KR20100109474A - Liquid crystal aligning agent, process for forming liquid crystal aligning film, and liquid crystal display device - Google Patents

Abstract

This invention provides the liquid crystal aligning agent which is excellent in liquid crystal aligning property, is able to form the liquid crystal aligning film which is high in heat resistance and light resistance, and is excellent in electrical characteristics, and is excellent in storage stability.
The liquid crystal aligning agent is a polyolefin having a Si-X 'bond (where X' is a group containing a structure having liquid crystal alignment capability) and a Si-X ^I bond (where X ^I is a group containing an epoxy structure). 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 organosiloxane (A) and the molecule It contains the compound (B) which has 2 or more of 1 or more types of structures chosen.

Description

A liquid crystal aligning agent, the formation method of a liquid crystal aligning film, and a liquid crystal display element TECHNICAL FIELD [LIQUID CRYSTAL ALIGNING AGENT, PROCESS FOR FORMING LIQUID CRYSTAL ALIGNING FILM, AND LIQUID CRYSTAL DISPLAY DEVICE}

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

Currently, as a liquid crystal display element, the liquid crystal aligning film containing organic resin etc. is formed in the surface of the board | substrate with which the transparent conductive film is provided, and it is set as the board | substrate for liquid crystal display elements, The two sheets are opposingly arranged, and the positive dielectric anisotropy in the clearance gap is carried out. TN type liquid crystal having a so-called TN type liquid crystal cell in which a layer of nematic type liquid crystals is formed to form a sandwich cell, and the long axis of the liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other substrate. Display elements are known. In addition, a super twisted nematic (STN) type liquid crystal display element capable of achieving a high contrast ratio compared to a TN type liquid crystal display element, an IPS (In-Plane Switching) type liquid crystal display element having a low viewing angle dependency, and a nema having negative dielectric anisotropy VA (Vertical Alignment) type liquid crystal display elements using tick liquid crystals, etc. have been developed (Patent Documents 1 to 5).

The operating principle of these various liquid crystal display elements is largely divided into a transmission type and a reflection type. The transmissive liquid crystal display element displays by using the intensity change of the transmitted light of the backlight light source from the back of an element at the time of element drive. The reflective liquid crystal display device displays the light using a change in intensity of reflected light from outside light, such as sunlight, when the device is driven without using a light source for backlighting. It is considered to be particularly advantageous for use.

In a transmissive liquid crystal display element, the liquid crystal aligning film provided in this is exposed to light from a backlight light source for a long time. In particular, not only for business use but also for liquid crystal projector use which is increasing in demand as a home theater in recent years, the light source of very high irradiation intensity, such as a metal halide lamp, is used. Moreover, it is thought that the temperature of the system itself of a liquid crystal display element rises at the time of driving with the light irradiation with strong intensity | strength.

Reflective liquid crystal display elements are likely to be used outdoors, and in this case, sunlight containing strong ultraviolet light becomes a light source. In addition, in the reflection type, the distance that light passes through the element is longer than the transmission type due to its principle.

In addition, both the transmissive liquid crystal display element and the reflective liquid crystal display element tend to be widely used in installation in, for example, automobiles, and the like. Realized.

However, in the manufacturing process of a liquid crystal display element, what started to be used from a viewpoint of process shortening and a yield improvement is a liquid crystal dropping method, ie, an ODF (One Drop Fill) system. Unlike the conventional method of injecting a liquid crystal into an empty liquid crystal cell assembled by using a thermosetting sealant in advance, the ODF method applies a UV light curable sealant to a required location of one substrate to which a liquid crystal alignment film is applied, and then liquid crystal. Is added dropwise to the required place, the other substrate is bonded, and then the entire surface is irradiated with ultraviolet light to cure the sealant to produce a liquid crystal cell. Ultraviolet light irradiated at this time is generally stronger than several joules (J) per cm 2. That is, in the liquid crystal display element manufacturing process, a liquid crystal aligning film is exposed to this strong ultraviolet light with a liquid crystal.

As described above, the liquid crystal display device is exposed to harsh environments such as high-intensity light irradiation, high temperature environment, long-time driving, and the like, which are difficult to be considered in accordance with its high functionality, versatility, and improvement in manufacturing process. The electrical characteristics, such as voltage retention, or display characteristics are required to be more excellent than before, and furthermore, the lifespan of a liquid crystal display element is calculated | required further.

As a material of the liquid crystal aligning film which comprises a liquid crystal display element, organic resins, such as a polyimide, a polyamic acid, polyamide, and polyester, are known conventionally. In particular, polyimides are used in many liquid crystal display elements because they exhibit excellent physical properties such as heat resistance, affinity with liquid crystals, mechanical strength, and the like in organic resins (Patent Documents 6 to 8).

However, in recent liquid crystal display devices, new demands have been intensified due to the severity of the manufacturing environment and use environment as described above, and insufficient heat resistance and light resistance to attain organic resins that have been conventionally accepted.

Therefore, examination of the liquid crystal aligning film excellent in heat resistance and light resistance is performed. For example, Patent Document 9 discloses a vertically oriented 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, and is a vertical alignment, heat resistance and uniformity as a liquid crystal alignment film. It is demonstrated that it is excellent in the property and also excellent in stability as a coating liquid. However, the liquid crystal aligning film according to this technology cannot satisfy the required performance due to the current production environment and the severe use of the use environment, and the storage stability of the coating liquid is still insufficient, and thus there is a problem in convenience in industrial use. have.

Further, there is still a strong demand for the development of a liquid crystal aligning agent in which no afterimage problem occurs, that is, excellent in electrical characteristics, as a liquid crystal display element.

On the other hand, when the liquid crystal aligning film is formed by a rubbing process, dust and static electricity are easily generated in the process, and thus, there is a problem that dust adheres to the surface of the alignment film and causes display defects. The photo-alignment method which gives a liquid crystal aligning ability by irradiating polarized light or non-polarization radiation to photosensitive thin films, such as vinyl cinnamate, a polyimide, and an azobenzene derivative, is known (patent documents 10-12). 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 exhibited a good pretilt angle at the beginning of formation, a phenomenon that the pretilt angle expressability disappears over time occurs, so that the stability over time of the pretilt angle is decreased. It is pointed out that it is not enough.

As mentioned above, the liquid crystal aligning agent which can provide the liquid crystal aligning film which has sufficient heat resistance and light resistance in a very severe current manufacturing environment and use environment, is excellent in storage stability, and shows the outstanding electrical property when it is set as a liquid crystal display element, Not known Moreover, when formed by the photo-alignment method, the liquid crystal aligning agent which shows stability with time-lapse of sufficient pretilt angle is not known yet.

In order to solve this problem, the present inventors have recently reported a liquid crystal aligning agent containing a liquid crystal aligning polyorganosiloxane obtained by introducing a structure having liquid crystal aligning ability using the reactivity of a polyorganosiloxane having an epoxy group ( Patent Documents 13-16).

However, the above-mentioned harshness of the use environment tends to be intensified, and in particular, further improvement is required in the heat resistance of the liquid crystal alignment film.

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

 "Science of the Sol-Gel Method," Agne Shofusa, 1988, pp. 155-161  T. J. Scheffer et. al. J. Appl. Phys. vo.19, p. 2013 (1980)

This invention is made | formed in view of the above circumstances, The objective is excellent in liquid crystal orientation, high heat resistance and light resistance, especially in high temperature environment, there is little fall of voltage retention by high intensity light irradiation, and is excellent in electrical characteristics A liquid crystal aligning film can be formed and it is providing the liquid crystal aligning agent with favorable storage stability.

Another object of the present invention is to provide a liquid crystal display device which is excellent in heat resistance, light resistance and electrical properties, and excellent in stability over time of the pretilt angle when the photo alignment method is used in forming the liquid crystal alignment film.

Still other objects and advantages of the present invention are apparent from the following description.

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

Polyorganosiloxane (A) having a Si—X ′ bond (where X ′ is a group containing a structure having liquid crystal alignment capability) and a Si—X ^I bond (where X ^I is a group including an epoxy structure) , 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 a molecule thereof Compound (B) having two or more

It is achieved by the liquid crystal aligning agent containing.

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

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

The liquid crystal aligning agent of this invention is excellent in liquid crystal aligning property, is high in heat resistance and light resistance, especially in high temperature environment, there is little fall of voltage retention by high-intensity light irradiation, can form the liquid crystal aligning film excellent in electrical characteristics, and is preserve | saved Excellent stability

The liquid crystal display element of this invention provided with the liquid crystal aligning film formed from such a liquid crystal aligning agent of this invention is excellent in heat resistance, light resistance, and an electrical property, and even if the photo-alignment method is used at the time of formation of a liquid crystal aligning film, the time progress of a pretilt angle is carried out. It is excellent in stability.

The liquid crystal aligning agent of this invention contains a polyorganosiloxane (A) and a compound (B) at least as mentioned above.

<Polyorganosiloxane (A)>

Polyorganosiloxane (A) in the present invention is a Si-X 'bond (where X' is a group containing a structure having a liquid crystal alignment capability) and Si-X ^I bond (where X ^I includes an epoxy structure Polyorganosiloxane).

As a structure which has liquid crystal aligning ability in said group X ', For example, C1-C20 group, C2-C20 alkyl group, C1-C20 fluoroalkyl group, cyclohexyl group, carbon number which have a steroid skeleton 1 selected from an alkylcyclohexyl group having 1 to 20 alkyl groups, 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 It is preferable that it is a structure containing species or more.

The group having 17 to 51 carbon atoms having the steroid skeleton is preferably 17 to 30 carbon atoms. Specific examples thereof include, for example, a cholestan-3-yl group, a cholesta-5-en-3-yl group, a cholesta-24-en-3-yl group, a cholesta-5,24-diene-3-yl group, and a lano. Stan-3-yl group etc. are mentioned.

As said C2-C20 alkyl group, for example, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, 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 Etc. can be mentioned. It is preferable that carbon number of this alkyl group is 4-20.

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, 4,5,5,5-pentafluoropentyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, etc. are 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 and n-heptyl Cyclohexyl group, n-octyl cyclohexyl group, etc. are mentioned.

Examples of the fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms include trifluoromethylcyclohexyl group and the like;

As a fluoro alkoxy cyclohexyl group which has the said C1-C20 fluoro alkoxyl group, it is a 4,4,4- trifluoro butoxy cyclohexyl group, 4,4,5,5,5-pentafluoro, for example. A lopentoxy cyclohexyl group etc. are mentioned, respectively.

The alkylcyclohex structure having the liquid crystal alignment ability has 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, and an alkyl group having 1 to 20 carbon atoms. In addition to at least one member selected from the group consisting of a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, and a structure represented by the following general formula (X'-1), The liquid crystal aligning agent obtained becomes a liquid crystal aligning film by the photo-alignment method. As m in the following general formula (X'-1), it is preferable that it is 0 or 1, and it is more preferable that it is zero.

(In formula (X'-1), m is an integer of 0-4.)

The "epoxy structure" in the above-mentioned group X ^I means a 1,2-epoxy structure.

Examples of the above group X ^I, for example, the following formulas (X ^I -1 ') or (X ^I -2') is to be a group which can be mentioned, and particularly preferably of the formula (X ^I -1) or (X ^I -2).

Of (formula (X ^I -1 ') and (X ^I -2'), s is an integer from 0 to 3, t is an integer from 1 to 6, u is an integer from 0 to 2, v is from 0 to Is an integer of 6, and "*" each represents a bonding hand)

(In formulas (X ^I -1) and (X ^I -2), "*" each represents a bonding hand.)

"As the proportion of the group X 'group X of the polyorganosiloxane (A) in the present invention and groups of it, and more preferably preferably from 20 to 80 mol%, from 10 to 90 mol% of the total of the X ^I It is especially preferable that it is 25-75 mol%.

The weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) with respect to the polyorganosiloxane (A) in this invention becomes like this. Preferably it is 1,000-10,000,000, More preferably, it is 5,000-100,000, 7,000 It is more preferable that it is to 50,000.

Such polyorganosiloxane (A) may be, for example, a polyorganosiloxane having a Si—X ^I bond, provided that X ^I has the same meaning as X ^I in the polyorganosiloxane (A). A reaction product of a compound having a structure having a liquid crystal alignment capability and at least one group selected from the group consisting of a carboxyl group and a hydroxyl group and a compound having a liquid crystal alignment ability (hereinafter referred to as "compound a") having an epoxy group) Can be.

As for the polyorganosiloxane which has an epoxy structure, it is preferable that the weight average molecular weights of polystyrene conversion measured by the gel permeation chromatography (GPC) are 500-100,000, It is more preferable that it is 1,000-10,000, It is 1,000-5,000 More preferred.

Wherein these groups X ^I is a polyorganosiloxane group like the group X ^I at (A) represented by the above formula (X ^I -1) or (X ^I -2) is especially preferred.

The polyorganosiloxane having such an epoxy group preferably hydrolyzes or hydrolyzes a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group with another silane compound in the presence of a suitable organic solvent, water and a catalyst. ㆍ Can be synthesized by condensation.

As a silane compound which has the said epoxy group, 3-glycidyloxy propyl trimethoxysilane, 3-glycidyl oxypropyl triethoxy silane, 3-glycidyl oxypropyl methyl dimethoxy silane, 3-glycol, for example Cydyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. are mentioned, It is preferable to use 1 or more types chosen from these.

As said other silane compound, for example, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxycysilane, tetra- sec-butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxy Silane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri- sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, Methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorocysilane, 2- (tri Fluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyl Tri-i-propoxysilane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n -Hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n -Hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-butoxy Silane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyl Trimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysil , 2- (perfluoro-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-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) acryloxypropyl Triethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propoxysilane, 3- (meth) acryloxypropyltri-n-part Methoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- Mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3 Mercaptopropyltri-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n- Propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, 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, dimeth Dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane,

(Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro R-n-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-i-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) die Methoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di -n-butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) Diethoxysilane, (methyl) (vinyl) di-n-prop Foxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, Divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxy Silane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, di Phenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-pro Foxtrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethyl Column, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl) In addition to the silane compound which has one silicon atom, such as diphenylsilane,

As a brand name, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, 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-41-1053, 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 Co., Ltd.); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray Dow Corning Corporation); FZ3711 and FZ3722 (above, manufactured 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, and XMS-5025 (above, manufactured by Chisso Corporation);

Methyl silicate MS51 and methyl silicate MS56 (above, manufactured by Mitsubishi Chemical Corporation); Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, manufactured by Colcot Co., Ltd.); And partial condensates such as GR100, GR650, GR908, and GR950 (above, manufactured by Showa Denko Co., Ltd.).

Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltri Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, One or more types selected from the group consisting of 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane are preferable.

It is preferable that the epoxy equivalent of the polyorganosiloxane which has the said epoxy group is 100-10,000 g / mol, and it is more preferable that it is 150-1,000 g / mol. Therefore, when synthesize | combining the polyorganosiloxane which has an epoxy group, it is preferable to adjust and set so that the epoxy equivalent of the polyorganosiloxane obtained can obtain the usage ratio of the silane compound which has an epoxy group, and another silane compound.

As an organic solvent which can be used when synthesize | combining the polyorganosiloxane which has an epoxy group, a hydrocarbon, a ketone, ester, an ether, alcohol, etc. are mentioned, for example.

As said hydrocarbon, toluene, xylene, etc. are mentioned, for example;

As said ketone, For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, etc .;

As said ester, For example, ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .;

As said ether, For example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc .;

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, and ethylene glycol mono-n-butyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. It is preferable to use a water-insoluble organic solvent among these.

These organic solvents can be used individually or in mixture of 2 or more types.

The use amount of the organic solvent is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight based on 100 parts by weight of the total silane compounds.

The amount of water used when producing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 times mole, more preferably 1 to 30 times mole based on the total 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.

As said alkali metal compound, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc. are mentioned, for example.

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;

And quaternary organic amines such as tetramethylammonium hydroxide, and the like. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine;

Preference is given to quaternary organic amines, such as tetramethylammonium hydroxide.

As a catalyst in manufacturing the polyorganosiloxane which has an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, since the target polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without generating side reactions such as ring opening of an epoxy group, the production stability is excellent and is preferable. . Moreover, the liquid crystal aligning agent of this invention containing the reaction material of the polyorganosiloxane which has the epoxy group synthesize | combined using the alkali metal compound or the organic base as a catalyst and cinnamic acid derivative is preferable since it is very excellent in storage stability. The reason for this is the catalyst in hydrolysis and condensation reactions, as pointed out in Non-Patent Document 1 ("Science of the Sol-Gel Method", Agne Shofusa Co., 1988, p. 154 to 161). When an alkali metal compound or an organic base is used as a structure, a three-dimensional structure such as a random structure or a cage structure is formed, and it is presumed that the polyorganosiloxane having a low content of silanol groups is obtained. When the content ratio of silanol groups is small, condensation reaction of silanol groups is suppressed, and when the liquid crystal aligning agent of this invention contains another polymer mentioned later, condensation reaction of a silanol group and another polymer is suppressed, and it is storage stability It is assumed that this is an excellent result.

As the catalyst, an organic base is particularly preferable. The amount of the organic base used varies depending on the type of the organic base, reaction conditions such as temperature, and the like, and should be appropriately set. 1 mole

The hydrolysis or hydrolysis / condensation reaction in preparing the polyorganosiloxane having an epoxy group is carried out by dissolving a silane compound having an epoxy group and another silane compound in an organic solvent, if necessary, and mixing the solution with an organic base and water. For example, it is preferable to carry out by heating by oil bath etc.

In the case of the hydrolysis-condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. . During heating, the mixed solution may be stirred or placed under reflux.

It is preferable to wash | clean the organic solvent layer fractionated from the reaction liquid after completion | finish of reaction with water. At the time of this washing | cleaning, washing | cleaning operation becomes easy by washing with water containing a small amount of salt, for example, about 0.2 weight% of ammonium nitrate aqueous solution, etc., and it becomes easy. The washing is performed until the aqueous layer after washing is neutral, and then the organic solvent layer is dried with a desiccant such as calcium sulfate anhydride or molecular sieve, if necessary, and then the solvent is removed to remove the polyorganosiloxane having the desired epoxy group. You can get it.

In this invention, what is marketed can also be used as polyorganosiloxane which has an epoxy group. As such a commercial item, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, Tosoh Co., Ltd. product) etc. are mentioned, for example.

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 the alcoholic hydroxyl group.

Preferred as compound a are compounds represented by the following formula (a-1).

(In formula (a-1), R is group containing the structure which has liquid crystal aligning ability, Z is a carboxyl group or a hydroxyl group.)

Compound a is a compound in which group Z in compound a reacts with group X ^I in the polyorganosiloxane having the epoxy structure to form a bonding group, thereby inducing group X 'in the polyorganosiloxane (A). The content of the structure having the liquid crystal alignment capability of R can be understood in the same manner as the content of the structure having the liquid crystal alignment capability in the group X 'of the polyorganosiloxane (A). It is apparent to those skilled in the art that the addition of a bonding group formed by the reaction of the group Z and the group X ^I to the group R becomes the group X '.

As Z in the said general formula (a-1), it is preferable that it is a carboxyl group.

Hereinafter, the aspect of preferable compound a is demonstrated.

R (hence, X ') is an alkylcyclohex having 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, and an alkyl group having 1 to 20 carbon atoms As a compound a in the case of including the structure represented by the said general formula (X'-1) other than the fluoroalkylcyclohexyl group which has a real group or a C1-C20 fluoroalkyl group, it is a following general formula (A-1), for example. Preference is given to compounds represented by each of () to (A-8).

(In Formula (A-1), R ^I is 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 or a cyclohexyl group having a steroid skeleton, or having 1 to 20 carbon atoms. An alkylcyclohexyl group having an alkyl group 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 chemical formula (X ² -1 ) to (a group represented by any one of X ² -6),

(In the above formula, "*" indicates that the bond to which it is attached is the X ¹ side.)

X ³ represents a single bond, phenylene _{group, * -O- (CH 2) a} -, * -O- (CH 2) a -CO-,

, Or _{* - (CH 2) a -OCO-} (CH 2) a - ( However, a is each independently an integer of 1-6, "*" is attached coupling hand is -CH = CH-CO- this cheukin Group),

Z has the same meaning as Z in the formula (a-1),

However, when two adjacent bonds are all single bonds, these are combined to be one single bond)

(In Formula (A-2), R ^I and Z have the same meanings as R ^I and Z in the formula (A-1), respectively.)

X ⁴ is a single bond, oxygen atom, sulfur atom, * -COO-, * -OCO-, * -NHCO-, * -CONH- or * -CO- (wherein "*" is the bond of R ^I side)

X ⁵ is a single bond or a phenylene group,

X ⁶ is a single bond or a group represented by the following formula (X ⁶ -1),

(Formula (X ⁶ -1), wherein "*" indicates a bond hand pasted this indicates that X ⁷ cheukin)

X ⁷ represents 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 of 1 to 6, and "*" indicates that the bonding hand to which it is attached is the X ⁶ side.)

However, when two adjacent bonds are all single bonds, they are combined to be one single bond)

(In Formula (A-3), R ^I and Z have the same meanings as R ^I and Z in the formula (A-1), respectively, and X ⁸ is a single bond or * -O- (CH ₂ ) _a- ( A is an integer of 1 to 6, and "*" indicates that the bond to which it is attached is -CH = CH-CO-side), and m is an integer of 0 to 4).

(In Formulas (A-4) to (A-6), R ^I and Z have the same meanings as R ^I and Z in the general formula (A-1), and X ⁹ is a single bond, an oxygen atom, and sulfur, respectively. An atom, * -COO-, * -OCO-, * -NHCO-, * -CONH- or * -CO- (wherein "*" indicates that the bond to which it is attached is on the R ^I side), and 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 "*" indicates that the bond to which it is attached is the Z side)

(In Formulas (A-7) and (A-8), R ^I and Z have the same meanings as R ^I and Z in the formula (A-1), respectively, and X ¹¹ is a single bond, *-(CH), respectively. ₂ ) _a -COO-, * -COO- (CH ₂ ) _a -or * -O- (CH ₂ ) _a -O- (where a is an integer of 1 to 6 and "*" is a bond Is on the Z side)

However, in the above formulas (A-1) to (A-8), combinations of substituents on which an O-O bond or an α, β-diketo structure are formed are not allowed.

As said C2-C20 alkyl group of R <^I> , an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n is mentioned, for example. -Dodecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc. are mentioned. It is preferable that carbon number of this alkyl group is 4-20.

Examples of the fluoroalkyl group having 1 to 20 carbon atoms in R ^I include, for example, a trifluoromethyl group, a perfluoroethyl group, a 3,3,3-trifluoropropyl group, and a 4,4,4-trifluorobutyl group. , 4,4,5,5,5-pentafluoropentyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, and the like.

As the monovalent organic group of R ^I having a steroid skeleton in R ^I, preferably a carbon number of 17 to 30. As a specific example of R <^I> which has a steroid skeleton, it is a cholestan-3-yl group, a cholesta-5-en-3-yl group, a cholesta-24-en-3-yl group, a cholesta-5,24-diene, for example. A -3-yl group, a lanostane-3-yl group, etc. are mentioned.

As a more preferable example of such a compound a, when Z in the formula (a-1) is -COOH, a compound represented by the formula (A-1), for example, the following formulas (A-1-C1) to ( A-1-C22) The compound etc. which are represented by each;

As a compound represented by the said General formula (A-2), For example, the compound etc. represented by each of following General formula (A-2-C1)-(A-2-C5);

As a compound represented by the said General formula (A-3), For example, the compound etc. represented by the following general formula (A-3-C1) or (A-3-C2);

As a compound represented by the said General formula (A-4), For example, the compound etc. represented by each of following General formula (A-4-C1)-(A-4-C3);

As a compound represented by the said General formula (A-5), For example, the compound etc. represented by the following general formula (A-5-C1);

As a compound represented by the said General formula (A-6), For example, the compound etc. represented by the following general formula (A-6-C1) or (A-6-C2);

As a compound represented by the said General formula (A-7), For example, the compound etc. represented by the following general formula (A-7-C1);

As a compound represented by the said General formula (A-8), the compound etc. which are represented by the following general formula (A-8-C1) or (A-8-C2) are mentioned, for example.

(In the above, R ^I are the same meaning as those in the formulas (A-1) to (A-8), respectively, and a is an integer of 1 to 6, respectively.)

As another preferable example of compound a when R is a group containing the structure represented by said general formula (X'-1), when Z is -OH, it is a compound represented by the said general formula (A-1), for example Compounds represented by the following formulas (A-1-O1) to (A-1-O7), and the like;

As a compound represented by the said General formula (A-2), For example, the compound etc. represented by each of following formula (A-2-O1)-(A-2-O3);

As a compound represented by the said General formula (A-8), the compound etc. which are represented by the following general formula (A-8-O1) are mentioned, for example.

(Wherein R ^I is the same as in formula (A-1), (A-2) and (A-8), respectively)

On the other hand, in the formula (a-1), R is 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. As a compound a in the case of having an alkylcyclohexyl group which has an or a fluoroalkylcyclohexyl group which has a C1-C20 fluoroalkyl group, but does not include the structure represented by the said General formula (X'-1), For example, the compound etc. which are represented by each of following formula (A-9)-(A-11) are preferable.

(R ^I and Z in the above formula have the same meanings as R ^I and Z in the formula (A-1), respectively.

In formulas (A-10) and (A-11), X ¹² represents a single bond, an oxygen atom, * -COO- or * -OCO- (wherein "*" indicates that the bond to which it is attached is the R ^I side). ),

P in formula (A-11) is 1 or 2)

Examples of the compound represented by the formula (A-9) wherein Z is -COOH include, for example, n-butanoic acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-no Difficult 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-eicanoic acid, tetrahydroavietic acid, monocholestanyl succinate, monocholestanyl glutarate, a compound represented by the following general formula (A-9-1);

(In formula (A-9-1), h is an integer of 1-3, i is an integer of 3-18.)

Examples of the compound represented by the formula (A-10) wherein Z is -COOH include 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-pro Foxy) 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, Compounds represented by the formulas (A-9-2) to (A-9-4), and the like;

(Wherein j is an integer of 5 to 20, k is an integer of 1 to 3, m is an integer of 0 to 18, n is an integer of 1 to 18)

As a specific example of the compound represented by the said general formula (A-11) whose Z is -COOH, it is 4- (n-butyl) cyclohexylcarboxylic acid, 4- (n-pentyl) cyclohexylcarboxylic acid, 4, for example. -(n-butyl) bicyclohexyl carboxylic acid, 4- (n-pentyl) bicyclohexyl carboxylic acid, etc. are mentioned, respectively.

Moreover, as an example of the compound represented by the said general formula (A-9) whose Z is -OH, it is 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1- Decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1 Nonadecanol, 1-eicosanol, etc. are mentioned.

The compounds represented by each of the above formulas (A-1) to (A-11) may be obtained as commercially available products, or may be synthesized by appropriately combining the methods of organic chemistry. Or less, R ^I is described as the alkyl group, mainly an example, but, R ^I is or the same as this also to a compound other than an alkyl group, or in fact that pursuant be synthesized by the method is information that can be easily understood to those skilled in the art .

For example, the compound represented by the formula (A-1-C1) is reacted by heating a halogenated alkyl having an alkyl group corresponding to hydroxycinnamic acid and R ^I in the presence of a suitable base such as potassium carbonate. Then, it can obtain by hydrolyzing with suitable aqueous alkali solution, such as sodium hydroxide.

The compound represented by the above formula (A-1-C2) is a carboxylic acid chloride having an alkyl group corresponding to hydroxycinnamic acid and R ^I , for example, at a temperature of 0 ° C. to room temperature in the presence of a suitable base such as potassium carbonate. It can obtain by making it react at temperature.

The compound represented by the above formula (A-1-C4) is, for example, halogenated alkyl or tosylated alkyl having an alkyl group corresponding to methyl hydroxybenzoate and R ^I in a suitable base such as potassium carbonate at room temperature to 100 ° C. After reacting at a temperature of, it is hydrolyzed with a suitable aqueous alkali solution such as sodium hydroxide, which is converted to an acid chloride with thionyl chloride, which is then reacted with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at 0 ° C to room temperature. It can obtain by making it react at the temperature of.

The compound represented by the above formula (A-1-C5) is, for example, an alkylcarboxylic acid chloride having an hydroxybenzoic acid and an alkyl group corresponding to R ^I at 0 ° C to room temperature in the presence of a suitable base such as triethylamine. After making it react at temperature, it can be obtained by making an acid chloride with thionyl chloride, and making this react with hydroxycinnamic acid at the temperature of 0 degreeC-room temperature in presence of a suitable base, such as potassium carbonate.

The compound represented by the above formula (A-1-C6) is, for example, 4-alkylbenzoic acid as thionyl chloride as an acid chloride, which is hydroxycinnamic acid and 0 ° C. in the presence of a suitable base such as potassium carbonate. It can obtain by making it react at the temperature of-room temperature.

The compound represented by the above formula (A-1-C7) is, for example, methyl hydroxycyclohexyl carboxylic acid and alkyl halide having an alkyl group corresponding to R ^I of a suitable alkali such as sodium hydride or metal sodium. The reaction is carried out in the presence of an ether, followed by hydrolysis with an aqueous alkali solution such as sodium hydroxide, and the like with thionyl chloride, followed by acid chloride with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate. It can obtain by making it react at temperature.

The compound represented by the said general formula (A-1-C8) is what made the acid chloride with thionyl chloride the 4-alkylcyclohexyl carboxylic acid which has an alkyl group corresponded to R <^I> , for example, potassium carbonate, etc. It can be obtained by reacting hydroxycinnamic acid with a suitable base at a temperature of 0 ° C to room temperature.

The compound represented by the above formula (A-1-C9) reacts an alkyl halide having a alkyl group corresponding to R ^I with hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond, followed by 4-acetylbenzoic acid. Can be obtained by aldol condensation in the presence of sodium hydroxide. The compounds represented by each of the above formulas (A-1-C10) to (A-1-C15) can also be obtained by the same method.

The compound represented by the above formula (A-2-C1) is reacted with, for example, alkyl acrylate having an alkyl group corresponding to 4-iodophenol and R ^I using palladium and amine as catalyst (generally "hex ( Heck) reaction ", and then ring-opening addition of the target cyclic acid anhydride, such as succinic anhydride or glutaric anhydride, to the reaction product.

The compound represented by the above formula (A-2-C2) can be obtained by aldol condensation of 4-alkylacetophenone and 4-formylbenzoic acid having an alkyl group corresponding to R ^I in the presence of sodium hydroxide. The compound represented by the said general formula (A-2-C3) can also be obtained by the method according to it.

The compound represented by the formula (A-2-C4) can be obtained by aldol condensation of 4-alkylacetophenone and 4-hydroxybenzaldehyde having an alkyl group corresponding to R ^I in the presence of sodium hydroxide. The compound represented by the said general formula (A-2-C5) can also be obtained by the method according to it.

The compound represented by the above formula (A-3-C1) can be obtained by a method (generally called a hex reaction) of obtaining an acrylate ester and 4-bromocinnamic acid having an alkyl group corresponding to R ^I using a palladium catalyst. have. The compound represented by the said general formula (A-3-C2) can also be obtained by the method similar to this.

The compound represented by the above formula (A-4-C1) is, for example, when R ^I is an alkyl group, alkylsuccinic anhydride and 4-aminocinnamic acid having an alkyl group corresponding to R ^I under reflux in acetic acid, Or by reaction under reflux in toluene or xylene in the presence of a suitable base catalyst such as triethylamine,

In the case where R ^I is a fluoroalkyl group, maleic anhydride is protected by a suitable protecting group such as p-toluidine and then coupled by Grignard reaction with a fluoroalkyl iodide having a fluoroalkyl group corresponding to R ^I. After ringing, it can be obtained by a method of deprotection by hydrolysis, dehydration ring closure, and reaction with 4-aminocinnamic acid.

The compound represented by the said general formula (A-4-C2) can be synthesize | combined by either of the following two routes, for example.

As the first route, maleic anhydride is protected with a suitable protecting group such as p-toluidine, and Michael is added to an alcohol having an alkyl group corresponding to R ^I in the presence of a suitable base of potassium carbonate, followed by deprotection by hydrolysis. And dehydration ring closure, and the product thereof 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).

A second route, acid methyl and a halogenated alkyl having an alkyl group corresponding to R ^I, for example, by reacting in the presence of silver oxide decomposition and then with ether, singer, and subjected to dehydration ring-closure, wherein the product formula (A- The method of making it react with 4-amino cinnamic acid similarly to the thing in the synthesis | combination of the compound represented by 4-C1) is mentioned.

The compound represented by the above formula (A-4-C3), for example, except that a thiol having an alkyl group corresponding to R ^I in place of the alcohol having an alkyl group corresponding to R ^I, the formula (A-4 It can obtain similarly to the 1st route in the synthesis | combination of the compound represented by -C2).

The compound represented by the above formula (A-5-C1) is, for example, after having 1,2,4-tricarboxycyclohexane anhydride as thionyl chloride acid chloride, and an alcohol having an alkyl group corresponding to R ^I. It is obtained by reacting in the presence of a suitable base such as triethylamine and esterifying the product, 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). have.

For example, the compound represented by the above formula (A-6-C1) reacts the compound R ^I -OH corresponding to the desired compound with a trimellitic anhydride anhydride to synthesize an ester compound which is an intermediate, and then the ester It can synthesize | combine by making a compound and 4-amino cinnamic acid react. The synthesis of the intermediate ester compound is preferably carried out in the presence of a basic compound in a suitable solvent. As a solvent which can be used here, tetrahydrofuran etc. are mentioned, for example, As a basic compound, triethylamine etc. are mentioned, respectively. The reaction of an ester compound with 4-aminocinnamic acid is, for example, a method of refluxing protons in acetic acid, a suitable catalyst in toluene or xylene (for example, an acid catalyst such as sulfuric acid or a base catalyst such as triethylamine). And refluxing in the presence of

The compound represented by the formula (A-6-C2) is 5-hydroxyphthalic acid, for example, refluxed in diethylbenzene, dehydrated and closed to give an acid anhydride, and then reacted with 4-aminocinnamic acid in the same manner as described above. to a first intermediate, already synthesized and the imide compound, and then the imide compound and a compound R ^I -X compound corresponding to the desired can be synthesized by reacting (where, X is a halogen atom). At this time, Preferably it is performed in presence of a basic compound in a suitable solvent. As a solvent which can be used here, amide compounds, such as N, N- dimethylacetamide, etc. are mentioned, for example, As a basic compound, potassium carbonate etc. are mentioned, respectively.

The compound represented by the formula (A-7-C1) is, for example, 4-nitrocinnamic acid is reacted with an alkyl halide having an alkyl group corresponding to R ^I in the presence of potassium carbonate to make an ester, and examples thereof are nitro groups. For example, it can be obtained by reducing with tin chloride to make an amino group and then reacting the product with 1,2,4-tricarboxycyclohexylcyclohexane anhydride. The latter reaction can be carried out, for example, by refluxing the raw material compound in acetic acid or refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine. By the method similar to this, the compound represented by the said general formula (A-8-C1) can also be synthesize | combined.

The compound represented by the formula (A-8-C2) is hydroxyphthalic acid instead of 1,2,4-tricarboxycyclohexylcyclohexane anhydride in the synthesis of the compound represented by the formula (A-7-C1). After synthesize | combining the cinnamic acid derivative which has an imide ring using, it can obtain by making it react 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. 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 the method described above.

The compound represented by the above formula (A-2-O1) is reacted with, for example, an alkyl acrylate having an alkyl group corresponding to 4-iodophenol and R ^I using palladium and amine as a catalyst (generally "hex reaction "," To obtain.

The compound represented by the formula (A-2-O2) can be obtained by aldol condensation of 4-alkylacetophenone and 4-hydroxybenzaldehyde having an alkyl group corresponding to R ^I in the presence of sodium hydroxide. The compound represented by the said general formula (A-2-O3) can also be obtained by the method according to the above.

The compound represented by the above formula (A-8-O1) is, for example, 4-nitrocinnamic acid as an acid chloride with thionyl chloride, and then reacted with an alcohol having an alkyl group corresponding to R ^I to obtain an ester. The nitro group can be reduced by, for example, tin chloride to be an amino group, and then the product can be obtained by reacting the product with hydroxyphthalic anhydride. The latter reaction can be carried out, for example, by refluxing the raw material compound in acetic acid or refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine.

Among these compounds a, preferably R in the formula (a-1) has a structure represented by the formula (X'-1), wherein the formulas (A-1-C1) and (A-1-C3) ), (A-1-C4), (A-1-C6) to (A-1-C8), (A-1-C16), (A-1-C19), (A-1-C21), A compound represented by (A-4-C1), (A-4-C2), (A-5-C1) and (A-7-C1), respectively,

R does not have a structure represented by the formula (X'-1) as n-butanoic acid, n-hexanoic acid, n-octanoic acid, n-lauric acid, n-stearic acid, 4-n-octadecyl Benzoic 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-heptane thiol, 1-octanethiol, 1-nonanethiol, 1-decanthiol, 1-undecantithiol, 1-dodecanethiol, 1-tetradecane Thiol, 1-hexadecanethiol, 1-octadecanethiol, molecholestanyl succinate and compounds represented by the following formulas (A-9-3-1) to (A-9-3-3), respectively.

In this specification, the compound a in which R does not have a structure represented by the said general formula (X'-1) is called "another pretilt-angle expressing compound" below.

The polyorganosiloxane (A) in the present invention requires that some of the Si-X ^I bonds derived from the polyorganosiloxane having an epoxy structure remain. Thus, while when both of the reaction, it is preferred to use a polyorganosiloxane compound of group molar amount less than the molar amount of X ^I having a having an epoxy structure.

The proportion of the compound a at the time of synthesizing the polyorganosiloxane (A) in the present invention, it is preferable that 0.1 to 0.9 mol per 1 mol of the group X ^I having the polyorganosiloxane having an epoxy structure, and It is more preferable to set it as 0.2-0.8 mol, and it is still more preferable to set it as 0.25-0.75 mol.

It is preferable to perform reaction of the polyorganosiloxane which has an epoxy structure, and compound a in presence of a catalyst. As such a catalyst, for example, a compound known as a so-called curing accelerator that promotes the reaction of an organic base or an epoxy compound with 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;

And quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Preference is given to quaternary organic amines, such as tetramethylammonium hydroxide.

As said hardening accelerator, For example, tertiary amines, such as benzyl dimethylamine, 2,4,6- tris (dimethylaminomethyl) phenol, cyclohexyl dimethylamine, and triethanolamine;

2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methyldi Midazole, 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-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimelli Tate, 1- (2-cyanoethyl) -2-phenylimirazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-dia Mino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s- Triazine, 2,4-di Amino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, 2-phenylimidazole Imidazole compounds such as isocyanuric acid adducts of isocyanuric acid adducts of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine;

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine and triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide Nium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazoleate, tetra-n-butylphosphonium Quaternary phosphonium salts such as tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 or organic acid salts thereof;

Organometallic compounds such as zinc octylate, octylate tin, and 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 halide compounds such as zinc chloride and ditin chloride;

High-melting-point dispersion | distribution type latent hardening accelerators, such as an amine addition type accelerator, such as a dicyandiamide, the addition product of an amine, and an epoxy resin;

Microcapsule-type latent curing accelerators in which a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;

Amine salt type latent curing agent accelerators;

And latent curing accelerators such as high-temperature dissociation-type thermal cationic polymerization-type latent curing accelerators such as Lewis salts and Bronsted salts.

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

These catalysts are preferably used in an amount of 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 polyorganosiloxane having an epoxy structure.

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC.

The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

The synthesis reaction of the said polyorganosiloxane (A) can be performed in presence of an organic solvent as needed. As such an organic solvent, a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound etc. are mentioned, for example. Of these, ether compounds, ester compounds, and ketone compounds are preferred in view of solubility of raw materials and products and ease of purification of products. The solvent is used at a ratio such that the solid content concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 50% by weight.

The said polyorganosiloxane (A) makes the polyorganosiloxane which has an epoxy structure, and compound a react, and introduce | transduces the group which has liquid crystal aligning property into the polyorganosiloxane using ring-opening addition of an epoxy group. This manufacturing method is not only simple but also a very preferable method in that the introduction ratio of the structure having the liquid crystal alignment ability can be increased.

In the above, only one compound a may be used alone, or two or more compounds a may be mixed and used. In this case, when the use ratio of the compound a which has group represented by the said General formula (X'-1) is 50 mol% or more with respect to whole quantity of the compound a preferably, the liquid crystal aligning containing this polyorganosiloxane (A) An agent can form the liquid crystal aligning film which shows favorable liquid crystal aligning property by the photo-alignment method.

In addition, when group Z which compound a has above is -COOH, part of compound a can also be substituted by another carboxylic acid, and reaction can also be performed. In this case, as a use ratio of another carboxylic acid, it is preferable that it is 50 mol% or less with respect to the sum total of compound a and another carboxylic acid.

<Compound (B)>

The compound (B) in the present invention has acetal ester structure of carboxylic acid, ketal ester structure of carboxylic acid, 1-alkylcycloalkyl ester structure of carboxylic acid and t-butyl ester structure of carboxylic acid in a molecule thereof. It is a compound which has 2 or more types of 1 or more types chosen from the group which consists of. The compound (B) may be a compound having two or more structures of the same kind among these structures, or may be a compound having two or more kinds of different kinds of structures in these structures.

As group which forms the acetal ester structure of the said carboxylic acid, group represented by each of following General formula (B-1) and (B-2) is mentioned.

(In formula (B-1), R <^1> and R <^2> is a C1-C20 alkyl group, a C3-C10 alicyclic group, a C6-C10 aryl group, or a C7-C10 aralkyl group, respectively,

In formula (B-2), n1 is an integer of 2 to 10)

Here, as an alkyl group of R <^1> in the said General formula (B-1), a methyl group;

As an alicyclic group, Cyclohexyl group;

As an aryl group, a phenyl group;

As an aralkyl group, a benzyl group is preferable, respectively.

As an alkyl group of R <^2> , a C1-C6 alkyl group;

As an alicyclic group, C6-C10 alicyclic group;

As an aryl group, a phenyl group;

As an aralkyl group, a benzyl group or 2-phenylethyl group is preferable respectively, and it is preferable that it is 3 or 4 as n1 in general formula (B-2).

Examples of the group represented by the above formula (B-1) include 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group and 1-i-propoxyethoxy Carbonyl 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-phenethyloxyethoxycarbonyl group, (cyclohexyl) (methoxy) methoxycarbonyl group, (cyclohexyl) (ethoxy) methoxycarbonyl group, (cyclohexyl) (n-propoxy ) Methoxycarbonyl group, (cyclohexyl) (i-propoxy) methoxycarbonyl group, (cyclohexyl) (cyclohexyl Methoxycarbonyl group, (cyclohexyl) (phenoxy) methoxycarbonyl group, (cyclohexyl) (benzyloxy) methoxycarbonyl group, (phenyl) (methoxy) methoxycarbonyl group, (phenyl) (ethoxy) methoxy Carbonyl group, (phenyl) (n-propoxy) methoxycarbonyl group, (phenyl) (i-propoxy) methoxycarbonyl group, (phenyl) (cyclohexyloxy) methoxycarbonyl group, (phenyl) (phenoxy) methoxy Carbonyl 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 .;

As group represented by the said General formula (B-2), 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, etc. are mentioned, for example. Among these, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, etc. are preferable. .

As group which forms the ketal ester structure of the said carboxylic acid, group represented by each of following General formula (B-3)-(B-5) is mentioned, for example.

(In formula (B-3), R <^3> is a C1-C12 alkyl group, R <^4> and R <^5> is a C1-C12 alkyl group, a C3-C20 alicyclic group, a C6-C20 aryl group, respectively, or 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, n3 is an integer of 2 to 8)

Here, as the alkyl group of R ³ in the formula (B-3), a methyl group is preferable,

As an alkyl group of R <^4> , a methyl group;

As an alicyclic group, Cyclohexyl group;

As an aryl group, a phenyl group;

As an aralkyl group, a benzyl group is preferable, respectively.

As an alkyl group of R <^5> , a C1-C6 alkyl group;

As an alicyclic group, C6-C10 alicyclic group;

As an aryl group, a phenyl group;

As an aralkyl group, a benzyl group or 2-phenylethyl group is preferable, respectively, As an alkyl group of R <^6> in General formula (B-4), a methyl group;

As n2, it is preferable that it is 3 or 4, respectively.

As an alkyl group of R <^7> in general formula (B-5), a methyl group;

As n3, it is preferable that it is 3 or 4, respectively.

As a group represented by the said General formula (B-3), it is a 1-methyl-1- methoxy ethoxy carbonyl group, the 1-methyl-1- ethoxy ethoxy carbonyl group, 1-methyl-1- n-propoxy, for example. Ethoxycarbonyl group, 1-methyl-1-i-propoxyoxycarbonyl group, 1-methyl-1-n-butoxyethoxycarbonyl group, 1-methyl-1-i-butoxyethoxycarbonyl group, 1-methyl- 1-sec-butoxyethoxycarbonyl group, 1-methyl-1-t-butoxyethoxycarbonyl group, 1-methyl-1-cyclopentyloxyethoxycarbonyl group, 1-methyl-1-cyclohexyloxyethoxycarbonyl group, 1-methyl-1-norbornyloxyethoxycarbonyl group, 1-methyl-1-bornyloxyethoxycarbonyl group, 1-methyl-1-phenoxyethoxycarbonyl group, 1-methyl-1- (1-naphthyl Oxy) ethoxycarbonyl group, 1-methyl-1-benzyloxyethoxycarbonyl group, 1-methyl-1-phenethyloxyethoxycarbonyl group, 1-cyclohexyl-1-methoxyethoxycarbonyl group, 1-cyclohexyl-1 Ethoxyethoxycarbonyl group, 1- Clohexyl-1-n-propoxyethoxycarbonyl group, 1-cyclohexyl-1-i-propoxyethoxycarbonyl group, 1-cyclohexyl-1-cyclohexyloxyethoxycarbonyl group, 1-cyclohexyl-1-phenoxy Ethoxycarbonyl group, 1-cyclohexyl-1-benzyloxyethoxycarbonyl group, 1-phenyl-1-methoxyethoxycarbonyl 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-propoxyoxycarbonyl group, 1-benzyl-1-cyclohexyloxyethoxycarbonyl group, 1-benzyl-1-phenoxyethoxycarbonyl group, 1-benzyl-1-benzyloxyethoxycarbonyl group, etc .;

Examples of the group represented by the above formula (B-4) include 2- (2-methyltetrahydrofuranyl) oxycarbonyl group, 2- (2-methyltetrahydropyranyl) oxycarbonyl group and the like;

As group represented by the said General formula (B-5), a 1-methoxycyclopentyloxycarbonyl group, a 1-methoxycyclohexyloxycarbonyl group, etc. are mentioned, for example. Among them, 1-methyl-1-methoxyethoxycarbonyl group, 1-methyl-1-cyclohexyloxyethoxycarbonyl group, and the like are preferable.

As group which forms the 1-alkylcycloalkylester structure of the said carboxylic acid, group represented by following General formula (B-6) is mentioned, for example.

(In formula (B-6), R <^8> is a C1-C12 alkyl group and n4 is an integer of 1-8.)

Here, as an alkyl group of R <^8> in the said General formula (B-6), a C1-C10 alkyl group is preferable.

Examples of the group represented by the above formula (B-6) include 1-methylcyclopropoxycarbonyl group, 1-methylcyclobutoxycarbonyl group, 1-methylcyclopentoxycarbonyl group, 1-methylcyclohexyloxycarbonyl group and 1- Methylcycloheptyloxycarbonyl group, 1-methylcyclooctyloxycarbonyl group, 1-methylcyclononyloxycarbonyl group, 1-methylcyclodecyloxycarbonyl group, 1-ethylcyclopropoxycarbonyl group, 1-ethylcyclobutoxycarbonyl group, 1-ethylcyclo Pentoxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1-ethylcycloheptyloxycarbonyl group, 1-ethylcyclooctyloxycarbonyl group, 1-ethylcyclononyloxycarbonyl group, 1-ethylcyclodecyloxycarbonyl group, 1- (iso) propyl Cyclopropoxycarbonyl group, 1- (iso) propylcyclobutoxycarbonyl group, 1- (iso) propylcyclopentoxycarbonyl group, 1- (iso) propylcyclohexyloxy L- (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 Carbonyl 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) Butyl bicyclo-nonyl oxy-carbonyl group, 1- (isobutyl), cyclo-pentyl-decyl-oxy 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 Heptylcyclopropoxycarbonyl group, 1- (iso) heptylcyclobutoxycarbonyl group, 1- (iso) heptylcyclopentoxycarbonyl group, 1- (iso) heptylcyclohexyloxycarbonyl group, 1- (iso) heptylcycloheptyloxycarbonyl group , 1- (iso) heptylcyclooctyloxycarbonyl group, 1- (iso) heptylcyclononyloxycarbonyl group, 1- (iso) heptylcyclodecyloxycarbonyl group, 1- (iso) octylcyclopropoxycarbonyl group, 1- (iso) Octylcyclobutoxycarbonyl group, 1- (iso) octylcyclopentoxycarbon Neyl group, 1- (iso) octylcyclohexyloxycarbonyl group, 1- (iso) octylcycloheptyloxycarbonyl group, 1- (iso) octylcyclooctyloxycarbonyl group, 1- (iso) octylcyclononyloxycarbonyl group, 1- (iso ) Octylcyclodecyloxycarbonyl group, etc. are mentioned.

The group which forms the t-butylester structure of the said carboxylic acid is a t-butoxycarbonyl group.

As a compound (B) in this invention, the compound represented by following General formula (B) is preferable. As n, it is preferable that it is 2 or 3.

(In Formula (B), B is a group or t-butoxycarbonyl group represented by any one of said Formula (B-1)-(B-5), n is 2, R is a single bond, or n is 2 An integer of 10 to 10 and R is a group obtained by removing n-valent hydrogen from a heterocyclic compound having 3 to 10 carbon atoms or an n-valent hydrocarbon group having 1 to 18 carbon atoms)

As a specific example of R in the said General formula (B), when n is 2, a single bond, a methylene group, a C2-C12 alkylene group, 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, etc .;

When n is 3, group represented by the following formula, benzene-1,3,5-triyl group, etc. are mentioned, respectively. As said alkylene group, what is linear is preferable.

The compound (B) represented by the above formula (B) can be synthesized by the method of organic chemistry or by appropriately combining the methods of organic chemistry.

For example, the compound in which the group B in the formula (B) is a group represented by the formula (B-1) (except when R ¹ is a phenyl group) is preferably a compound R in the presence of a phosphoric acid catalyst. -(COOH) _n (wherein R and n each have the same meaning as in formula (B) above) and compound R ² -O-CH = R ^{1 '} (where R ² is in formula (B) And R ^{1 '} is a group obtained by removing a hydrogen atom from the 1-position carbon of the group R ¹ in the formula (B).

The group compound in which the group B in the formula (B) is represented by the formula (B-2) is preferably a compound R- (COOH) _{n in} the presence of a p-toluenesulfonic acid catalyst, wherein R and n are each Synonymous with the said general formula (B)) and the compound represented by the following general formula.

(N1 in the formula is the same meaning as in the formula (B-2))

As a use ratio of the compound (B) in the liquid crystal aligning agent of this invention, the acetal ester structure of the carboxylic acid which a compound (B) has, the ketal ester structure of carboxylic acid, and the 1-alkylcycloalkyl ester structure of carboxylic acid And the total number of moles of at least one structure selected from the group consisting of t-butyl ester structures of carboxylic acids is 0.1 to 10 moles with respect to 1 mole of Si-X ^I bond of the polyorganosiloxane (A). It is preferable to set it as the ratio which becomes 0.4-4 mol, and it is still more preferable to set it as the ratio which becomes 1.5-2 mol. Therefore, in the case of using the compound represented by Formula (B) as the compound (B), the proportion of the compound (B) is a polyorganosiloxane (A) is with respect to the Si-X ^I combine 1 mol of 0.1 with / It is preferable to set it as n-10 / n mol, It is more preferable to set it as 0.4 / n-4 / n mol, It is still more preferable to set it as 1.5 / n-2 / n mol. However, in the above, n is synonymous with the thing in the said General formula (B).

Since the liquid crystal aligning agent of this invention can form the liquid crystal aligning film excellent in heat resistance and light resistance by containing such a compound (B), since it is excellent in storage stability, it is preferable.

<Other ingredients>

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

The liquid crystal aligning agent of this invention may contain other components other than the above-mentioned polyorganosiloxane (A) and a compound (B) unless the effect of this invention is impaired. As such other components, for example, 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, provided that Except the thing corresponding to a organosiloxane (A), it is hereafter called an "epoxy compound", a functional silane compound, a hardening | curing agent, a curing catalyst, surfactant, etc. are mentioned.

The 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 characteristic of the obtained liquid crystal aligning film further. As such another polymer, for example, at least one polymer (C1) selected from the group consisting of polyamic acid and polyimide, and polyorganosiloxane (C2) other than the polyorganosiloxane (A) (hereinafter referred to as "other poly Organosiloxane (C2) "), polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like. have.

{Polyamic acid}

The said polyamic acid can be obtained by making tetracarboxylic dianhydride and diamine react.

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid in this invention, an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. Can be. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butanetetracarboxylic dianhydride etc .;

As the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro -3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6 -Dianhydrides, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 3,5: 6- dianhydrides, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] Undecane-3,5,8,10-tetraon and the like;

As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride etc. can be mentioned, respectively, In addition, tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2009-84462 can be used.

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, it is preferable to contain alicyclic tetracarboxylic dianhydride among these, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, and 1, It is more preferable to contain 1 or more types chosen from the group which consists of 2,3, 4- cyclobutane tetracarboxylic dianhydride, It is especially preferable to contain 2,3,5- tricarboxycyclopentyl acetic dianhydride. Do.

As tetracarboxylic dianhydride used for synthesizing the polyamic acid, the group consisting of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride It is preferable to contain 10 mol% or more with respect to all the tetracarboxylic dianhydrides, More preferably, it contains 20 mol% or more, and 2,3,5-tricarboxycyclopentyl acetic dianhydride is selected from the above. And one or more selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

As diamine used for synthesize | combining a polyamic acid, aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. are mentioned, for example. As these specific examples, As an aliphatic diamine, For example, 1, 1-methacrylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, 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'-diamino Diphenyl 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- Phenylenediisopropylidene) 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, dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2, 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecaneoxy-2,5- Diaminobenzene,

Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, chole Stenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 , 5-diaminobenzoic acid cholesterol, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane , 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) 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-hep Ylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -piperidine and the compound represented by the following general formula (D-1);

(In Formula (D-1), X ^I represents an alkyl group having 1 to 3 carbon atoms, * -O-, * -COO- or * -OCO-, provided that a bond with "*" is bonded to the diaminophenyl group.) ), X is 0 or 1, y is an integer from 0 to 2, z is an integer from 1 to 20)

Examples of the diaminoorganosiloxanes include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and diamines described in Japanese Patent Application No. 2009-84462 can be used. .

X ^I in the formula (D-1) is preferably an alkyl group having 1 to 3 carbon atoms, * -O- or * -COO-, provided that the bond to which "*" is attached is combined with a diaminophenyl group. . Group C _z H _{2z + 1} - Specific examples of, for example, methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, n- octyl, 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-eicosyl group, etc. are mentioned. Two amino groups in the diaminophenyl group are preferably at the 2,4-position or 3,5-position relative to the other group.

As a specific example of a compound represented by the said General formula (D-1), the compound etc. which are respectively represented by following General formula (D-1-1)-(D-1-4) are mentioned, for example.

In the above formula (D-1), x and y are preferably not zero at the same time.

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

The use ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group contained in the diamine compound. More preferably, it is the ratio which becomes 0.3 to 1.2 equivalent.

The synthesis reaction of the polyamic acid is preferably in an organic solvent, preferably at a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C, preferably 0.5 to 24 hours, more preferably 2 to 10 hours. Is done during. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Aprotic polar solvents such as N, N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphotriamide;

Phenolic solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, etc. are mentioned. The amount (a) of the organic solvent used is preferably 0.1 to 50% by weight, more preferably 5 to 5%, based on the total amount (b) of the tetracarboxylic dianhydride and the diamine compound. It is the quantity used as 30 weight%.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, may be used for the production of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or after the isolated polyamic acid is purified to prepare a liquid crystal aligning agent. Can also be used for

When the polyamic acid is dehydrated and closed to give a polyimide, the reaction solution may be used as it is for the dehydration ring-closure reaction, or the polyamic acid contained in the reaction solution may be isolated and then used for the dehydration ring-closure reaction, or the isolated polyamic acid. After purification, it can be used for dehydration ring closure reaction.

Isolation of the polyamic acid can be performed by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, drying the precipitate under reduced pressure, or distilling off the organic solvent in the reaction solution with an evaporator under reduced pressure. Further, the polyamic acid is dissolved in an organic solvent again, and then precipitated with a poor solvent, or after washing the solution after re-dissolution, the step of distilling off the organic solvent in the solution by evaporation under reduced pressure is carried out once or several times. Polyamic acid can be refine | purified by a method etc.

[Polyimide]

The polyimide can be produced by dehydrating and closing the amic acid structure of the polyamic acid obtained as described above. At this time, all the amic acid structures may be dehydrated and completely imidized, or only a part of the amic acid structures may be dehydrated and closed to be a partial imide in which the amic acid structure and the imide structure coexist.

The dehydration ring closure of the polyamic acid may be carried out by (i) a method of heating the polyamic acid, or (ii) by dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating it as necessary. Is done.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall. 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, as a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said polyamic acid of said (ii). It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of polyamic-acid structural units. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

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

[Other Polyorganosiloxanes (C2)]

The other polyorganosiloxane (C2) is preferably one or more silane compounds (hereinafter, also referred to as "raw silane compounds") selected from the group consisting of alkoxysilane compounds and halogenated silane compounds. It can synthesize | combine by hydrolysis or hydrolysis-condensation in presence of water and a catalyst in the inside.

As a raw silane compound which can be used here, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec- Butoxysilane, 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-propoxysilane, ethyl tree -n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane; Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, etc. are mentioned. Among them, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and trimethylmethoxysilane Or trimethylethoxysilane is preferred.

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

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

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

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene And partial ethers of polyhydric alcohol compounds such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether. These alcohol compounds can also be used 1 type or in combination of 2 or more types.

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

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

As said amide compound, for example, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N -Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. These amide compounds can also be used 1 type or in combination of 2 or more types.

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

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

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

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

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

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

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

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

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

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

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

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

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

Preferred among these catalysts are metal chelate compounds, organic acids or inorganic acids, more preferably titanium chelate compounds or organic acids.

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

The water added at the time of synthesis | combination of another polyorganosiloxane (C2) can be added intermittently or continuously in the silane compound which is a raw material, or in the solution which melt | dissolved a silane compound in the organic solvent.

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

As reaction temperature at the time of the synthesis | combination of another polyorganosiloxane (C2), Preferably it is 0-100 degreeC, More preferably, it is 15-80 degreeC. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

[Use ratio of other polymer (C)]

When the liquid crystal aligning agent of this invention contains another polymer (C) with the polyorganosiloxane (A) mentioned above, 10,000 weight part with respect to 100 weight part of polyorganosiloxane (A) as a content rate of another polymer. It is preferable that it is the following. The more preferable content rate of another polymer (C) changes with kinds of another polymer.

The more preferable use ratio of both when the liquid crystal aligning agent of this invention contains a polyorganosiloxane (A) and 1 or more types of polymers (C1) chosen from the group which consists of a polyamic acid and a polyimide is polyor The total amount of polyamic acid and polyimide relative to 100 parts by weight of the organosiloxane (A) is 200 to 5,000 parts by weight.

On the other hand, the more preferable use ratio of the case where the liquid crystal aligning agent of this invention contains a polyorganosiloxane (A) and another polyorganosiloxane (C2) is 100 weight part to polyorganosiloxane (A) parts. The amount of other polyorganosiloxane (C2) relative to 100 to 2,000 parts by weight.

In the case where the liquid crystal aligning agent of the present invention contains another polymer (C) together with the polyorganosiloxane (A), as the kind of the other polymer (C), at least one polymer selected from the group consisting of polyamic acid and polyimide It is preferable that it is (C1) or other polyorganosiloxane (C2). As another polymer (C), it is especially preferable that it is at least 1 type of polymer (C1) chosen from the group which consists of a polyamic acid and a 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 board | substrate surface of the liquid crystal aligning film formed more. As such an epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-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'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl -Aminomethylcyclohexane etc. are mentioned as a preferable thing. The blending ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 100 parts by weight of the total of the polymer (the total of the polyorganosiloxane (A) and the other polymer (C), which is the same below). Is 0.1 to 30 parts by weight. When the liquid crystal aligning agent of this invention contains an epoxy compound, you may use together base catalysts, such as 1-benzyl- 2-methylimidazole, for the purpose of efficiently causing the crosslinking reaction of an epoxy group.

[Functional silane compound]

The said functional silane compound can be used for the purpose of improving the adhesiveness with the board | substrate of the liquid crystal aligning film obtained. As a functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3, 6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-amino Lofiltriethoxysilane, 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 the like. The reactant of the tetracarboxylic dianhydride and the silane compound which has an amino group described in patent document 17 (Unexamined-Japanese-Patent No. 63-291922) is mentioned.

When the liquid crystal aligning agent of this invention contains a functional silane compound, As the content rate, Preferably it is 50 weight part or less with respect to a total of 100 weight part of polymers, More preferably, it is 20 weight part or less.

[Curing agent, curing catalyst]

The said hardening | curing agent and a hardening catalyst can be contained in the liquid crystal aligning agent of this invention for the purpose of strengthening crosslinking of polyorganosiloxane (A), respectively, and raising the intensity | strength of a liquid crystal aligning film more. When the liquid crystal aligning agent of this invention contains a hardening | curing agent, you may use together a hardening accelerator further.

As said hardening | curing agent, the hardening | curing agent generally used for hardening of an epoxy group can be used. As such a hardening | curing agent, polyhydric amine, polyhydric carboxylic anhydride, polyhydric carboxylic acid can be used, for example. Specific examples of the polyhydric carboxylic anhydride include cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, and the like. Can be mentioned. In addition, as cyclohexane tricarboxylic anhydride, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4- anhydride, cyclohexane-1,3,5-tricarboxylic acid-3, Α-terpinene, allo, in addition to 5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-acid anhydride, 4-methyltetrahydrophthalic anhydride, methylnadic acid anhydride, dodecenylsuccinic anhydride Diels-Alder reaction products of alicyclic compounds having a conjugated double bond and maleic anhydride, such as osmenene, hydrogenated products thereof, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, and the like. The compound illustrated above can be mentioned as tetracarboxylic dianhydride to be mentioned.

As said hardening accelerator, For example, diazabicyclo alkenes, such as an imidazole compound, a quaternary phosphorus compound, a quaternary amine compound, 1, 8- diazabicyclo [5.4.0] undecene-7, and its organic acid salt;

Organometallic compounds such as zinc octylate, octylate tin, and aluminum acetylacetone complex;

Boron compounds such as boron trifluoride and triphenyl borate; High-melting-point dispersion type latent curing accelerators such as metal chloride compounds such as zinc chloride and ditin chloride, amine addition accelerators such as dicyandiamide, amine and epoxy resin adducts;

Microcapsule-type latent curing accelerators in which a surface of a curing accelerator such as quaternary phosphonium salt is coated with a polymer; Amine salt type latent curing accelerators; Latent curing accelerators, such as a high temperature dissociation type | mold thermal cationic polymerization type latent hardening accelerator, such as a Lewis acid salt and Bronsted salt, are mentioned.

As the curing catalyst, for example, an antimony hexafluoride compound, a phosphorus hexafluoride compound, an aluminum trisacetylacetonate, or the like can be used.

[Surfactants]

As said surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant etc. are mentioned, for example.

When the liquid crystal aligning agent of this invention contains surfactant, it is 10 weight part or less with respect to all 100 weight part of liquid crystal aligning agents as the content rate, More preferably, it is 1 weight part or less.

<Liquid crystal aligning agent>

Although the liquid crystal aligning agent of this invention contains a polyorganosiloxane (A) and a compound (B) as an essential component as mentioned above, and also contains another component as needed in addition, Preferably each component is organic It is prepared as a solution phase composition dissolved in a solvent.

As an organic solvent which can be used for manufacturing the liquid crystal aligning agent of this invention, it is preferable to melt a polyorganosiloxane (A), a compound (B), and the other components used arbitrarily, and to not react with these.

The preferable organic solvent which can be used suitably for the liquid crystal aligning agent of this invention changes with kinds of the other polymer (C) added arbitrarily.

As a preferable organic solvent in the case where the liquid crystal aligning agent of this invention contains 1 or more types of polymers (C1) chosen from the group which consists of a polyorganosiloxane (A), a polyamic acid, and a polyimide, it is used for synthesis | combination of a polyamic acid. As an organic solvent, the organic solvent illustrated above can be mentioned. These organic solvents can be used individually or in combination of 2 or more types.

On the other hand, when the liquid crystal aligning agent of this invention contains only a polyorganosiloxane (A) as a polymer, or when it contains a polyorganosiloxane (A) and another polyorganosiloxane (C2), it is preferable. Examples of the solvent include 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, Dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol Monohexyl ether, diethylene glycol, methyl cellosolve acetate, e 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- acetate Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cycloacetate Hexyl, octyl acetate, amyl acetate, isoamyl acetate and the like. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, etc. are mentioned preferably.

The preferable solvent used for manufacture of the liquid crystal aligning agent of this invention is obtained by combining 1 type (s) or 2 or more types of the above-mentioned organic solvent according to the presence or absence of the use of another polymer, and its kind, and liquid-crystal orientation in the following preferable solid content concentration Each component contained in the agent does not precipitate, and the surface tension of the liquid crystal aligning agent is in a range of 25 to 40 mN / m.

Solid content concentration of the liquid crystal aligning agent of this invention, ie, the ratio which the weight of all components other than the solvent in a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., Preferably it is 1-10 weight It is% of range. Although the liquid crystal aligning agent of this invention forms on the surface of a board | substrate, and forms the coating film used as a liquid crystal aligning film, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and it may be difficult to obtain a favorable liquid crystal aligning film. . On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes large too much and it is difficult to obtain a favorable liquid crystal aligning film, the viscosity of a liquid crystal aligning agent may increase, and coating characteristics may be inadequate. The range of especially preferable solid content concentration changes with methods used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% is especially 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 the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 10 degreeC-60 degreeC.

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention as mentioned above.

As for the method of forming a liquid crystal aligning film using the liquid crystal aligning agent of this invention, the structure which has the liquid crystal aligning ability which compound a used for the synthesis | combination of the liquid crystal aligning polyorganosiloxane in this invention has (therefore, polyorganosiloxane The structure which has the liquid-crystal orientation ability in group X 'of (A) differs depending on whether it has a structure represented by the said general formula (X'-1).

When the polyorganosiloxane (A) does not have a structure represented by the said general formula (X'-1), by apply | coating the liquid crystal aligning agent of this invention on a board | substrate, forming a coating film and performing a rubbing process as needed. It can be set as a liquid crystal aligning film.

On the other hand, when the polyorganosiloxane (A) has a structure represented by the said general formula (X'-1), the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, a coating film is formed, and then this coating film is a radiation By irradiating, it can be set as a liquid crystal aligning film.

[When the polyorganosiloxane (A) does not have a structure represented by the said general formula (X'-1)]

First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and then a coating film is formed on a board | substrate by heating a coating surface. Two board | substrates with which the patterned transparent conductive film is provided are paired, and the liquid crystal aligning agent of this invention is respectively apply | coated by the roll coater method, the spinner method, the printing method, and the inkjet method on each transparent conductive film formation surface. do. Furthermore, a coating film is formed by preheating (prebaking) and then baking (post-baking) the said coating surface. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-baking conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably Preferably 10 to 100 minutes. The film thickness of the coating film after post-baking becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

As said board | substrate, For example, glass, such as float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and alicyclic polyolefin can be used.

Examples of the transparent conductive film provided on one side of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). Etc. can be used. In order to obtain a patterned transparent conductive film, for example, a transparent conductive film is formed without a pattern, and then a pattern is formed by photoetching, a method using a mask having a target pattern when forming a transparent conductive film, or the like. Can be. At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, and the like are previously applied to the surface on which the coating film should be formed on the substrate surface. Pretreatment can also be performed.

When the liquid crystal aligning agent of this invention is used for formation of the liquid crystal aligning film for vertical alignment liquid crystal display elements, the coating film formed as mentioned above can be used as a liquid crystal aligning film for vertical alignment liquid crystal display elements as it is, but this coating film surface The rubbing process may be optionally performed. On the other hand, when using the liquid crystal aligning agent of this invention for formation of the liquid crystal aligning film for horizontal alignment type liquid crystal display elements, it can be set as a liquid crystal aligning film by performing a rubbing process to the coating film formed as mentioned above.

The rubbing treatment can be performed, for example, by rubbing in a predetermined direction with a roll wound with a cloth containing fibers such as nylon, rayon, cotton or the like. In this case, as described in Patent Document 18 (Japanese Patent Laid-Open No. 6-222366) and Patent Document 19 (Japanese Patent Laid-Open No. 6-281937) for the formed liquid crystal alignment film, for example. Similarly, the process which changes a pretilt angle by irradiating a part of liquid crystal aligning film with an ultraviolet-ray, or as described in patent document 20 (Unexamined-Japanese-Patent No. 5-107544), the formed liquid crystal A horizontal liquid crystal obtained by forming a resist film on a part of the surface of the alignment film, then performing a rubbing treatment in a direction different from the rubbing treatment previously performed, and then removing the resist film and subjecting the liquid crystal alignment film to have different liquid crystal alignment capabilities for each region. The viewing characteristics of the display element can also be improved.

Two board | substrates with a liquid crystal aligning film are prepared as mentioned above, and a liquid crystal cell is manufactured by arrange | positioning a liquid crystal between these two board | substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a method known in the art. First, two substrates are disposed to face each other with a gap (cell spacing) so that the respective liquid crystal alignment films face each other, the peripheral portions of the two substrates are bonded together using a sealant, and the cell partitioned by the substrate surface and the sealing agent. After the injection filling of the liquid crystal within the interval, the liquid crystal cell can be produced by sealing the injection hole.

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

In any case, it is preferable that the liquid crystal cell is subsequently heated to a temperature at which the used liquid crystal takes an isotropic phase and then gradually cooled to room temperature to remove the flow orientation during injection.

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

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

As said liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. can be used, for example. When manufacturing the liquid crystal display element which has a TN type liquid crystal cell or STN type liquid crystal cell, what has positive dielectric anisotropy (positive liquid crystal) in a nematic type liquid crystal is preferable, for example, a biphenyl type liquid crystal and a phenyl cyclohexane Type liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, and cuban liquid crystals. To these liquid crystals, For example, cholesteric liquid crystals, such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate; Chiral agent sold as brand names C-15 and CB-15 (made by Merck); Ferroelectric liquid crystals such as p-disiloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.

On the other hand, in the case of a vertically aligned liquid crystal cell, one having a negative dielectric anisotropy (negative liquid crystal) among nematic liquid crystals is preferable, for example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, and a Schiff salt. Mechanical liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals and the like are used.

As a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate which consists of H film itself, etc. are mentioned. .

[When polyorganosiloxane (A) has a structure represented by the said general formula (X'-1)]

In this case, in the manufacturing method of the liquid crystal aligning film in case the said polyorganosiloxane (A) does not have a structure represented by the said general formula (X'-1), a liquid crystal display element is performed by irradiating radiation instead of a rubbing process. Can be prepared.

As the radiation used for the irradiation treatment, linearly or partially polarized radiation or non-polarized radiation can be used, and for example, ultraviolet rays or visible rays containing light having a wavelength of 150 to 800 nm can be used. Preference is given to ultraviolet rays comprising light having a wavelength of 300 to 400 nm. When the radiation to be used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an inclined direction in order to give a pretilt angle, or a combination thereof may be performed. In the case of irradiating non-polarized radiation, the irradiation direction needs to be inclined direction.

As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used. Ultraviolet rays in the preferred wavelength region can be obtained by means of using the light source together with a filter, a diffraction grating, or the like, for example.

The irradiation amount of the radiation is preferably 1 J / m 2 or more and less than 10,000 J / m 2, more preferably 10 to 3,000 J / m 2. Moreover, when providing liquid crystal aligning ability to the coating film formed from the liquid crystal aligning agent known conventionally by the photo-alignment method, the radiation amount of 10,000 J / m <2> or more was required. However, when the liquid crystal aligning agent of this invention is used, even if the radiation dose in the photo-alignment method is 3,000 J / m <2> or less, Furthermore, 1,000 J / m <2> or less, Especially 500 J / m <2> or less, favorable liquid crystal alignability can be provided, It is effective for reducing the manufacturing cost of a liquid crystal display element.

It is preferable that the liquid crystal display element of this invention is a vertical alignment liquid crystal display element.

The liquid crystal display device 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 used in forming the liquid crystal alignment film.

[Example]

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.

In the following Examples, the weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.

Column: Toso Corporation, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68 kgf / ㎠

Epoxy equivalent was measured according to the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

The following synthesis example ensured the product of the required amount to be used by the following synthesis example and the Example by repeating on the following synthesis scale as needed.

<Synthesis of polyorganosiloxane having epoxy structure>

Synthesis Example 1

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. And mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise over 30 minutes from the dropping funnel, followed by reaction at 80 ° C. for 6 hours while mixing under reflux. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous ammonium nitrate solution until the water after washing became neutral, and then viscous polyorganosiloxane EPS-1 was obtained by distilling off the solvent and water under reduced pressure. (Iii) obtained as a transparent liquid.

¹ H-NMR analysis of the polyorganosiloxane EPS-1 showed that a peak based on the oxiranyl group was obtained according to the theoretical strength near the chemical shift (δ) = 3.2 ppm, and no side reaction of the epoxy group occurred during the reaction. It was confirmed.

Mw of this polyorganosiloxane EPS-1 was 2,200, and epoxy equivalent was 186.

Synthesis of Compound a

Synthesis Example a-1

According to Scheme 1 below, compound (A-1-C1-1) was synthesized.

82 g of p-hydroxycinnamic acid, 304 g of potassium carbonate, and 400 mL of N-methyl-2-pyrrolidone were added to a 1 L branched flask, followed by stirring at room temperature for 1 hour, followed by 1-bromo 166 g of pentane were added and stirred at 100 ° C. for 5 hours. Thereafter, the solvent was distilled off under reduced pressure. 48 g of sodium hydroxide and 400 mL of water were added thereto, and the mixture was 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

According to Scheme 2 below, compound (A-1-C4-1) was synthesized.

91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate, and 320 mL of N-methyl-2-pyrrolidone were added to a 1 L branched flask, and stirred at room temperature for 1 hour, followed by 1-bromo 99.7 g of pentane were added and the reaction was carried out at 100 ° C. for 5 hours with stirring. After the reaction was completed, reprecipitation was carried out with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to undergo a hydrolysis reaction. After the reaction was completed, 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) were taken into a reaction vessel, and 1 L of thionyl chloride and 770 µL of N, N-dimethylformamide were added thereto, followed by stirring at 80 ° C for 1 hour. Subsequently, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with an aqueous sodium bicarbonate solution, dried over magnesium sulfate, concentrated, and tetrahydrofuran was added to make a solution.

Subsequently, 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 added to a separate 5 L three-neck flask. This aqueous solution was ice-cooled, and the tetrahydrofuran solution containing the reaction product of the compound (A-1-C4-1A) and thionyl chloride described above was slowly added dropwise, and the reaction was further performed under stirring for 2 hours. After completion of the reaction, neutralization was performed by adding hydrochloric acid to the reaction mixture, followed by extraction with ethyl acetate. The extract was dried over magnesium sulfate, concentrated and recrystallized with ethanol to give white crystals of compound (A-1-C4-1). 90 g was obtained.

Synthesis Example a-3

According to Scheme 3 below, compound (A-1-C4-2) was synthesized.

82 g of methyl 4-hydroxybenzoate, 166 g of potassium carbonate, and 400 mL of N, N-dimethylacetamide were added to a 1 L branched flask, followed by stirring at room temperature for 1 hour, followed by 4,4,4- 95 g of trifluoro-1-iodobutane were added and the reaction was carried out at room temperature for 5 hours with stirring. After the reaction was completed, reprecipitation was carried out with water. Subsequently, 32 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 4 hours to undergo a hydrolysis reaction. After the reaction was completed, 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) were taken into a reaction vessel, to which 200 mL of thionyl chloride and 0.2 mL of N, N-dimethylformamide were added and stirred at 80 ° C for 1 hour. Subsequently, 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.

Subsequently, 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 added to a separate 2 L three-neck flask. This aqueous solution was ice-cooled, the tetrahydrofuran solution containing the reaction product of the compound (A-1-C4-2A) and thionyl chloride mentioned above was dripped slowly, and reaction was performed under stirring for 2 hours. After the completion of the reaction, the reaction mixture was neutralized by addition of hydrochloric acid, extracted with ethyl acetate, the extract was dried over magnesium sulfate, concentrated and recrystallized with ethanol to give white crystals of compound (A-1-C4-2). 39 g was obtained.

Synthesis Example a-4

According to Scheme 4 below, compound (A-1-C8-1) was synthesized.

That is, in Synthesis Example a-2, except that 9.91 g of 4-pentyl-transcyclohexylcarboxylic acid was used in place of Compound (A-1-C4-1A), the compound of Synthesis Example a-2 (A-1 13g of white crystals of a compound (A-1-C8-1) were obtained by carrying out similarly to the synthesis of -C4-1).

Synthesis Example a-5

According to Scheme 5, Compound (A-1-C16-1) was synthesized.

In a 500 mL three-necked flask equipped with a reflux tube, thermometer, and 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, triethylamine 56 mL, 8.2 mL of acrylic acid and 200 mL of N, N-dimethylacetamide were added thereto, and the reaction was carried out at 120 ° C. for 3 hours with stirring. 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 twice with dilute hydrochloric acid and three times with water. 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 a crystal of Compound (A-1-C16-1).

Synthesis Example a-6

According to Scheme 6, Compound (A-1-C17-1) was synthesized.

That is, the compound (A-1-C17-) was carried 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). 16 g of 1) was obtained.

Synthesis Example a-7

According to Scheme 7 below, compound (A-4-C1-1) was synthesized.

12 g of decylsuccinic anhydride, 8.2 g of 4-aminocinnamic acid and 100 mL of acetic acid were added to a 200 mL eggplant flask equipped with a reflux tube, and the reaction was performed under reflux for 2 hours. After the completion of the reaction, the reaction mixture was extracted with ethyl acetate, the organic layer was washed with water, dried over magnesium sulfate, purified by silica column and recrystallized with a mixed solvent of ethanol and tetrahydrofuran (A-4- 10g of white crystals (purity 98.0%) of C1-1) were obtained.

Synthesis Example a-8

In the synthesis example a-5, except that 28 g of the compound (A-1-C16-2A) represented by the following formula instead of the compound (A-1-C16-1A) was used, and in the same manner as in the synthesis example a-5 14g of crystals of the compound (A-1-C16-2) represented by the following formula were obtained.

Synthesis Example a-9

According to Scheme 8 below, compound (A-9-4-1) was synthesized.

Into a 500 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube, 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 were added. And reaction under reflux for 8 hours. After the completion of the reaction, the organic layer obtained by adding 200 mL of tetrahydrofuran to the reaction mixture was washed sequentially with 2 N aqueous hydrochloric acid and three times with water, dried over magnesium sulfate, and then the solvent was removed under reduced pressure. 38g of white crystals of a compound (A-9-4-1) were obtained by recrystallization from ethyl acetate.

<Synthesis of Polyorganosiloxane (A)>

Synthesis Example VE-1

10.0 g of polyorganosiloxane EPS-1, 30.28 g of methyl isobutyl ketone, and 3.82 g of stearic acid (50 mol% with respect to the epoxy group which polyorganosiloxane EPS-1 has in a 200 mL three neck flask) Equivalent to) and 0.10 g of UCAT 18X (trade name, manufactured by San Apro Co., Ltd., a curing accelerator for epoxy compounds) was added thereto, and the reaction was carried out at 100 ° C. for 48 hours with stirring. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. The precipitate was dissolved in ethyl acetate, washed three times with water, the organic layer was dried using magnesium sulfate, and then the solvent was distilled off to remove the polyorgano. 8.1 g of a white powder of siloxane S-VE-1 was obtained. The weight average molecular weight of S-VE-1 was 10,100.

Synthesis Example VE-2

9.0 g of a white powder of polyorganosiloxane S-VE-2 in the same manner 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. Got. The weight average molecular weight of S-VE-2 was 9,900.

Synthesis Example CE-1

Compound (A-1-C4-1) obtained in Synthesis Example a-2 as 5.0 g of polyorganosiloxane EPS-1 obtained in Synthesis Example 1, 46.4 g of methyl isobutyl ketone, and Compound a in a 200 mL three-neck flask. 4.76 g (corresponding to 50 mol% of the epoxy group of the polyorganosiloxane EPS-1) and 0.10 g of tetrabutylammonium bromide were added thereto, and the reaction was carried out at 80 ° C. for 8 hours with stirring. After the completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution. The solution was washed three times, and then the solvent was distilled off to give polyorganosiloxane S-CE-1 as a white powder. g was obtained. The weight average molecular weight Mw of this polyorganosiloxane S-CE-1 was 9,500.

Synthesis Examples CE-2 to 12

Various polyorganosiloxane (A) by carrying out similarly to synthesis example CE-1 except having used the compound of Table 1 instead of compound (A-1-C4-1) as compound a in said synthesis example CE-1. Were synthesized, respectively. The weight average molecular weight Mw of each polyorganosiloxane obtained here is put together in Table 1, and is shown.

The use ratio of the compound a in Table 1 is mol% with respect to the epoxy group which polyorganosiloxane EPS-1 has.

In addition, in the synthesis examples CE-6-8 and 12, the compound a was used 2 types, respectively.

Synthesis of Compound (B)

Synthesis Example B-1

According to Scheme 9 below, compound (B-1-1) was synthesized.

To a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, 21 g of trimesic acid, 60 g of n-butyl vinyl ether, and 0.09 g of phosphoric acid were added, and the reaction was carried out at 50 ° C. for 30 hours with stirring. . After the completion of the reaction, the organic layer obtained by adding 500 mL of hexane to the reaction mixture was separated and washed two times with 1 M aqueous sodium hydroxide solution and three times with water. Then, 50 g of compounds (B-1-1) were obtained as a colorless transparent liquid by distilling a solvent off from the organic layer.

Synthesis Example B-2 and 3

Except for using 17 g of isophthalic acid or 35 g of the compound represented by the following formula (B-1-3a) in place of trimesic acid in Synthesis Example B-1, 45 g of the compound represented by B-1-2) and 63 g of the compound represented by the following formula (B-1-3) were obtained, respectively.

<Synthesis of other polymer (C)>

[Synthesis of Polyamic Acid]

Synthesis Example PA-1

1,96 g (1.0 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine (1.0 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

86.3 g (0.44 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 96.0 g (0.44 mol) of pyromellitic dianhydride, 2,2'-dimethyl as diamine 20 weights of polyamic acid (PA-2) was dissolved by dissolving 191.0 g (0.90 mol) of -4,4'-diaminobiphenyl in 1,490 g of N-methyl-2-pyrrolidone and reacting at 40 DEG C for 4 hours. The solution containing% was obtained. The polyamic acid solution was aliquoted in small amounts, and the viscosity of the solution obtained by adding N-methyl-2-pyrrolidone to 10% by weight was 43 mPa · s.

Synthesis of Polyimide

Synthesis Example PI-1

20.9 g (0.093 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 9.2 g (0.085 mol) of p-phenylenediamine as diamine and represented by the following general formula (D-2) 4.9 g (0.009 mol) of the compound was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing polyamic acid. A little aliquot of the obtained polyamic-acid solution was added, N-methyl- 2-pyrrolidone was added, and the solution viscosity was measured as a solution of 10 weight% of polymer concentration, and it was 126 mPa * s.

Subsequently, 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 to dehydrate and close the ring at 110 ° C. for 4 hours. After the dehydration ring closure, about 210 g of a solution containing 16.1% by weight of polyimide (PI-1) having an imidization rate of about 54% was obtained by solvent substitution of the solvent in the system with fresh N-methyl-2-pyrrolidone. .

The solution viscosity measured as a small amount of this polyimide solution, the addition of N-methyl- 2-pyrrolidone, and the solution of 10 weight% of polymer concentrations was 75 mPa * s.

Synthesis Example PI-2

20.0 g (0.089 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 6.8 g (0.063 mol) of p-phenylenediamine as diamine, 4,4'-diaminodiphenyl 3.6 g (0.018 mol) of methane 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 reacted at 60 ° C. for 4 hours to remove polya. The solution containing 20 weight% of mymic acid was obtained. It was 2,200 mPa * s when the solution viscosity of the obtained polyamic-acid solution was measured.

Subsequently, 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 a dehydration ring closing reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closure reaction, about 160 g of a solution containing 20% by weight of polyimide (PI-2) having an imidization rate of about 65% was obtained by solvent substitution of the solution in the system with fresh N-methyl-2-pyrrolidone. .

Synthesis Example PI-3

19.2 g (0.086 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 5.2 g (0.034 mol) of 3,5-diaminobenzoic acid as diamine and the following general formula (D-3) 25.5 g (0.052 mol) of diamine represented by the above 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. It was 1,450 mPa * s when the solution viscosity of the obtained polyamic-acid solution was measured.

Subsequently, 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-closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closure reaction, about 230 g of a solution containing 20% by weight of polyimide (PI-3) having an imidization rate of about 67% was obtained by solvent substitution of the solution in the system with fresh N-methyl-2-pyrrolidone. .

Synthesis Example PI-4

21.3 g (0.095 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 4.3 g (0.029 mol) of 3,5-diaminobenzoic acid as diamine, formula (D-3) 18.8 g (0.038 mol) of the compound represented by the formula and 5.5 g (0.029 mol) of N- (2,4-diaminophenyl) -piperidine, which is a compound represented by the following formula (D-4), were N-methyl-2 -A solution containing 20% by weight of polyamic acid was obtained by dissolving in 200 g of pyrrolidone and reacting at 60 DEG C for 4 hours. It was 900 mPa * s when the solution viscosity of the obtained polyamic-acid solution was measured.

Subsequently, 250 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 11.29 g of pyridine and 14.58 g of acetic anhydride were added to carry out a dehydration ring closure reaction at 110 ° C. for 4 hours. After dehydration ring closure, about 230 g of a solution containing 20% by weight of polyimide (PI-4) having an imidization rate of about 69% was obtained by solvent substitution of the solution in the system with fresh N-methyl-2-pyrrolidone. .

Synthesis Example PI-5

22.9 g (0.10 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 6.7 g (0.062 mol) of m-phenylenediamine as diamine and represented by the above formula (D-4) 20.4 g (0.041 mol) of the resulting compound 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. It was 1,200 mPa * s when the solution viscosity of the obtained polyamic-acid solution was measured.

Subsequently, 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-closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closure reaction, about 230 g of a solution containing 20% by weight of polyimide (PI-5) having an imidization rate of about 65% was obtained by solvent substitution of the solution in the system with fresh N-methyl-2-pyrrolidone. .

[Synthesis of Other Polyorganosiloxanes (C2)]

Synthesis Example PS-1

20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated to 60 ° C and stirred. To this was added an aqueous solution of maleic anhydride in which 0.26 g of maleic anhydride prepared in a separate flask having a volume of 20 mL was dissolved in 10.8 g of water, and the reaction was carried out at 60 ° C. for 4 hours under stirring. After the completion of the reaction, the solvent was distilled off from the obtained reaction mixture, 1-ethoxy-2-propanol was added to the residue and concentrated again to obtain a solution containing 10% by weight of polyorganosiloxane PS-1. It was 5,100 when the weight average molecular weight Mw of this polyorganosiloxane PS-1 was measured.

<Production of Liquid Crystal Alignment Agent and Evaluation of Storage Stability>

Example VE-1

As other polymer (C), the amount equivalent to 1,000 parts by weight in terms of PA-1 of the solution containing polyamic acid PA-1 synthesized in Synthesis Example PA-1 was taken, and polyorganosiloxane (A) was added thereto. 100 parts by weight of polyorganosiloxane S-VE-1 synthesized in Synthesis Example VE-1 and 47 parts by weight of Compound (B-1-1) obtained in Synthesis Example B-1 were added as Compound (B), Furthermore, N-methyl-2-pyrrolidone and butyl cellosolve were added, and a solvent composition was N-methyl- 2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio), and solid content concentration is 3.0 weight%. Solution. The liquid crystal aligning agent A-VE-1 was manufactured by filtering this solution with the filter of 1 micrometer of pore diameters.

The storage stability of the liquid crystal aligning agent A-VE-1 was "good" when the storage stability was evaluated by the following method and the criterion about this liquid crystal aligning agent A-VE-1.

[Evaluation Method of Preservation Stability (1)]

The liquid crystal aligning agent is apply | coated on the glass substrate by spin coating as a variable, and it heats at 200 degreeC for 60 minutes, then forms a coating film and irradiates the rotation speed which the film thickness of the coating film after solvent removal becomes 1,000 kPa. It was.

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

If no insoluble matter is observed after 5 weeks of storage, the film is applied by spin coating at a rotational speed of 1,000 kPa prior to storage using a liquid crystal aligning agent after storage on a glass substrate, followed by 60 at 200 ° C. The coating film was formed by heating for minutes, and the film thickness after solvent removal was measured. When this film thickness has a 10% or more deviation from 1,000 mm, it is determined as storage stability "poor", and when the film thickness is less than 10%, it is determined as storage stability "good".

In addition, the measurement of the film thickness of the said coating film was performed using the etch-resistant step film thickness meter by KLA-Tencor Corporation.

Examples VE-2 to 4

Liquid crystal aligning agents A-VE-2 to 4 were carried out in the same manner as in Example VE-1 except that the kind of polyorganosiloxane (A), the kind and amount of compound (B) were as described in Table 2. Were prepared respectively and the storage stability was evaluated. The evaluation results are shown in Table 2.

Example VE-5

The amount equivalent to 500 parts by weight in terms of PS-1 of the solution containing polyorganosiloxane PS-1 synthesized in Synthesis Example PS-1 was taken, and this was synthesized in Synthesis Example VE-1. 100 parts by weight of the organosiloxane 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 give a solid content of 4.0. It was set as the weight% solution. The liquid crystal aligning agent A-VE-5 was manufactured by filtering this solution with the filter of 1 micrometer of pore diameters.

The storage stability of this liquid crystal aligning agent A-VE-5 was evaluated like Example VE-1. The evaluation results are shown in Table 2.

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

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 transparent electrode containing the ITO film by using a spinner, and prebaking was performed for 1 minute on an 80 ° C. hot plate. After carrying out, the coating film (liquid crystal aligning film) with a film thickness of 0.1 micrometer was formed by heating at 200 degreeC for 1 hour in oven substituted with nitrogen. This operation was repeated and a pair (two sheets) of board | substrates which have a liquid crystal aligning film were manufactured.

After apply | coating by screen printing the aluminum oxide sphere containing epoxy resin adhesive of 5.5 micrometers in diameter to the outer peripheral part of the surface which has one liquid crystal aligning film among the said board | substrates, it overlaps and crimps | bonds the liquid crystal aligning film surface of a pair of board | substrate, and is 150 degreeC The adhesive was heat cured by heating at 1 h. Subsequently, the negative liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) was filled in the gap between the substrates from the liquid crystal injection hole, and then the liquid crystal injection hole was sealed with an epoxy adhesive, and this was removed at 150 ° C. in order to remove the flow orientation during liquid crystal injection. After heating for 10 minutes, it was cooled slowly to room temperature.

Moreover, the vertical alignment type liquid crystal display element was manufactured by bonding the polarizing plate to the outer both surfaces of the board | substrate so that the polarization direction of two polarizing plates may mutually orthogonally cross.

[Evaluation of Vertically Oriented Liquid Crystal Display Element]

(1) Evaluation of liquid crystal alignment

The presence or absence of an abnormal domain in the change in contrast when the voltage of 5 V was turned ON / OFF (applied / released) to the liquid crystal display device manufactured above was visually observed.

When no light leakage is observed from the cell when the voltage is OFF, and the cell drive region is white when the voltage is applied, and there is no light leakage from the other region, the liquid crystal alignment property is "good", and the light is emitted from the cell when the voltage is OFF. When leakage was observed or when light leakage was observed from regions other than the cell drive region at the time of voltage ON, the liquid crystal alignment property "good" was evaluated as liquid crystal alignment property "poor".

(2) Evaluation of voltage retention

About the liquid crystal display element manufactured above, after applying the voltage of 5V at 60 degreeC with 60 microseconds application time and 167 milliseconds span, the voltage retention after 167 milliseconds after application | release cancellation was measured. As a measuring apparatus of voltage retention, Toyo Technica Corporation make, VHR-1 was used.

When the voltage retention was 97% or more as the voltage retention "good", the voltage retention of this liquid crystal display element was "good".

(3) evaluation of heat resistance

About the liquid crystal display element manufactured by carrying out similarly to the above, the initial voltage retention was measured on the conditions similar to the evaluation of the said voltage retention. Thereafter, the mixture was allowed to stand for 1,000 hours in an oven at 120 ° C., and the voltage retention was measured under the same conditions as described above. When the value of the voltage retention was less than ± 2% of the initial value as the heat resistance "good", and the case where ± 2% or more was evaluated as the heat resistance "poor", the heat resistance of this liquid crystal display element was "good".

(4) Evaluation of Afterimage Characteristics

To the liquid crystal display device manufactured in the same manner as above, a voltage of DC 17 V 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 cut off (residual DC voltage) was measured. It calculated | required by the flicker cancellation method. When the value of this residual DC voltage was 500 mV or less, when the heat resistance "good" and the case exceeding 500 mV were evaluated as heat resistance "poor", the afterimage characteristic of this liquid crystal display element was "good".

Examples VE-7 to 10

Except having used what was shown in Table 3 as the liquid crystal aligning agent in Example VE-6, respectively, it carried out similarly to Example VE-6, and manufactured and evaluated the vertical alignment type liquid crystal display element. The results are shown in Table 3.

<Production of Liquid Crystal Alignment 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-1 obtained in Synthesis Example PA-1 as another polymer (C). 41 parts by weight of the compound (B-1-2) obtained in Synthesis Example B-2 as a compound (B) and 2,000 parts by weight in terms of PA-1 of the solution to be added were added thereto. 2-pyrrolidone and butyl cellosolve were added 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 liquid crystal aligning agent A-CE-1 was manufactured by filtering this solution with the filter of 1 micrometer of pore diameters.

The storage stability of the liquid crystal aligning agent A-CE-1 was "good" when the storage stability was evaluated by the following method and the criterion about this liquid crystal aligning agent A-CE-1.

[Evaluation Method of Preservation Stability (2)]

The liquid crystal aligning agent was stored at -15 degreeC for 6 months. The viscosity was measured by the E-type viscosity meter at 25 degreeC before and after storage. The case where the rate of change before and after the storage of the solution viscosity was less than 10% was evaluated as storage stability "good" and 10% or more as storage stability "bad".

Examples CE-2 to 31

Liquid crystal aligning agents A-CE-2 to A- in the same manner as in Example CE-1 except that the kind of polyorganosiloxane (A) and the kind of other polymer (C) were each as described in Table 4. CE-31 was prepared respectively. In Examples CE-30 and 31, two different polymers were used, respectively.

About these liquid crystal aligning agents, storage stability was evaluated similarly to Example CE-1. The evaluation results are shown in Table 4.

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

Example CE-32

[Production of Vertically Oriented Liquid Crystal Display Device]

The liquid crystal aligning agent A-CE-1 manufactured in the said Example CE-1 was apply | coated using the spinner on the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO membrane, and prebaking was carried out for 1 minute on 80 degreeC hotplate. After performing, the inside of the system was heated at 200 ° C. for 1 hour in an oven substituted with nitrogen to form a coating film having a thickness of 0.1 μm. Subsequently, using a Hg-Xe lamp and a glan taylor prism on this coating film surface, polarized ultraviolet-ray 200 J / m <2> containing 313 nm bright line was irradiated from the 40 degree tilt direction from the board | substrate normal, and it was set as the liquid crystal aligning film. The same operation was repeated and a pair (two sheets) of board | substrates which have a liquid crystal aligning film were manufactured.

After screen-printing the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer on the outer peripheral part of the surface which has one liquid crystal aligning film among the said board | substrates, the liquid crystal aligning film surface of a pair of board | substrate is made to oppose, and the ultraviolet-ray of each board | substrate is It crimp | bonded so that the projection direction with respect to the board | substrate surface of the optical axis might become antiparallel, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Subsequently, after filling a negative liquid crystal (MLC-6608 by Merck Co., Ltd.) in the clearance gap between a liquid crystal injection hole and a board | substrate, the liquid crystal injection hole was sealed with the epoxy adhesive. Moreover, in order to remove the flow orientation at the time of liquid crystal injection, after heating at 150 degreeC, it cooled gradually to room temperature. Next, the vertically-aligned liquid crystal display element was manufactured by bonding a polarizing plate to the outer both surfaces of a board | substrate so that the polarization direction may orthogonally cross, and to make an angle of 45 degrees with the projection direction with respect to the substrate surface of the optical axis of the ultraviolet-ray of a liquid crystal aligning film.

[Evaluation of Vertically Oriented Liquid Crystal Display Element]

About the liquid crystal display element manufactured as mentioned above, not only (1) liquid crystal alignability evaluation and (3) heat resistance evaluation were performed similarly to the said Example VE-6, but the said Example VE-6 In the same manner as in (2), the voltage retention was measured. Moreover, stability evaluation of the pretilt angle was performed as follows. The evaluation results are shown in Table 5.

(5) Evaluation of the stability of the pretilt angle

For the liquid crystal display device manufactured as described above, He-Ne based on the method described in Non-Patent Document 2 (TJ Scheffer et. Al. J. Appl. Phys. Vo. 19, p. 2013 (1980)). The pretilt angle was measured by the crystal rotation method using a laser beam (initial pretilt angle).

Subsequently, after leaving the said liquid crystal display element after the initial pretilt angle measurement for 30 days at 23 degreeC, the pretilt angle was measured again by the same method as the above (pretilt angle after storage).

At this time, the amount of change to the initial pretilt angle of the pretilt angle after storage was examined. When this value was less than 1 °, it was said that the stability over time of the pretilt angle was "good".

Examples CE-33-62

Except having performed the kind of the used liquid crystal aligning agent as Table 5, the vertically-aligned type liquid crystal display element was produced and evaluated similarly to the said Example CE-32. The results are shown in Table 5.

Claims (11)

Polyorganosiloxane (A) having a Si—X ′ bond (where X ′ is a group containing a structure having liquid crystal alignment capability) and a Si—X ^I bond (where X ^I is a group including an epoxy structure) , 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 a molecule thereof Compound (B) having two or more
It contains, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 1 wherein the polyorganosiloxane (A) a liquid crystal orientation of 10 to 90 mol% of the total of the group X 'is a group X of the ratio "and the group of the X ^I. The polyor according to claim 1 or 2, wherein the polyorganosiloxane (A) has a Si-X ^I bond, provided that X ^I has the same meaning as X ^I in the polyorganosiloxane (A). Of a compound having a structure having an organosiloxane, at least one group selected from the group consisting of a carboxyl group and a hydroxyl group, and a liquid crystal alignment ability, provided that the use ratio of the compound is 0.1 to 0.9 mole with respect to 1 mole of the group X ^I. Liquid crystal aligning agent which is a reaction product. The liquid crystal aligning agent according to claim 1 or 2, wherein the group X ^I is a group represented by the following formula (X ^I -1 ') or (X ^I -2').

Of (formula (X ^I -1 ') and (X ^I -2'), s is an integer from 0 to 3, t is an integer from 1 to 6, u is an integer from 0 to 2, v is from 0 to Is an integer of 6, and "*" each represents a bonding hand) The liquid crystal aligning agent according to claim 4, wherein the group X ^I is a group represented by the following general formula (X ^I -1) or (X ^I -2).

(In formulas (X ^I -1) and (X ^I -2), "*" each represents a bonding hand.) The structure having the liquid crystal alignment ability is 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 carbon atoms From the group consisting of an alkylcyclohexyl group having 1 to 20 alkyl groups, a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms and a fluoroalkoxycyclohexyl group having a fluoroalkoxy group having 1 to 20 carbon atoms The liquid crystal aligning agent which is a structure containing 1 or more types selected. The liquid crystal aligning agent of Claim 6 whose structure which has the said liquid crystal aligning ability is a structure containing the structure represented by following General formula (X'-1) further.

(In formula (X'-1), m is an integer of 0-4.) The liquid crystal aligning agent of Claim 1 or 2 containing 1 or more types of polymers (C1) further chosen from the group which consists of a polyamic acid and a polyimide. The liquid crystal aligning agent of Claim 1 or 2 which further contains polyorganosiloxane (C2) other than the said polyorganosiloxane (A). After apply | coating the liquid crystal aligning agent of Claim 7 on a board | substrate, it heats, forms a coating film, and irradiates the said coating film, The formation method of the liquid crystal aligning film characterized by the above-mentioned. The liquid crystal aligning film formed from the liquid crystal aligning agent of Claim 1 or 2 is provided. The liquid crystal display element characterized by the above-mentioned.