystallized from ethyl acetate to obtain 38 g of white crystals of the compound (A-9-4-1).

<Synthesis of polyorganosiloxane (A)>
Synthesis Example VE-1
In a 200 mL three-necked flask, 10.0 g of polyorganosiloxane EPS-1 synthesized in Synthesis Example 1 above, 30.28 g of methyl isobutyl ketone, 3.82 g of stearic acid (based on the epoxy group of polyorganosiloxane EPS-1) 0.10 g of UCAT 18X (trade name, manufactured by San Apro Co., Ltd., an epoxy compound curing accelerator) and charged at 100 ° C. for 48 hours with stirring. . After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. A solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and the organic layer was dried using magnesium sulfate. By leaving, 8.1 g of white powder of polyorganosiloxane S-VE-1 was obtained. The weight average molecular weight of S-VE-1 was 10,100.
Synthesis Example VE-2
The same procedure as in Synthesis Example VE-1, except that 3.98 g of 4-n-dodecyloxybenzoic acid was used instead of stearic acid in Synthesis Example VE-1, and polyorganosiloxane S-VE-2 9.0 g of white powder was obtained. The weight average molecular weight of S-VE-2 was 9,900.

Synthesis Example CE-1
In a 200 mL three-necked flask, 5.0 g of polyorganosiloxane EPS-1 obtained in Synthesis Example 1 above, 46.4 g of methyl isobutyl ketone, and compound a obtained in Synthesis Example a-2 as Compound a (A-1-C4) -1) 4.76 g (corresponding to 50 mol% with respect to the epoxy group possessed by polyorganosiloxane EPS-1) and 0.10 g of tetrabutylammonium bromide were charged, and the reaction was conducted at 80 ° C. with stirring for 8 hours. It was. After completion of the reaction, reprecipitation with methanol was performed, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed with water three times, and then the solvent was distilled off to obtain polyorganosiloxane S-CE-1. As a white powder, 2.8 g was obtained. The weight average molecular weight Mw of this polyorganosiloxane S-CE-1 was 9,500.
Synthesis Example CE-2 to 12
In Synthesis Example CE-1, the same procedure as in Synthesis Example CE-1 was carried out except that the compound described in Table 1 was used as compound a instead of compound (A-1-C4-1). Polyorganosiloxane (A) was synthesized. The weight average molecular weight Mw of each polyorganosiloxane obtained here is shown in Table 1 together.
The use ratio of compound a in Table 1 is mol% with respect to the epoxy group of polyorganosiloxane EPS-1.
In Synthesis Examples CE-6 to 8 and 12, two types of compounds a were used.

<Synthesis of Compound (B)>
Synthesis Example B-1
Scheme 9 below

Thus, compound (B-1-1) was synthesized.
A 500 mL three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube was charged with 21 g of trimesic acid, 60 g of n-butyl vinyl ether and 0.09 g of phosphoric acid, and reacted at 50 ° C. with stirring for 30 hours. After completion of the reaction, the organic layer obtained by adding 500 mL of hexane to the reaction mixture was separated and washed successively with 1M aqueous sodium hydroxide solution twice and water three times. Then, 50g of compounds (B-1-1) were obtained as a colorless and transparent liquid by distilling a solvent off from an organic layer.
Synthesis Examples B-2 and 3
In the synthesis example B-1, in the same manner as in the synthesis example B-1, except that 17 g of isophthalic acid or 35 g of the compound represented by the following formula (B-1-3a) was used instead of trimesic acid, 45 g of a compound represented by the following formula (B-1-2) and 63 g of a compound represented by the following formula (B-1-3) were obtained.

<Synthesis of other polymer (C)>
[Synthesis of polyamic acid]
Synthesis example PA-1
196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g (1, .2) of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine. 0 mol) was dissolved in 4,050 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours to obtain 4,400 g of a solution containing 10% by weight of polyamic acid (PA-1). The solution viscosity of this polyamic acid solution was 170 mPa · s.
Synthesis example PA-2
As tetracarboxylic dianhydride, 86.3 g (0.44 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 96.0 g (0.44 mol) of pyromellitic dianhydride and as diamine Polyamic acid was obtained by dissolving 191.0 g (0.90 mol) of 2,2′-dimethyl-4,4′-diaminobiphenyl in 1,490 g of N-methyl-2-pyrrolidone and reacting at 40 ° C. for 4 hours. A solution containing 20% by weight of (PA-2) was obtained. A small amount of this polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added to a concentration of 10% by weight. The viscosity of the solution was 43 mPa · s.
[Synthesis of polyimide]
Synthesis example PI-1
As tetracarboxylic dianhydride, 20.9 g (0.093 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 9.2 g (0.085 mol) of p-phenylenediamine as diamine and the following formula ( D-2)

A solution containing polyamic acid was obtained by dissolving 4.9 g (0.009 mol) of the compound represented by formula (I) in 140 g of N-methyl-2-pyrrolidone and reacting at 60 ° C. for 4 hours. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polymer concentration of 10% by weight. As a result, it was 126 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 7.4 g of pyridine and 9.5 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, whereby about 210 g of a solution containing 16.1% by weight of polyimide (PI-1) having an imidation ratio of about 54% Got.
A small amount of this polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 75 mPa · s.

Synthesis example PI-2
2,3,5-tricarboxycyclopentylacetic acid dianhydride 20.0 g (0.089 mol) as tetracarboxylic dianhydride and 6.8 g (0.063 mol) p-phenylenediamine as diamine, 4,4 ′ -3.6 g (0.018 mol) of diaminodiphenylmethane and 4.7 g (0.0090 mol) of the compound represented by the above formula (D-2) were dissolved in 140 g of N-methyl-2-pyrrolidone and dissolved at 60 ° C. By reacting for 4 hours, a solution containing 20% by weight of polyamic acid was obtained. When the solution viscosity of the obtained polyamic acid solution was measured, it was 2,200 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 10.5 g of pyridine and 13.6 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solution in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain about 160 g of a solution containing 20% by weight of polyimide (PI-2) having an imidation ratio of about 65%. It was.
Synthesis example PI-3
19.2 g (0.086 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 5.2 g (0.034 mol) of 3,5-diaminobenzoic acid as diamine and Formula (D-3)

Was dissolved in 200 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid. When the solution viscosity of the obtained polyamic acid solution was measured, it was 1,450 mPa · s.
Next, 250 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 10.2 g of pyridine and 13.2 g of acetic anhydride were added, and a dehydration ring-closing reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solution in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain about 230 g of a solution containing 20% by weight of polyimide (PI-3) having an imidation ratio of about 67%. It was.
Synthesis example PI-4
2,3,5-tricarboxycyclopentylacetic acid dianhydride 21.3 g (0.095 mol) as tetracarboxylic dianhydride and 4.3 g (0.029 mol) 3,5-diaminobenzoic acid as diamine, as described above 18.8 g (0.038 mol) of the compound represented by the formula (D-3) and the following formula (D-4)

By dissolving 5.5 g (0.029 mol) of N- (2,4-diaminophenyl) -piperidine in 200 g of N-methyl-2-pyrrolidone and reacting at 60 ° C. for 4 hours. A solution containing 20% by weight of polyamic acid was obtained. It was 900 mPa * s when the solution viscosity of the obtained polyamic acid solution was measured.
Next, 250 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 11.29 g of pyridine and 14.58 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 solution in the system was solvent-substituted with new N-methyl-2-pyrrolidone to obtain about 230 g of a solution containing 20% by weight of polyimide (PI-4) having an imidation ratio of about 69%. It was.

Synthesis example PI-5
2,2.9-tricarboxycyclopentylacetic acid dianhydride 22.9 g (0.10 mol) as tetracarboxylic dianhydride and 6.7 g (0.062 mol) m-phenylenediamine as diamine and the above formula (D -4) 20.4 g (0.041 mol) of the compound represented by N-methyl-2-pyrrolidone is dissolved in 200 g and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid. Obtained. It was 1,200 mPa * s when the solution viscosity of the obtained polyamic acid solution was measured.
Next, 250 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 12.12 g of pyridine and 15.64 g of acetic anhydride were added, and a dehydration ring-closing reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solution in the system is solvent-substituted with new N-methyl-2-pyrrolidone, thereby obtaining about 230 g of a solution containing 20% by weight of polyimide (PI-5) having an imidation ratio of about 65%. It was.

[Synthesis of other polyorganosiloxane (C2)]
Synthesis example PS-1
In a 200 mL three-necked flask equipped with a condenser, 20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol were charged, heated to 60 ° C. and stirred. A maleic anhydride aqueous solution prepared by dissolving 0.26 g of maleic anhydride in 10.8 g of water, which was prepared in another flask having a volume of 20 mL, was added thereto, and the reaction was further performed at 60 ° C. with stirring for 4 hours. After completion of the reaction, the solvent was distilled off from the obtained reaction mixture, 1-ethoxy-2-propanol was added to the residue, and the mixture was concentrated again to obtain a solution containing 10% by weight of polyorganosiloxane PS-1. Obtained. It was 5,100 when the weight average molecular weight Mw of this polyorganosiloxane PS-1 was measured.

<Preparation of liquid crystal aligning agent and evaluation of storage stability>
Example VE-1
As another polymer (C), an amount corresponding to 1,000 parts by weight in terms of PA-1 of a solution containing the polyamic acid PA-1 synthesized in the above synthesis example PA-1 was taken. 100 parts by weight of polyorganosiloxane S-VE-1 synthesized in Synthesis Example VE-1 as siloxane (A) and Compound (B-1-1) 47 obtained in Synthesis Example B-1 as Compound (B) Part by weight, N-methyl-2-pyrrolidone and butyl cellosolve are added, and the solvent composition is N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio) and a solid content concentration of 3.0% by weight. It was. The solution was filtered through a filter having a pore size of 1 μm to prepare liquid crystal aligning agent A-VE-1.
When the storage stability of this liquid crystal aligning agent A-VE-1 was evaluated by the following method and criteria, the storage stability of liquid crystal aligning agent A-VE-1 was “good”.
[Storage Stability Evaluation Method (1)]
On a glass substrate, a liquid crystal aligning agent is applied by changing the number of rotations by a spin coating method, and then heated at 200 ° C. for 60 minutes to form a coating film. After removing the solvent, the coating film has a thickness of 1,000 mm. The number of revolutions 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 “bad”.
If no insoluble matter was observed after storage for 5 weeks, it was further coated on a glass substrate by spin coating at a rotational speed of 1,000 mm before storage using a liquid crystal aligning agent after storage. Then, a film was formed by heating at 200 ° C. for 60 minutes, and the film thickness after removing the solvent 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 by KLA-Tencor.

Examples VE-2-4
Liquid crystal aligning agent A-VE-2 was carried out in the same manner as in Example VE-1, except that the type and amount of polyorganosiloxane (A) and compound (B) were as shown in Table 2. Each of ˜4 was prepared and evaluated for storage stability. The evaluation results are shown in Table 2.
Example VE-5
The amount corresponding to 500 parts by weight in terms of PS-1 of the solution containing polyorganosiloxane PS-1 synthesized in the above synthesis example PS-1 was taken, and this was added to the polyorgano synthesized in the above synthesis example VE-1. 100 parts by weight of siloxane S-VE-1 and 43 parts by weight of the compound (B-1-2) synthesized in Synthesis Example B-2 were added, and 1-ethoxy-2-propanol was further added to obtain a solid content concentration of 4. The solution was 0% by weight. The solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent A-VE-5.
The storage stability of this liquid crystal aligning agent A-VE-5 was evaluated in the same manner as in Example VE-1. The evaluation results are shown in Table 2.

<Manufacture and evaluation of vertical alignment type liquid crystal display element>
Example VE-6
The liquid crystal aligning agent A-VE-1 prepared in Example VE-1 was applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a spinner, and then on a hot plate at 80 ° C. for 1 minute. After pre-baking, the coating film (liquid crystal aligning film) with a film thickness of 0.1 μm was formed by heating at 200 ° C. for 1 hour in an oven substituted with nitrogen. This operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing, and then the liquid crystal alignment film surfaces of the pair of substrates are overlapped. The adhesive was heat-cured by heating 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, a vertical alignment type liquid crystal display element was manufactured by bonding polarizing plates on both outer surfaces of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other.

[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 the voltage of 5 V was turned ON / OFF (applied / released) in the liquid crystal display element manufactured above was visually observed.
When the voltage is off, light leakage from the cell is not observed, the cell drive area is displayed white when voltage is applied, and no light leakage from other areas. When it was observed or when light leakage was observed from a region other than the cell drive region when the voltage was ON, the liquid crystal alignment property was evaluated as “Poor”.
(2) Evaluation of voltage holding ratio After applying a voltage of 5 V to the liquid crystal display element manufactured above at 60 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, 167 milliseconds after the application release. The voltage holding ratio was measured. As a voltage holding ratio measuring apparatus, VHR-1 manufactured by Toyo Corporation was used. When the voltage holding ratio was 97% or more was evaluated as “good”, the voltage holding ratio of this liquid crystal display element was “good”. (3) Evaluation of heat resistance For the liquid crystal display element, the initial voltage holding ratio was measured under the same conditions as in the evaluation of the voltage holding ratio. Then, after leaving still in a 120 degreeC oven for 1,000 hours, the voltage holding rate was measured on the same conditions as the above again. When the voltage holding ratio was less than ± 2% compared to the initial value, the heat resistance was evaluated as “good”, and when it was ± 2% or higher, the heat resistance was evaluated as “bad”. The heat resistance of the device was “good”.
(4) Evaluation of afterimage characteristics For a liquid crystal display device manufactured in the same manner as described above, a voltage of 17 V DC was applied for 20 hours at an environmental temperature of 100 ° C., and the voltage remaining in the liquid crystal cell immediately after the DC voltage was turned off ( Residual DC voltage) was determined by the flicker elimination method. When the residual DC voltage value was 500 mV or less, the heat resistance was “good”, and when the residual DC voltage was more than 500 mV, the heat resistance was “bad”. The afterimage characteristics of the liquid crystal display element were “good”. .

Examples VE-7-10
In Example VE-6, vertical alignment liquid crystal display elements were produced and evaluated in the same manner as in Example VE-6, except that the liquid crystal alignment agents shown in Table 3 were used. The results are shown in Table 3.

<Preparation of liquid crystal aligning agent and evaluation of storage stability>
Example CE-1
100 parts by weight of polyorganosiloxane S-CE-1 obtained in Synthesis Example CE-1 as polyorganosiloxane (A), and polyamic acid PA- obtained in Synthesis Example PA-1 as another polymer (C) The amount corresponding to 2,000 parts by weight in terms of PA-1 of the solution containing 1 and 41 parts by weight of the compound (B-1-2) obtained in Synthesis Example B-2 as the compound (B) are combined. N-methyl-2-pyrrolidone and butyl cellosolve were added thereto to obtain a solution having a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio) and a solid content concentration of 3.0% by weight. The solution was filtered through a filter having a pore size of 1 μm to prepare liquid crystal aligning agent A-CE-1.
When the storage stability of this liquid crystal aligning agent A-CE-1 was evaluated by the following method and criteria, the storage stability of the liquid crystal aligning agent A-CE-1 was “good”.
[Storage Stability Evaluation Method (2)]
The liquid crystal aligning agent was stored at −15 ° C. for 6 months. The viscosity was measured with an E-type viscometer at 25 ° C. before and after storage. When the change rate of the solution viscosity before and after storage was less than 10%, the storage stability was evaluated as “good”, and when it was 10% or more, the storage stability was evaluated as “bad”.

Examples CE-2 to 31
A liquid crystal aligning agent A-CE- was prepared in the same manner as in Example CE-1, except that the type of polyorganosiloxane (A) and the type of other polymer (C) were as shown in Table 4. 2-A-CE-31 was prepared respectively. In Examples CE-30 and 31, two other polymers were used.
With respect to these liquid crystal aligning agents, the storage stability was evaluated in the same manner as in Example CE-1. The evaluation results are shown in Table 4.

<Manufacture and evaluation of vertical alignment type liquid crystal display element>
Example CE-32
[Manufacture of vertical alignment type liquid crystal display elements]
The liquid crystal aligning agent A-CE-1 prepared in Example CE-1 was applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner, and then on a hot plate at 80 ° C. for 1 minute. After pre-baking, it was heated at 200 ° C. for 1 hour in an oven in which the inside of the cabinet was replaced with nitrogen to form a coating film having a thickness of 0.1 μm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays 200 J / m ² containing a 313 nm emission line from a direction inclined by 40 ° from the normal to the liquid crystal alignment film using a Hg—Xe lamp and a Grand Taylor prism. The same operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface of the substrate having the liquid crystal alignment film by screen printing, and the liquid crystal alignment film surfaces of the pair of substrates are made to face each other. The adhesive was pressure-bonded so that the projection direction of the optical axis of the ultraviolet rays of each substrate onto the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, after filling the gap between the substrates from the liquid crystal injection port with negative type liquid crystal (MLC-6608, manufactured by Merck), the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 150 ° C. and then gradually cooled to room temperature. Next, the polarizing plates are bonded to both the outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and form an angle of 45 ° with the projection direction of the optical axis of the liquid crystal alignment film onto the substrate surface. A vertically aligned liquid crystal display device was manufactured.

[Evaluation of vertical alignment liquid crystal display element]
The liquid crystal display device produced as described above was subjected to (1) evaluation of liquid crystal orientation and (3) evaluation of heat resistance in the same manner as in Example VE-6. (2) The voltage holding ratio was measured in the same manner as in 6. Furthermore, the stability of the pretilt angle was evaluated as follows. The evaluation results are shown in Table 5.
(5) Evaluation of stability of pretilt angle The liquid crystal display device manufactured as described above is disclosed in Non-Patent Document 2 (TJ Scheffer et. Al. J. Appl. Phys. Vo. 19, p2013 (1980). The pretilt angle was measured by the crystal rotation method using He—Ne laser light in accordance with the method described in (1).
Next, the liquid crystal display element after the initial pretilt angle measurement was allowed to stand at 23 ° C. for 30 days, and then the pretilt angle was measured again by the same method as described above (pretilt angle after storage).
At this time, the amount of change of the pretilt angle after storage with respect to the initial pretilt angle was examined. When this value was less than 1 °, the pre-tilt angle over time was assumed to be “good”.

Example CE-33-62
A vertical alignment type liquid crystal display device was produced and evaluated in the same manner as in Example CE-32 except that the type of liquid crystal alignment agent used was as described in Table 5. The results are shown in Table 5.

Claims (11)

A polyorganosiloxane having a Si—X ′ bond (where X ′ is a group containing a structure having liquid crystal alignment ability) and a Si— ^XI bond (where X ^I is a group containing an epoxy structure) (A And at least one structure selected from the group consisting of an acetal ester structure of carboxylic acid, a ketal ester structure of carboxylic acid, a 1-alkylcycloalkyl ester structure of carboxylic acid, and a t-butyl ester structure of carboxylic acid in the molecule. Compound (B) having two or more
Liquid crystal aligning agent characterized by containing. The polyorganosiloxane (A) in the group X 'proportion of the group X' is 10 to 90 mol% based on the sum of and groups X ^I, the liquid crystal aligning agent of claim 1. The polyorganosiloxane (A) is
^{Si-X I} binding (although ^{X I} has the same meaning as ^{X I} in the polyorganosiloxane (A).) Polyorganosiloxane having,
Compounds having a structure having at least one base and the liquid crystal alignment capability is selected from a carboxyl group and a group consisting of a hydroxyl group, provided that 0.1 to 0.9 moles per mole of the proportion of the group X ^I of the compound The liquid crystal aligning agent of Claim 1 or 2 which is a reaction product with these. The group X ^I is represented by the following formula (X ^I -1 ′) or (X ^I −2 ′)

(In the formulas ( ^XI- 1 ') and ( ^XI- 2'), s is an integer of 0-3, t is an integer of 1-6, u is an integer of 0-2, v Is an integer of 0 to 6, and “*” indicates a bond.
The liquid crystal aligning agent as described in any one of Claims 1-3 which is group represented by these. The group X ^I is represented by the following formula (X ^I -1) or (X ^I -2)

(Wherein ^(X I -1) and ^(X I -2), "*", respectively, indicating that a bond.)
The liquid crystal aligning agent of Claim 4 which is group represented by these.   The structure having liquid crystal alignment ability is a group having 17 to 51 carbon atoms having a steroid skeleton, an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, or an alkyl having 1 to 20 carbon atoms. A structure containing at least one selected from the group consisting of an alkylcyclohexyl group having a group, a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, and a fluoroalkoxycyclohexyl group having a fluoroalkoxyl group having 1 to 20 carbon atoms The liquid crystal aligning agent as described in any one of Claims 1-5 which is these. The structure having the liquid crystal alignment ability is further represented by the following formula (X′-1)

(In formula (X′-1), m is an integer of 0 to 4.)
The liquid crystal aligning agent of Claim 6 which is a structure containing the structure represented by these.   Furthermore, the liquid crystal aligning agent as described in any one of Claims 1-7 containing the at least 1 type of polymer (C1) selected from the group which consists of a polyamic acid and a polyimide.   Furthermore, the liquid crystal aligning agent as described in any one of Claims 1-7 containing polyorganosiloxane (C2) other than the said polyorganosiloxane (A).   A method for forming a liquid crystal alignment film, comprising: applying a liquid crystal aligning agent according to claim 7 on a substrate; then heating to form a coating film; and irradiating the coating film with radiation.   A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1.