JP5642435B2 - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal aligning agent that provides a liquid crystal alignment film excellent in alignment regulating power of liquid crystal molecules and a liquid crystal display element excellent in display quality.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy is sandwiched with a substrate with a transparent electrode having a liquid crystal alignment film, and the major axis of the liquid crystal molecules is continuously twisted between 0 and 360 ° between the substrates as necessary. There are known liquid crystal display elements such as TN (Twisted Nematic) type and STN (Super Twisted Nematic) type (see Patent Documents 1 and 2).
In such a liquid crystal display element, in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface, it is necessary to provide a liquid crystal alignment film on the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon. However, when the liquid crystal alignment film is formed by a rubbing process, dust and static electricity are likely to be generated in the process, so that there is a problem that dust adheres to the alignment film surface and causes display defects. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, there has been a problem that the circuit damage of the TFT element occurs due to the generated static electricity, resulting in a decrease in yield. Furthermore, in liquid crystal display elements that will be further refined in the future, unevenness is generated on the substrate surface as the density of pixels increases, and it is becoming difficult to perform rubbing treatment uniformly.
As another means of regulating the alignment of liquid crystal molecules in a liquid crystal display device, the liquid crystal alignment ability is improved by irradiating a photosensitive thin film such as polyvinyl cinnamate, polyimide, azobenzene derivative, etc. formed on the substrate surface with polarized or non-polarized radiation. The photo-alignment method to provide is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (see Patent Documents 3 to 13).

On the other hand, as an operation mode of a liquid crystal display element different from the above, a VA (Vertical Alignment) type liquid crystal display element in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known. In this operation mode, when a voltage is applied between the substrates and the liquid crystal molecules are tilted in the direction parallel to the substrate, the liquid crystal molecules must be tilted from the substrate normal direction to one direction in the substrate surface. There is. As a means for this, for example, a method of providing protrusions on the substrate surface, a method of providing stripes on the transparent electrode, or using a rubbing alignment film, liquid crystal molecules are slightly directed from the substrate normal direction to one direction in the substrate surface. A method of tilting (pretilting) has been proposed.
The photo-alignment method is known to be useful as a method for controlling the tilt direction of liquid crystal molecules in a vertical alignment type liquid crystal display element. That is, it is known that the tilt direction of liquid crystal molecules during voltage application can be uniformly controlled by using a vertical alignment liquid crystal alignment film imparted with alignment regulating ability and pretilt angle expression by a photo alignment method (patent) Reference 11-12 and 14-16).
However, when a liquid crystal alignment film applied to a TN type, STN type, or vertical alignment type liquid crystal display element is to be formed by a photo-alignment method, an industrially sufficient degree of liquid crystal alignment regulation power is stably expressed. The liquid crystal aligning agent to do is not known at present. In particular, when applied to a vertical alignment type liquid crystal display element, the polymer used as the liquid crystal alignment film has a rigid liquid crystal-like structure in order to develop a liquid crystal alignment regulating force in a direction perpendicular to the substrate surface. A vertical alignment type liquid crystal aligning agent that has both good liquid crystal alignment and good application properties up to the present, due to the problem that the coating property or printability of the liquid crystal aligning agent containing the same is impaired. Is not known.

Recently, a lateral electric field type (IPS mode) liquid crystal display element has been proposed in which electrodes are formed only on the side of a pair of substrates arranged opposite to each other and an electric field is generated in a direction parallel to the substrate (Patent Document 17). This horizontal electric field type liquid crystal display element is a liquid crystal display element of a type in which an electrode is formed only on the side of a pair of substrates arranged opposite to each other and an electric field is generated in a direction parallel to the substrate, and electrodes are formed on both substrates. As compared with the conventional vertical electric field type liquid crystal display element that generates an electric field in a direction perpendicular to the substrate, it is known that it has a wide viewing angle characteristic and can display a high quality. Since the horizontal electric field type liquid crystal display element responds to the electric field only in the direction in which the liquid crystal molecules are parallel to the substrate, the change in the refractive index in the major axis direction of the liquid crystal molecules is not a problem. There is little change in the contrast and display color density that are visually recognized, and therefore, high-quality display is possible regardless of the viewing angle.
However, it has been pointed out that when a liquid crystal alignment film applied to such a horizontal electric field type liquid crystal display element is formed by a photo-alignment method, the alignment regulating power of liquid crystal molecules is not sufficient, and improvement is required. Yes.

JP 56-91277 A JP-A-1-120528 JP-A-6-287453 JP-A-10-251646 Japanese Patent Laid-Open No. 11-2815 JP-A-11-152475 JP 2000-144136 A JP 2000-319510 A JP 2000-281724 A JP-A-9-297313 JP 2003-307736 A JP 2004-163646 A JP 2002-250924 A JP 2004-83810 A Japanese Patent Laid-Open No. 9-21468 JP 2003-114437 A US Pat. No. 5,928,733 JP-A 63-291922 JP 2010-097188 A

"Sol-gel method science", published by Agne Jofusha Co., Ltd., 1988, pages 154-161

The present invention has been made in view of the above circumstances, and the object thereof is to apply alignment regulating force of liquid crystal molecules by a photo-alignment method and is applied to a vertical alignment type liquid crystal display element. The liquid crystal aligning agent provides a liquid crystal alignment film having an excellent balance between the vertical alignment regulating force and the coating property, and on the other hand, when applied to a TN type, STN type or lateral electric field type liquid crystal display element. Is to provide.
Another object of the present invention is to provide a liquid crystal display element having excellent liquid crystal alignment regulating power and excellent display quality.
Further objects and advantages of the present invention will become apparent from the following description.

The above objects and advantages of the present invention are primarily as follows:
The following formulas (1 ′) to (3 ′)

(In the formulas (1 ′) to (3 ′), R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms or a fluoroalkyl group having 1 to 30 carbon atoms, or 1 having a steroid skeleton. R ² is a cyclohexylene group or a phenylene group, R ³ is a phenylene group or the following formula (R ³ -1)

(In the formula (R ³ -1), X ¹ is ⁺ -COO-, ⁺ -OCO- (where a bond attached with "+" is bonded to a phenylene group) or an oxygen atom, and d is 0. Or, when d is 0, e is an integer of 0 to 12, and when d is 1, e is an integer of 1 to 12.)
X is a single bond, oxygen atom, sulfur atom, methylene group, alkylene group having 2 or 3 carbon atoms, —CH═CH—, —NH—, ^* —COO— or ^* —OCO—. (However, a bond marked with “*” is bonded to R ^2. ), One of Z ¹ and Z ² is a carbonyl group, the other is a methylene group or an oxygen atom, and a is 0 Is an integer of ˜3, b is 0 or 1, c is an integer of 0 to 3, provided that when a is 2 or 3, a plurality of R ² and X may be the same or different You may do it. )
It is achieved by a liquid crystal aligning agent containing a radiation-sensitive polymer having at least one structure selected from the group consisting of structures represented by each of the above.
The above objects and advantages of the present invention are, secondly,
This is achieved by a liquid crystal display element comprising a liquid crystal alignment film formed from the above liquid crystal aligning agent.

The liquid crystal aligning agent of the present invention can impart the alignment regulating force of liquid crystal molecules by a photo-alignment method, and when applied to a vertical alignment type liquid crystal display element, the vertical alignment regulating force and application property of the liquid crystal molecules. On the other hand, when applied to a TN type, STN type or lateral electric field type liquid crystal display element, it is possible to provide a liquid crystal alignment film having excellent alignment regulating power of liquid crystal molecules.
Since the liquid crystal display element of the present invention comprising the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention can display high quality and is inexpensive, it can be effectively applied as various display devices. Can do.

The liquid crystal aligning agent of this invention contains the radiation sensitive polymer which has at least 1 type of group selected from the group which consists of group represented by each of said formula (1 ')-(3').
Examples of the skeleton of the radiation-sensitive polymer include polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose and derivatives thereof, polyacetal, polystyrene and derivatives thereof, poly (styrene-phenylmaleimide) and Derivatives, poly (meth) acrylates and the like can be mentioned, and among these, polyorganosiloxane is preferred. That is, the radiation-sensitive polymer contained in the liquid crystal aligning agent of the present invention includes at least one group selected from the group consisting of groups represented by formulas (1 ′) to (3 ′). It is preferable that it is a radiation sensitive polyorganosiloxane.

<Radiation sensitive polyorganosiloxane>
The radiation-sensitive polyorganosiloxane preferably contained in the liquid crystal aligning agent of the present invention has at least one group selected from the group consisting of groups represented by each of the above formulas (1 ′) to (3 ′). It is what you have.
Examples of the alkyl group having 1 to 30 carbon atoms of R ^{1 in} the above formulas (1 ′) to (3 ′) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl, etc .;
Examples of the fluoroalkyl group having 1 to 30 carbon atoms include trifluoromethyl group, pentafluoroethyl group, nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, and nonadecafluorononyl. Group etc .;
Examples of the monovalent group having a steroid skeleton include a 3-cholestanyl group and a 3-cholestenyl group. As said alkyl group and fluoroalkyl group, a linear thing is preferable.
When this R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, the liquid crystal aligning agent of the present invention is a TN type, STN type or lateral electric field type liquid crystal It can be suitably applied to a display element,
When R ¹ is an alkyl group having 2 to 30 carbon atoms, a fluoroalkyl group having 2 to 30 carbon atoms, or a monovalent group having a steroid skeleton, the liquid crystal aligning agent of the present invention is a vertical alignment type liquid crystal It can be suitably applied to a display element.
The phenylene group and cyclohexylene group of R ² are preferably 1,4-phenylene group and 1,4-cyclohexylene group, respectively.
The phenylene group of R ³ is preferably a 1,4-phenylene group. When R ³ is a group represented by the above formula (R ³ -1), the phenylene group contained therein is 1,4-phenylene. It is preferably a group. E in the formula (R ³ -1) is preferably an integer of 0 to 4 when d is 0, and preferably an integer of 1 to 4 when d is 1.
X is preferably a single bond or ^* —COO— (where a bond marked with “*” is bonded to R ² ).

  Specific examples of the group of the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention include, for example, the following formulas (1′-1) to (1) as groups represented by the above formula (1 ′). '-36)

A group represented by each of the following:
Examples of the group represented by the above formula (2 ′) include the following formulas (2′-1) to (2′-12):

A group represented by each of the following:
Examples of the group represented by the above formula (3 ′) include the following formulas (3′-1) to (3′-6):

And groups represented by each of the above. In the above examples, n is an integer of 0 to 20, and the group C _n H _{2n + 1} — may be substituted with one or more fluorine atoms.
The content ratio of at least one group selected from the group consisting of groups represented by each of the above formulas (1 ′) to (3 ′) in the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention. Is preferably 0.2 to 6 mmol / g-polymer, more preferably 0.3 to 5 mmol / g-polymer.
The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention is in addition to at least one group selected from the group consisting of groups represented by each of the above formulas (1 ′) to (3 ′). Further, it preferably has an epoxy group. In this case, the epoxy equivalent of the radiation sensitive polyorganosiloxane is preferably 150 g / mol or more, more preferably 200 to 10,000 g / mol, and further preferably 200 to 2,000 g / mol. By using such an epoxy equivalent radiation-sensitive polyorganosiloxane, the liquid crystal aligning agent of the present invention is superior in liquid crystal aligning property and excellent afterimage characteristics without impairing the storage stability of the liquid crystal aligning agent. Can be formed, which is preferable.
Regarding the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is preferably 1,000 to 200,000, and 2,000. Is more preferably from 100,000 to 100,000, and particularly preferably from 3,000 to 30,000.

<Synthesis of radiation-sensitive polyorganosiloxane>
The radiation-sensitive polyorganosiloxane preferably contained in the liquid crystal aligning agent of the present invention may be synthesized by any method as long as it is as described above. As a method for synthesizing the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, for example, at least one selected from the group consisting of groups represented by the above formulas (1 ′) to (3 ′), for example. A method of hydrolyzing and condensing a hydrolyzable silane compound having a seed group, or a mixture of the hydrolyzable silane compound and another hydrolyzable silane compound;
Polyorganosiloxane having an epoxy group and the following formulas (1) to (3)

(R ¹ , R ² , R ³ , X, Z ¹ , Z ² , a, b and c in the formulas (1) to (3) are the same as those in the above formulas (1 ′) to (3 ′), respectively. Is synonymous with.)
And a method of reacting at least one selected from the group consisting of compounds represented by each of the compounds (hereinafter referred to as “specific carboxylic acid”).
Of these, the latter method is preferred from the viewpoints of ease of synthesis of the raw material compound, ease of reaction, and the like.
Hereinafter, a method for reacting a polyorganosiloxane having an epoxy group with a specific carboxylic acid, which is a preferred method for synthesizing the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, will be described.

[Polyorganosiloxane having epoxy group]
The epoxy group in the polyorganosiloxane having an epoxy group is bonded to a silicon atom through an ethylene oxide skeleton or a 1,2-epoxycycloalkane skeleton either directly or through an alkylene which may be interrupted by an oxygen atom. It is preferable that it exists in polyorganosiloxane as what is contained in the group (group which has an epoxy group). Examples of the group having such an epoxy group include the following formula (EP-1) or (EP-2)

(In formulas (EP-1) and (EP-2), “*” indicates a bond).)
The group represented by these can be mentioned.
The epoxy equivalent of the polyorganosiloxane having an epoxy group is preferably 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol.
About the polyorganosiloxane having an epoxy group, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is preferably 500 to 100,000, more preferably 1,000 to 10,000, In particular, it is preferably 1,000 to 5,000.
Such polyorganosiloxane having an epoxy group is, for example, a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst. Can be synthesized by hydrolysis and condensation.
Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxy. Silane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy A silane etc. can be mentioned.

  Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, Trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, Fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, Rutriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) ) Ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (tri Fluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltri Methoxy Lan, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2 -(Perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane,

2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (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- (meta Acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propoxysilane, 3- (meth) acryloxypropyltri-n-butoxy Silane, 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, mercaptomethyltrieth Sisilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltri Methoxysilane, 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, methyl Dichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldi Ethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane,

(Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i -Propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (Methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercapto Propyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di-n -Butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl ) (Vinyl) di-n-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, Divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n- Lopoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxy Silane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane In addition to silane compounds having one silicon atom such as (ethoxy) (methyl) diphenylsilane,

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

Among other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltri Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercapto It is preferable to use one or more selected from the group consisting of methyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane.
In synthesizing the polyorganosiloxane having an epoxy group in the present invention, the use ratio of the silane compound having an epoxy group and the other silane compound is set so that the epoxy equivalent of the obtained polyorganosiloxane is within the above preferred range. It is preferable to prepare and set.
Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane having an epoxy group include hydrocarbons, ketones, esters, ethers, alcohols, and the like.

Examples of the hydrocarbon include toluene and xylene; examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone;
Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate;
Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;
Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl. Examples include ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like. Of these, water-insoluble ones are preferred.
These organic solvents can be used alone or in admixture of two or more.
The amount of the organic solvent used is preferably 10 to 10 parts by weight based on 100 parts by weight of the total of silane compounds (the total of silane compounds having an epoxy group and other silane compounds optionally used). 1,000 parts by weight, and more preferably 50 to 1,000 parts by weight.
The amount of water used when synthesizing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, relative to a total of 1 mol of the silane compound.

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

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

The hydrolysis and condensation reaction when synthesizing the polyorganosiloxane having an epoxy group is carried out by dissolving the silane compound having an epoxy group and, if necessary, another silane compound in an organic solvent, and dissolving this solution with an organic base and water. It is preferably carried out by mixing and heating using a suitable heating device such as an oil bath.
In the hydrolysis and condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During the heating, the mixed solution may be stirred or may not be stirred, or the mixed solution may be placed under reflux.
After completion of the reaction, the organic solvent layer separated from the reaction mixture is preferably washed with water. In this washing, washing with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by weight is preferred because the washing operation is facilitated. Washing is carried out until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with an appropriate desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the solvent is removed to remove the solvent. A polyorganosiloxane having an epoxy group can be obtained.
In the present invention, a commercially available polyorganosiloxane having an epoxy group may be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (manufactured by Chisso Corporation).

[Specific carboxylic acid]
Specific examples of the specific carboxylic acid include carboxylic acids formed by bonding a hydrogen atom to the bond of the group exemplified above as the group represented by each of the above formulas (1 ′) to (3 ′). it can.

[Synthesis of radiation-sensitive polyorganosiloxane]
The radiation-sensitive polyorganosiloxane preferably contained in the liquid crystal aligning agent of the present invention preferably reacts the polyorganosiloxane having an epoxy group as described above with a specific carboxylic acid, preferably in the presence of a catalyst and an organic solvent. By making it, it can obtain easily.
Here, the total amount of the specific carboxylic acid is preferably 0.01 to 5 mol, more preferably 0.05 to 2 mol, still more preferably 0.1 to 1 mol of the epoxy group of the polyorganosiloxane. Used in a proportion of ˜0.8 mol.
In the present invention, a part of the specific carboxylic acid is represented by the following formula (4) within a range not impairing the effects of the present invention.
R ^I -R ^II -COOH (4)
(In the formula (4), R ^I is an alkyl group or alkoxyl group having 8 to 20 carbon atoms, or a fluoroalkyl group or fluoroalkoxyl group having 1 to 21 carbon atoms, R ^II is a single bond, 1,4-cyclohexylene. Group or a 1,4-phenylene group.)
It may be used by replacing with a compound represented by In this case, the radiation-sensitive polyorganosiloxane is synthesized by reacting a polyorganosiloxane having an epoxy group with a mixture of a specific carboxylic acid and a compound represented by formula (4).
Preferred examples of the compound represented by the above formula (4) include, for example, the following formula (4-1) or (4-2):

(In the above formula, f is an integer of 1 to 3, g is an integer of 3 to 18, h is an integer of 1 to 20, and i is an integer of 0 to 18.)
The compounds represented by the following formulas (4-2-1) to (4-2-3)

The compound represented by either is preferable.
The compound represented by the above formula (4) is a compound that reacts with a polyorganosiloxane having an epoxy group together with a specific carboxylic acid, and becomes a site that imparts pretilt angle expression to the resulting liquid crystal alignment film. This liquid crystal aligning agent can be preferably used when applied to a vertical alignment type liquid crystal display element. In the present specification, the compound represented by the formula (4) is hereinafter referred to as “other carboxylic acid”.
In the present invention, when at least one other carboxylic acid selected from the group consisting of compounds represented by the specific carboxylic acid is used, the total usage ratio of the specific carboxylic acid and the other carboxylic acid is determined by the polyorganosiloxane. The amount is preferably 0.001 to 1.5 mol, more preferably 0.01 to 1 mol, and still more preferably 0.05 to 0.9 mol, with respect to 1 mol of the epoxy group possessed by. In this case, the other carboxylic acid is preferably used in a range of 50 mol% or less, more preferably 25 mol% or less, based on the total with the specific carboxylic acid. If the proportion of other carboxylic acids used exceeds 50 mol%, there may be a problem that abnormal domains occur when the liquid crystal display element is turned on.

As said catalyst, a well-known compound can be used as what is called a hardening accelerator which accelerates | stimulates reaction with an organic base or an epoxy compound, and an acid anhydride.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
A quaternary organic amine such as tetramethylammonium hydroxide can be used. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine;
Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine;
2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- ( 2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s -Triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2'-methyl] An imidazole compound such as an isocyanuric acid adduct of loumidazolyl- (1 ′)] ethyl-s-triazine;

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

Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.
The catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane having an epoxy group. .
Reaction of the polyorganosiloxane which has an epoxy group, and specific carboxylic acid can be performed in presence of an organic solvent as needed. Examples of such organic solvents include hydrocarbons, ethers, esters, ketones, amides, alcohols and the like. Of these, ethers, esters or ketones are preferred from the viewpoints of solubility of raw materials and products and ease of purification of the products. The solvent is used in such a ratio that the solid content concentration (the ratio of the weight of 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. Is done.
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
The radiation-sensitive polyorganosiloxane as described above is synthesized from the group consisting of the groups represented by the above formulas (1 ′) to (3 ′) by the ring-opening addition of the epoxy contained in the polyorganosiloxane having an epoxy group. It is a method for introducing at least one selected group. This synthesis method is simple, and can increase the introduction rate of at least one group selected from the group consisting of groups represented by formulas (1 ′) to (3 ′). This is a very suitable method.

<Other ingredients>
The liquid crystal aligning agent of the present invention contains a radiation sensitive polymer as described above, preferably a radiation sensitive polyorganosiloxane.
The liquid crystal aligning agent of the present invention may further contain other components in addition to the radiation-sensitive polymer as described above, preferably the radiation-sensitive polyorganosiloxane, as long as the effects of the present invention are not impaired. Examples of such other components include polymers other than radiation-sensitive polymers (hereinafter referred to as “other polymers”), curing agents, curing catalysts, curing accelerators, and at least one epoxy group in the molecule. (Excluding those corresponding to the radiation-sensitive polyorganosiloxane described above, hereinafter referred to as “epoxy compound”), functional silane compounds (however, those corresponding to the radiation-sensitive polyorganosiloxane described above) And a surfactant.

[Other polymers]
Said other polymer can be used in order to improve the solution characteristic of the liquid crystal aligning agent of this invention, and the electrical property of the liquid crystal aligning film obtained. Such other polymer is a polymer which does not have any of the groups represented by the above formulas (1 ′) to (3 ′), for example, polyamic acid, polyimide; Polyorganosiloxanes other than siloxane (hereinafter referred to as “other polyorganosiloxanes”); polyamic acid esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates Etc., and one or more of these can be used.
As the other polymer in the present invention, it is preferable to use at least one polymer selected from the group consisting of polyamic acid and polyimide or other polyorganosiloxane.

{Polyamic acid}
The polyamic acid can be obtained by reacting tetracarboxylic dianhydride and diamine.
Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid in the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride and the like. Can be mentioned. Specific examples thereof include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- No 1,2-dicarboxylic acid 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2 : 4,6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and the like;
As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride can be mentioned, respectively,
Tetracarboxylic dianhydrides described in JP 2010-097188 A (Patent Document 19) can be used.

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

Examples of the diamine used for synthesizing the polyamic acid include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and the like;
Examples of aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylene Riden) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 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, co Resta oxy-3,5-diaminobenzene, cholesteryl oxy-3,5-diaminobenzene, Lestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3 , 6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4′-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-heptylcyclohexyl) cyclohexane and the following formula (D-1)

(In the formula (D-1), ^{X I} is an alkyl group having 1 to 3 carbon ^atoms, * ^-O-, * -COO- or ^* -OCO- (where bond marked with "*" is diaminophenyl group And m is 0 or 1, n is an integer of 0 to 2, and p is an integer of 1 to 20.)
A compound represented by:
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, respectively.
Diamines described in JP 2010-097188 A (Patent Document 19) can be used.
The ^{X I} in the above formula (D-1) an alkyl group having 1 to 3 carbon ^atoms, * -O- or ^* -COO- (provided that a bond marked with "*" is bonded to the diamino phenyl group.) In Preferably there is. Specific examples of the group C _p H _{2p + 1} — include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n -An eicosyl group etc. can be mentioned. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.
Specific examples of the compound represented by the formula (D-1) include, for example, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2, 4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, The following formulas (D-1-1) to (D-1-4)

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

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

{Polyimide}
The polyimide can be synthesized by dehydrating and ring-closing the amic acid structure of the polyamic acid obtained as described above. At this time, all of the amic acid structure may be dehydrated and closed to completely imidize, or only a part of the amic acid structure may be dehydrated and closed to form a partially imidized product in which the amic acid structure and the imide structure coexist. Also good.
The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. It can be done by a method.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease. The reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.
On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of a polyamic acid structural unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., more preferably 10 to 150 ° C., and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

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

{Other polyorganosiloxanes}
The other polyorganosiloxane in the present invention is a polyorganosiloxane other than the above-mentioned radiation-sensitive polyorganosiloxane. Such other polyorganosiloxane is, for example, at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter also referred to as “raw silane compound”), preferably an appropriate organic solvent. In which it can be synthesized by hydrolysis and condensation in the presence of water and a catalyst.
Examples of the raw material silane compound used here include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert. -Butoxysilane, tetrachlorosilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxy Silane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxy Lan, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; dimethyldimethoxysilane, dimethyldiethoxysilane, Examples include dimethyldichlorosilane; trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and the like, and it is preferable to use one or more of these, particularly tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy It is preferred to use at least one selected from the run and the group consisting of trimethyl silane.
Other polyorganosiloxanes in the present invention can be synthesized in the same manner as described above as a method for synthesizing a polyorganosiloxane having an epoxy group, except that the raw material silane compound as described above is used.
For other polyorganosiloxanes, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably 1,000 to 100,000, and more preferably 5,000 to 50,000.

{Use ratio of other polymers}
When the liquid crystal aligning agent of this invention contains another polymer with the above-mentioned radiation sensitive polymer, as a use ratio of another polymer, it is 10 with respect to 100 weight part of radiation sensitive polymers. 1,000 parts by weight or less is preferable. The more preferable use ratio of the other polymer varies depending on the kind of the polymer contained in the liquid crystal aligning agent of the present invention.
In the case where the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation-sensitive polyorganosiloxane and polyamic acid and polyimide, a more preferable use ratio of both is radiation-sensitive. The total amount of polyamic acid and polyimide with respect to 100 parts by weight of the functional polyorganosiloxane is 100 to 5,000 parts by weight, and more preferably 200 to 2,000 parts by weight.
On the other hand, in the case where the liquid crystal aligning agent of the present invention contains a radiation-sensitive polyorganosiloxane and another polyorganosiloxane, the more preferable use ratio of both is other than 100 parts by weight of the radiation-sensitive polyorganosiloxane. The amount of polyorganosiloxane is 100 to 2,000 parts by weight.
When the liquid crystal aligning agent of this invention contains another polymer with a radiation sensitive polymer, as a kind of other polymer, it is at least 1 sort (s) selected from the group which consists of a polyamic acid and a polyimide. Preferably it is a polymer or other polyorganosiloxane or both.

[Curing agent and curing catalyst]
The curing agent and the curing catalyst can be contained in the liquid crystal aligning agent of the present invention for the purpose of further strengthening the crosslinking reaction of the radiation-sensitive polymer, preferably the radiation-sensitive polyorganosiloxane. It can be contained in the liquid crystal aligning agent of the present invention for the purpose of promoting the curing reaction governed by the curing agent.
As the curing agent, a curable compound having an epoxy group or a curing agent generally used for curing a curable composition containing a compound having an epoxy group can be used. An acid anhydride and polyhydric carboxylic acid can be illustrated.
Examples of the polyvalent carboxylic acid anhydride include cyclohexanetricarboxylic acid anhydride and other polyvalent carboxylic acid anhydrides.
Specific examples of the cyclohexanetricarboxylic acid anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane- 1,2,3-tricarboxylic acid-2,3-acid anhydride, and the like. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic acid anhydride, methylnadic acid anhydride, Dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, formula (CA-1)

(In formula (CA-1), q is an integer of 1 to 20.)
Diels-Alder reaction of maleic anhydride with cycloaliphatic compounds having conjugated double bonds such as α-terpinene and allocymene, in addition to tetracarboxylic dianhydrides generally used for the synthesis of compounds and polyamic acids Products and their hydrogenated products can be mentioned.
As the curing catalyst, for example, an antimony hexafluoride compound, a phosphorus hexafluoride compound, aluminum trisacetylacetonate, or the like can be used. These catalysts can catalyze the cationic polymerization of epoxy groups by heating.
Examples of the curing accelerator include imidazole compounds;
Quaternary phosphorus compounds;
Quaternary amine compounds;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as dicyandiamide, amine addition type accelerators such as adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator whose surface is covered with a polymer such as a quaternary phosphonium salt;
An amine salt type latent curing accelerator;
And high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

[Epoxy compound]
The said epoxy compound can be contained in the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness with respect to the substrate surface of the liquid crystal aligning film formed.
Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′— Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-dia Bruno diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, may be mentioned as being preferred.
When the liquid crystal aligning agent of this invention contains an epoxy compound, as the content rate, Preferably it is with respect to a total of 100 weight part of said radiation sensitive polymer and the other polymer used arbitrarily. It is 40 parts by weight or less, and more preferably 0.1 to 30 parts by weight.
In addition, when the liquid crystal aligning agent of this invention contains an epoxy compound, you may use together basic catalysts, such as 1-benzyl-2-methylimidazole, in order to raise | generate the crosslinking reaction efficiently.

[Functional silane compounds]
The said functional silane compound can be used in order to improve the adhesiveness with the board | substrate of the liquid crystal aligning film obtained. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3. -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltri Methoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7 Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And the patent text 18 such as those described in (JP 63-291922 JP), may be used reaction products of a silane compound having a tetracarboxylic dianhydride and an amino group.
When the liquid crystal aligning agent of the present invention contains a functional silane compound, the content ratio is 100 parts by weight in total of the radiation-sensitive polymer and other polymers optionally used. Preferably it is 50 weight part or less, More preferably, it is 20 weight part or less.

[Surfactant]
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. it can.
When the liquid crystal aligning agent of this invention contains surfactant, as the content rate, Preferably it is 10 weight part or less with respect to 100 weight part of the whole liquid crystal aligning agent, More preferably, it is 1 weight part or less. is there.

<Liquid crystal aligning agent>
As described above, the liquid crystal aligning agent of the present invention contains a radiation-sensitive polymer as an essential component, and additionally contains other components as necessary, but preferably each component is dissolved in an organic solvent. Prepared as a solution-like composition.
The organic solvent that can be used for preparing the liquid crystal aligning agent of the present invention is preferably one that dissolves the radiation-sensitive polymer and other components optionally used and does not react with them.
The organic solvent that can be preferably used in the liquid crystal aligning agent of the present invention varies depending on the type of polymer contained in the liquid crystal aligning agent of the present invention.
When the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation-sensitive polyorganosiloxane and polyamic acid and polyimide, and radiation-sensitive polyorganosiloxane, polyamic acid and As the preferable organic solvent in the case where it contains another polyorganosiloxane in addition to at least one polymer selected from the group consisting of polyimides, it is exemplified above as being used for the synthesis of polyamic acid. Mention may be made of organic solvents. These organic solvents can be used alone or in combination of two or more.

  On the other hand, when the liquid crystal aligning agent of the present invention contains only a radiation-sensitive polyorganosiloxane as a polymer, or contains a radiation-sensitive polyorganosiloxane and another polyorganosiloxane, but from polyamic acid and polyimide Preferred organic solvents in the case of not containing at least one polymer selected from the group consisting of, for example, 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, ethyl cellosolve acetate, propyl Cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-acetate Pentyl, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutylacetate , 2-ethylhexyl acetate, benzyl acetate, n- hexyl, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, and the like. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate and the like can be mentioned.

A preferred solvent used for the preparation of the liquid crystal aligning agent of the present invention is obtained by combining one or more of the above-described organic solvents according to the presence or absence of other polymers and their types, Each component contained in the liquid crystal aligning agent does not precipitate at a preferable solid content concentration, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mN / m.
The solid content concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, Preferably it is the range of 1-10 weight%. The liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal aligning film. When the solid content concentration is less than 1% by weight, the film thickness of this coating film becomes too small. In some cases, it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal aligning agent increases, resulting in insufficient coating characteristics. There is a case. The particularly preferable range of the solid content concentration varies depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by weight is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 0 ° C. to 200 ° C., more preferably 0 ° C. to 40 ° C.

<Method for forming liquid crystal alignment film>
The liquid crystal aligning agent of this invention can be used suitably in order to form the liquid crystal aligning film used for a TN type, STN type, a horizontal electric field system (IPS type), or VA type liquid crystal display element by the photo-alignment method. . When the liquid crystal aligning agent of the present invention is applied to a TN type, STN type or horizontal electric field type liquid crystal display element, particularly when applied to a horizontal electric field type liquid crystal display element, the effect of the present invention is maximized. This is preferable.
In order to form a liquid crystal alignment film using the liquid crystal aligning agent of the present invention, a method of applying a liquid crystal aligning agent of the present invention on a substrate to form a coating film and irradiating the coating film with radiation Can be.
Here, when the liquid crystal aligning agent of the present invention is applied to a TN-type, STN-type, or VA-type liquid crystal display element, a pair of two substrates each provided with a patterned transparent conductive film is used as a pair. On the conductive film forming surface, the liquid crystal aligning agent of the present invention is applied to form a coating film. On the other hand, when the liquid crystal aligning agent of the present invention is applied to a lateral electric field type liquid crystal display element, a substrate having an electrode in which a transparent conductive film or a metal film is patterned in a comb shape on one side and an electrode are provided. The liquid crystal aligning agent of this invention is apply | coated to the formation surface of a comb-like electrode, and the single side | surface of a counter substrate, respectively, and a coating film is formed in a pair.
In any case, as the substrate, for example, a glass such as float glass or soda glass, a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ —SnO _{2 or} a NESA (registered trademark) film made of SnO ₂ can be used. As the metal film, for example, a film made of a metal such as chromium can be used. For patterning the transparent conductive film and the metal film, for example, a method of forming a pattern by a photo-etching method or a sputtering method after forming a transparent conductive film without a pattern, or a mask having a desired pattern when forming the transparent conductive film It is possible to use a method using

In order to further improve the adhesion between the substrate or the conductive film or the electrode and the coating film when the liquid crystal aligning agent is applied on the substrate, a functional silane compound, titanate, or the like is previously applied on the substrate and the electrode. May be.
The liquid crystal aligning agent can be applied onto the substrate by an appropriate application method such as an offset printing method, a spin coating method, a roll coater method, or an ink jet printing method, and then the application surface is preheated (prebaked). And then baking (post-baking) to form a coating film. The pre-bake conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-bake conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
By irradiating the thus formed coating film with linearly or partially polarized radiation or non-polarized radiation, liquid crystal alignment ability is imparted. Here, as radiation, for example, ultraviolet rays and visible light containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination thereof. May be. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction.

As a light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter, a diffraction grating, or the like.
The irradiation dose of radiation, preferably less than 1 J / ^{m 2} or more 10,000 J / ^{m 2,} more preferably from 10~3,000J / ^{m 2.} In addition, when providing the liquid crystal aligning ability by the photo-alignment method to the coating film formed from the conventionally known liquid crystal aligning agent, the irradiation dose of 10,000 J / m < ² > or more was required. However, when the liquid crystal aligning agent of the present invention is used, a good liquid crystal aligning ability can be imparted even when the radiation irradiation amount in the photo-alignment method is 3,000 J / m ² or less, and further 1,000 J / m ² or less. This contributes to improving the productivity of liquid crystal display elements and reducing manufacturing costs.

<Method for manufacturing liquid crystal display element>
The liquid crystal display element formed using the liquid crystal aligning agent of this invention can be manufactured as follows, for example.
First, a pair of substrates on which a liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell having a configuration in which liquid crystals are sandwiched between the pair of substrates is manufactured. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.
The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.
In any case, it is desirable to remove the flow alignment at the time of filling the liquid crystal by heating the liquid crystal cell to a temperature at which the liquid crystal used has an isotropic phase and then gradually cooling it to room temperature.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell. Here, in the two substrates on which the liquid crystal alignment film is formed, a desired liquid crystal display element can be obtained by appropriately adjusting the angle formed by the polarization direction of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate. Can be obtained.

As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.
As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. Those having positive dielectric anisotropy forming a nematic liquid crystal are preferred, such as biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, Bicyclooctane liquid crystal, cubane liquid crystal, or the like is used. In addition, the liquid crystal includes, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate;
Chiral agents such as those sold under the trade names “C-15” and “CB-15” (Merck)
A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.
The polarizing plate used outside the liquid crystal cell is composed of a polarizing film called “H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine and sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate etc. can be mentioned.
The liquid crystal display element of the present invention thus produced is excellent in display characteristics since it is excellent in the alignment regulating power of liquid crystal molecules.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
The weight average molecular weight Mw in the following synthesis examples is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
In the following synthesis examples, the necessary amounts in the following examples were ensured by repeating the synthesis of the raw material compound and the polymer as necessary at the following synthesis scale.

<Synthesis Example of Polyorganosiloxane Having Epoxy Group>
Synthesis example ES1
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine at room temperature. Mixed.
Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the reaction was performed at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to have an epoxy group. Polyorganosiloxane (ES-1) was obtained as a viscous transparent liquid.
As a result of ¹ H-NMR analysis of the polyorganosiloxane having an epoxy group, a peak based on the epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred.
Table 1 shows the viscosity, Mw, and epoxy equivalent of the polyorganosiloxane (ES-1) having this epoxy group.
Synthesis example ES2-3
Polyorganosiloxanes (ES-2) and (ES-3) having an epoxy group were obtained as viscous transparent liquids in the same manner as in Synthesis Example 1 except that the raw materials used were as shown in Table 1.
Table 1 shows the Mw and epoxy equivalent of the polyorganosiloxane having these epoxy groups.
In Table 1, the abbreviations of the raw material silane compounds have the following meanings.
ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane MTMS: methyltrimethoxysilane PTMS: phenyltrimethoxysilane

<Example of synthesis of specific carboxylic acid>
Scheme 1 below

Thus, compounds (3-1), (3-2) and (3-3) were respectively prepared. However, in the scheme 1, the product when R is a hydrogen atom is the compound (3-1), the product when R is a fluorine atom is the compound (3-2), and R is cyclohexyl. When it is a group, the product is the compound (3-3).
The following synthesis operation was performed in an inert atmosphere.

Synthesis Example (3) -1
A 3 L three-necked flask equipped with a condenser and a dropping funnel was charged with 0.39 mol of indene and a 40 wt% ethanol solution of tetramethylammonium hydroxide (equivalent to 0.88 mol of benzyltrimethylammonium hydroxide) at 40 ° C. Heated. A 50% by weight aqueous solution of glyoxylic acid (corresponding to 0.59 mol of glyoxylic acid) was added dropwise thereto and reacted at 50 ° C. with stirring for 1 hour. After completion of the reaction, 700 mL of pure water and 1 L of toluene were added to the reaction mixture, and 1N sulfuric acid was further added to adjust the pH of the aqueous layer to about 2. Subsequently, after heating up to 70 degreeC and fully stirring, the organic layer was taken out and washed with water. This organic layer was extracted several times using a mixed aqueous solution (pH is about 8) composed of 1N aqueous ammonium chloride and 1N aqueous ammonia. The obtained aqueous layers were combined, 1,2-dichloroethane was added, 1N hydrochloric acid was further added to adjust the pH of the aqueous phase to about 2, and the mixture was shaken. The organic layer was taken out, and the solid obtained by distilling off the solvent was recrystallized from toluene to obtain 26.9 g of Compound (3-1).
Synthesis examples (3) -2 and (3) -3
In the synthesis example (3) -1, 0.39 mol of 5-fluoroindene (synthesis example (3) -2) and 5-cyclohexylindene (synthesis example (3) -3) was used instead of indene. Otherwise in the same manner as in Synthesis Example (3) -1, 33 g of Compound (3-2) and 29 g of Compound (3-3) were obtained.

<Comparative synthesis example of carboxylic acid>
Synthesis Example R-1
Scheme 2 below

The carboxylic acid for comparison (R-1) was synthesized according to
A 200 mL three-necked flask was charged with 11.21 g of 4-hydroxychalcone, 8.35 g of ethyl bromoacetate, 13.8 g of potassium carbonate and 100 mL of dimethylacetamide, and reacted at 120 ° C. with stirring for 7 hours. After completion of the reaction, the reaction solution was cooled at room temperature, and 100 mL of ethyl acetate was added. After washing the organic layer with water, the solid obtained by removing the solvent under reduced pressure was recrystallized from a mixed solvent consisting of ethanol and water (ethanol: water = 4: 1 (volume ratio)), 11.4 g of a certain compound (R-1a) was obtained.
Next, 6.2 g of the above compound (R-1a), 2 g of sodium hydroxide, 200 mL of ethanol and 50 mL of water were charged into a 500 mL three-necked flask equipped with a condenser, and the reaction was carried out with stirring for 3 hours under reflux. After completion of the reaction, the reaction mixture was cooled, acidified with dilute hydrochloric acid, and then 500 mL of ethyl acetate was added for liquid separation extraction. The obtained organic layer was washed with water, and then the solvent was removed under reduced pressure to obtain 4.1 g of Compound (R-1).

<Synthesis example of radiation-sensitive polyorganosiloxane>
Synthesis Example S-1
In a 100 mL three-necked flask, 9.3 g of polyorganosiloxane (ES-1) having an epoxy group obtained in Synthesis Example ES-1, 26 g of methyl isobutyl ketone, compound (3) obtained in Synthesis Example (3) -1 -1) 4.30 g and UCAT 18X (trade name, a quaternary amine salt manufactured by San Apro Co., Ltd.) 0.10 g were charged and reacted at 80 ° C. with stirring for 12 hours. After completion of the reaction, methanol was added to the reaction mixture to collect a precipitate, which was dissolved in ethyl acetate, washed with water three times, and then the solvent was distilled off to remove the radiation-sensitive polyorgano. 9 g of siloxane (S-1) was obtained as a white powder. The weight average molecular weight Mw of the radiation sensitive polyorganosiloxane (S-1) was 5,500.
Synthesis Examples S-2 and S-3
In Synthesis Example S-1, Synthesis Example S except that the types and amounts of the polyorganosiloxane having an epoxy group and the carboxylic acid (compound represented by the above formula (3)) were used as shown in Table 2 respectively. In the same manner as in Example 1, radiation-sensitive polyorganosiloxanes (S-2) and (S-3) were obtained. Table 2 shows the weight average molecular weights Mw of these radiation-sensitive polyorganosiloxanes.

<Comparative synthesis example of radiation-sensitive polyorganosiloxane>
Synthesis example RS-1
In Synthesis Example S-1, except that 3.52 g of Compound (R-1) obtained in Synthesis Example R-1 was used instead of Compound (3-1), the same as Synthesis Example S-1, Radiation sensitive polyorganosiloxane (RS-1) was obtained. Table 2 shows the weight average molecular weight Mw of the radiation-sensitive polyorganosiloxane (RS-1).

<Synthesis examples of other polymers>
[Synthesis example of polyamic acid]
Synthesis example PA-1
Cyclobutanetetracarboxylic dianhydride 19.61 g (0.1 mol) and 4,4′-diamino-2,2′-dimethylbiphenyl 21.23 g (0.1 mol) were combined with N-methyl-2-pyrrolidone 367. Then, the reaction was carried out at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was collected, washed with methanol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain 35 g of polyamic acid (PA-1).
Synthesis example PA-2
2,3,5-tricarboxycyclopentylacetic acid dianhydride (22.4 g, 0.1 mol) and cyclohexanebis (methylamine) (14.23 g, 0.1 mol) were mixed with N-methyl-2-pyrrolidone (329.3 g). And reacted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 32 g of polyamic acid (PA-2).
A part of this polyamic acid (PA-2) was subjected to preparation of a liquid crystal aligning agent in Examples described later, and the remaining part was subjected to synthesis of the following polyimide.

[Synthesis of polyimide]
Synthesis example PI-1
17.5 g of the polyamic acid (PA-2) obtained in Synthesis Example PA-2 was taken, and 232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine and 4.9 g of acetic anhydride were added thereto, and 120 The imidization reaction was performed at 4 ° C. for 4 hours. The resulting reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to obtain 15 g of polyimide (PI-1).

Example 1
<Preparation of liquid crystal aligning agent>
100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in Example S-1 and 1,000 parts by weight of the polyamic acid (PA-1) obtained in Synthesis Example PA-1 as another polymer Is dissolved in a mixed solvent consisting of N-methyl-2-pyrrolidone and butyl cellosolve (N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio)), and a solution having a solid content concentration of 3.0% by weight did. A liquid crystal aligning agent was prepared by filtering this solution through a filter having a pore diameter of 1 μm.
<Manufacture of liquid crystal display elements>
The liquid crystal aligning agent prepared above was applied to the electrode forming surface of the glass substrate having chromium metal electrodes patterned in a comb shape and one surface of the counter glass substrate not provided with an electrode using a spinner. Then, after pre-baking for 1 minute on an 80 ° C. hot plate, it was post-baked at 200 ° C. for 1 hour in an oven in which the inside of the cabinet was replaced with nitrogen to form a coating film having a thickness of 0.1 μm. Next, a pair of substrates having a liquid crystal alignment film is obtained by irradiating the surface of the coating film with polarized ultraviolet rays 600 J / m ² including a 313 nm emission line from the normal direction of the substrate using a Hg—Xe lamp and a Grand Taylor prism. It was.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface of the pair of substrates having a chromium metal electrode on which the liquid crystal alignment film is formed, and then the pair of substrates. The liquid crystal alignment film surfaces were opposed to each other, and the substrates were pressure-bonded so that the directions at the time of ultraviolet irradiation were opposite to each other, and heated at 150 ° C. for 1 hour to thermally cure the adhesive. Next, a liquid crystal injection, MLC-7028, was filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment during liquid crystal injection, this was heated at 150 ° C. and then gradually cooled to room temperature. Next, a polarizing plate is bonded to both the outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and the direction of projection of the optical axis of the liquid crystal alignment film to the substrate surface is orthogonal to each other. A liquid crystal display element was manufactured.

<Evaluation of liquid crystal display element>
This liquid crystal display element was evaluated by the following method. The evaluation results are shown in Table 3.
(1) Evaluation of liquid crystal alignment The presence or absence of an abnormal domain in a change in brightness when a voltage of 5 V is turned ON / OFF (applied / released) is observed with an optical microscope for the liquid crystal display element manufactured above. The case where it was not observed was evaluated as “good” liquid crystal alignment, and the case where an abnormal domain was observed was evaluated as “bad” liquid crystal alignment.
(2) Evaluation of voltage holding ratio After applying a voltage of 5 V to the liquid crystal display element manufactured above at 60 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, the voltage after 167 milliseconds from the release of application Retention was measured. As a measuring device, VHR-1 manufactured by Toyo Corporation was used.

Examples 2 to 8 and Comparative Example 1
In Example 1, a liquid crystal display element was prepared in the same manner as in Example 1 except that the type of radiation-sensitive polyorganosiloxane and the type and amount of other polymers were changed as shown in Table 3, respectively. A liquid crystal display element was manufactured and evaluated. The evaluation results are shown in Table 3.
In Comparative Example 1, the amount of polarized ultraviolet rays irradiated during the production of the liquid crystal display element was 1,000 J / m ² .

Claims (10)

The following formulas (1 ′) to (3 ′)

(In the formulas (1 ′) to (3 ′), R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms or a fluoroalkyl group having 1 to 30 carbon atoms, or 1 having a steroid skeleton. R ² is a cyclohexylene group or a phenylene group, R ³ is a phenylene group or the following formula (R ³ -1)

(In the formula (R ³ -1), X ¹ is ⁺ -COO-, ⁺ -OCO- (where a bond attached with "+" is bonded to a phenylene group) or an oxygen atom, and d is 0. Or, when d is 0, e is an integer of 0 to 12, and when d is 1, e is an integer of 1 to 12.)
X is a single bond, oxygen atom, sulfur atom, methylene group, alkylene group having 2 or 3 carbon atoms, —CH═CH—, —NH—, ^* —COO— or ^* —OCO—. (However, a bond marked with “*” is bonded to R ^2. ), One of Z ¹ and Z ² is a carbonyl group, the other is a methylene group or an oxygen atom, and a is 0 Is an integer of ˜3, b is 0 or 1, c is an integer of 0 to 3, provided that when a is 2 or 3, a plurality of R ² and X may be the same or different You may do it. )
A liquid crystal aligning agent comprising a radiation-sensitive polymer having at least one structure selected from the group consisting of the structures represented by each of:   The radiation-sensitive polymer is a radiation-sensitive polyorganosiloxane having at least one structure selected from the group consisting of structures represented by formulas (1 ′) to (3 ′). Item 2. A liquid crystal aligning agent according to Item 1. The radiation sensitive polyorganosiloxane is
A polyorganosiloxane having an epoxy group;
Following formula (1)-(3)

(R ¹ , R ² , R ³ , X, Z ¹ , Z ² , a, b and c in the formulas (1) to (3) are the same as those in the above formulas (1 ′) to (3 ′), respectively. Is synonymous with.)
The liquid crystal aligning agent of Claim 2 which is a reaction product with at least 1 sort (s) selected from the group which consists of a compound represented by each of these.   Furthermore, at least one polymer selected from the group consisting of polyamic acid and polyimide, provided that this polymer has any structure of the structures represented by the above formulas (1 ′) to (3 ′). The liquid crystal aligning agent as described in any one of Claims 1-3 containing.   Furthermore, it contains polyorganosiloxane, provided that this polyorganosiloxane does not have any of the structures represented by the above formulas (1 ′) to (3 ′). The liquid crystal aligning agent as described in any one of 3.   A liquid crystal alignment film comprising a step of applying a liquid crystal aligning agent according to any one of claims 1 to 5 on a substrate to form a coating film, and irradiating the coating film with radiation. Forming method.   A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1. The group R ¹ in the above formulas (1 ′) to (3 ′) is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, and the liquid crystal display element is a TN type The liquid crystal display element according to claim 7, wherein the liquid crystal display element is a STN type or a horizontal electric field type liquid crystal display element.   The liquid crystal display element according to claim 8, wherein the liquid crystal display element is a horizontal electric field type liquid crystal display element. The group R ¹ in the above formulas (1 ′) to (3 ′) is an alkyl group having 5 to 30 carbon atoms or a fluoroalkyl group having 5 to 30 carbon atoms, or a monovalent group having a steroid skeleton. The liquid crystal display element according to claim 7, wherein the liquid crystal display element is a vertical alignment type liquid crystal display element.