CN103992802A - Liquid crystal alignment agent, liquid crystal alignment film, method for forming liquid crystal alignment film, liquid crystal display element, and polyorganosiloxane compounds - Google Patents

Abstract

The present invention provides a liquid crystal alignment film which fully satisfies that as a liquid crystal display element in the practical aspects requires characteristics such as liquid crystal alignment properties, voltage retention and light resistance, etc.; a method for forming the liquid crystal alignment film; a liquid crystal alignment agent which has excellent storage stability suitable for as a forming material of the liquid crystal alignment film and can adopt the liquid crystal alignment film formed by photoalignment; and a liquid crystal display element having the liquid crystal alignment film. The liquid crystal alignment agent comprises [A] polyorganosiloxane compounds having at least one structure selected from the group consisting of a piperidine structure, a phenol structure and an aniline structure.

Description

Liquid crystal aligning agent, liquid crystal aligning film, method for forming liquid crystal aligning film, liquid crystal display element, and polyorganosiloxane compound

The present invention is a branch of the invention patent application No. 201110152309.9 filed on June 1, 2011 with the title of "liquid crystal aligning agent, liquid crystal aligning film, method for forming liquid crystal aligning film, liquid crystal display element, and polyorganosiloxane compound". case application.

technical field

The present invention relates to a liquid crystal aligning agent suitable as a material for forming a liquid crystal aligning film, a polyorganosiloxane compound used in the liquid crystal aligning agent, a liquid crystal aligning film formed from the liquid crystal aligning agent, a method for forming a liquid crystal aligning film, and The liquid crystal display element provided with this liquid crystal aligning film.

Background technique

Liquid crystal display elements have the advantages of low power consumption, easy miniaturization and planarization, and thus can be widely used in liquid crystal display devices such as mobile phones and liquid crystal televisions. As a display method of a liquid crystal display device, for example, Patent Documents 1 to 4 have disclosed that according to changes in the orientation state of liquid crystal molecules, there are twisted nematic (TN type), super twisted nematic (STN type), planar Liquid crystal display elements of internal switching type (IPS type), vertical alignment type (VA type) and other liquid crystal cells.

The operating principles of the above-mentioned various liquid crystal display elements can be roughly classified into transmissive type and reflective type. The transmissive type displays through the backlight from the back of the device. Since the liquid crystal aligning film included in the transmissive liquid crystal display element is exposed to the light from the backlight for a long time, when it is irradiated with a backlight with a high irradiation intensity such as a metal halide lamp, there may be problems involving temperature rise and occurrence Defects. On the other hand, the reflective type does not use a backlight, but displays by reflected light from outside light such as sunlight, so it consumes less power than the transmissive type, but it is always exposed to strong ultraviolet rays. Moreover, in the manufacturing process of a liquid crystal display element, the liquid crystal dropping method which can be used from a viewpoint, such as reduction of steps, includes an ultraviolet irradiation process. Therefore, any liquid crystal display element is required to have excellent heat resistance and light resistance. In addition to these, liquid crystal display elements in recent years are required to be excellent in electrical characteristics such as liquid crystal orientation and voltage retention, and not to cause afterimage problems.

Then, the technology of the liquid crystal aligning film excellent in heat resistance and light resistance formed from a specific polysiloxane solution was developed (refer patent document 5). However, as the manufacturing environment and usage environment have become more stringent in recent years, even this technology cannot satisfy the above-mentioned required performance, and the storage stability of the coating liquid is also insufficient, so it is not convenient for industrial use.

In view of this situation, it is desired to develop a liquid crystal display element that fully satisfies the characteristics of liquid crystal orientation, voltage retention and light resistance in practical aspects, and can be formed by photo-alignment methods. The storage stability of the liquid crystal alignment film is excellent. Liquid crystal alignment agent.

current technology

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 4-153622

[Patent Document 2] Japanese Patent Application Laid-Open No. 60-107020

[Patent Document 3] Japanese Patent Application Laid-Open No. 56-91277

[Patent Document 4] U.S. Patent No. 5,928,733

[Patent Document 5] Japanese Patent Application Laid-Open No. 9-281502

[Patent Document 6] Japanese Patent Application Laid-Open No. 6-287453

[Patent Document 7] Japanese Unexamined Patent Publication No. 2003-307736

[Patent Document 8] Japanese Unexamined Patent Publication No. 2004-163646

Contents of the invention

The present invention is carried out based on the above-mentioned circumstances, and its purpose is to provide a kind of liquid crystal aligning film that fully satisfies the characteristics such as liquid crystal orientation, voltage retention rate and light resistance as a liquid crystal display element practically; The formation method of this liquid crystal aligning film ; It is suitable as a liquid crystal aligning agent which is excellent in storage stability as a material for forming a liquid crystal aligning film, and can form a liquid crystal aligning film by a photo-alignment method; and a liquid crystal display element provided with a liquid crystal aligning film.

The invention for solving the above-mentioned problems is a liquid crystal aligning agent containing [A] a polyorganosiloxane compound having a piperidine structure, a phenol structure, or an aniline structure.

The storage stability of this liquid crystal aligning agent is excellent, and the liquid crystal aligning film formed from this liquid crystal aligning agent fully satisfies the required properties such as liquid crystal orientation, voltage retention, and light resistance as a liquid crystal display element practically.

The piperidine structure is preferably represented by the following formula (A-1'), the phenol structure is preferably represented by the following formula (A-2'), and the aniline structure is preferably represented by the following formula (A-3').

(In formula (A-1'),

R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 1,3-dioxobutyl group.

R ² to R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.

X ¹ is a single bond, a carbonyl group or ^** -CONH-. X ² to X ⁵ are each independently a single bond, a carbonyl group, ^** -CH ₂ -CO- or ^** -CH ₂ -CH(OH)-. The link indicated by ** is attached to the piperidine ring.

The linkage indicated by * is connected to the main chain or side chain of the polyorganosiloxane skeleton. )

(In the formula (A-2'), ^R6 is an alkyl group with 1 to 16 carbon atoms. And, the above-mentioned alkyl group can have an oxygen atom, a sulfur atom, a carbonyl group, an ester group or a combination of them in the skeleton chain A combination of two or more groups. n is an integer from 0 to 4. The link represented by * is connected to the main chain or side chain of the polyorganosiloxane skeleton.)

(In formula (A-3'), R ⁷ and R ⁸ are each independently an alkyl group with 1 to 16 carbon atoms. And, the above-mentioned alkyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group or a group combining two or more of them. * The linkage represented by * is connected to the main chain or side chain of the polyorganosiloxane skeleton.)

In this liquid crystal aligning agent, [A] the polyorganosiloxane compound preferably contains polyorganosiloxane having a structural unit represented by the following formula (1), its hydrolyzate, and condensation of the hydrolyzate at least one selected from the group consisting of compounds, and from the group consisting of compounds represented by the following formula (A-1), formula (A-2) and formula (A-3) A portion of at least one compound selected.

(In formula (1), X ^a is a monovalent organic group having an epoxy group. Y ^a is a hydroxyl group, an alkoxy group with 1 to 10 carbon atoms, an alkyl group with 1 to 20 carbon atoms, or a carbon An aryl group with 6 to 20 atoms.)

(In the formula (A-1), R ¹ to R ⁵ and X ¹ to X ⁵ have the same meaning as the above formula (A-1′).

In the formula (A-2), R ⁶ is synonymous with the above-mentioned formula (A-2').

In the formula (A-3), R ⁷ and R ⁸ have the same meaning as the above-mentioned formula (A-3′).

In the formulas (A-1) to (A-3), Y is a single bond and an alkanediyl group having 1 to 16 carbon atoms. In addition, the above-mentioned alkanediyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, or a combination of two or more of them in the structure. Z is carboxyl or hydroxyl. )

In this liquid crystal aligning agent, the [A] polyorganosiloxane compound is composed of a polyorganosiloxane having a structural unit represented by the above formula (1), a hydrolyzate thereof, and a condensate of the hydrolyzate Therefore, it is possible to easily introduce a structure having a free radical scavenging ability such as a piperidine structure into the [A] polyorganosiloxane compound, thereby improving light resistance.

In the liquid crystal aligning agent, X ^a in the above formula (1) is preferably a group represented by the following formula (X ^a -1) or formula (X ^a -2), and more preferably the following formula ( A group represented by X ^a -1-1) or (X ^a -2-1).

(In formula (X ^a -1) and formula (X ^a -2), s is an integer of 0 to 3. t is an integer of 1 to 6. u is an integer of 0 to 2. v is an integer of 0 to 6. *Denotes linkages to silicon atoms.)

(In formula (Xa ^- 1-1) and formula (Xa ^- 2-1), the linkage represented by * is connected to a silicon atom.)

By adopting the above-mentioned specific group as the above-mentioned monovalent organic group having an epoxy group, it is easy to use the compound derived from the above formula (A-1), formula (A-2) or formula (A-3) A part is introduced into [A] polyorganosiloxane compound of this liquid crystal aligning agent.

In this liquid crystal aligning agent, it is preferable that [A] polyorganosiloxane compound contains the structure which has liquid crystal aligning ability. [A] The polyorganosiloxane compound can further improve liquid crystal alignment ability by including a structure having liquid crystal alignment ability.

The above-mentioned structure having liquid crystal alignment ability preferably has an organic group having a steroid skeleton with 17 to 51 carbon atoms, an alkyl group with 2 to 20 carbon atoms, and a fluoroalkyl group with 1 to 20 carbon atoms. , cyclohexyl, an alkoxyaryl group having an alkyl group with 2 to 20 carbon atoms, an alkylcyclohexyl group with an alkyl group with 1 to 20 carbon atoms, a fluorinated group with 1 to 20 carbon atoms At least one group selected from the group consisting of a fluoroalkylcyclohexyl group of an alkyl group and a fluoroalkoxycyclohexyl group having a fluoroalkoxy group having 1 to 20 carbon atoms. The structure which has liquid crystal aligning ability can provide more excellent liquid crystal aligning ability to this liquid crystal aligning agent by having the said specific group (henceforth "a liquid crystal aligning group" may be called).

The above-mentioned structure having liquid crystal alignment ability preferably has a structure represented by the following formula (B-1).

(In formula (B-1), m is an integer of 0 to 4.)

Since the structure which has liquid-crystal aligning ability has the said specific structure, even if it is a photo-alignment method, a liquid crystal aligning film can be formed from this liquid crystal aligning agent.

It is preferable that this liquid crystal aligning agent further contains [B] at least 1 sort(s) of polymer selected from the group which consists of a polyamic acid and a polyimide (it may be called "[B] polymer hereafter). By producing a liquid crystal aligning film using the liquid crystal aligning agent further containing [B] polymer, the liquid crystal display element which electric characteristics, such as a voltage retention rate, improved further can be obtained.

It is preferable that this liquid crystal aligning agent further contains [C] the polyorganosiloxane compound (it may be called "[C] other polyorganosiloxane compounds" below) which has a structural unit represented by following formula (2).

(In formula (2), X ^b is a hydroxyl group, a halogen atom, an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an aryl group with 6 to 20 carbon atoms. Y ^b is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.)

When this liquid crystal aligning agent further contains [C] other polyorganosiloxane compounds, the crosslinking of [A] polyorganosiloxane compounds can be accelerated, and the voltage retention etc. of the obtained liquid crystal display element can be improved further.

The forming method of the liquid crystal alignment film of the present invention has:

(1) A process of coating a liquid crystal aligning agent comprising [A] a polyorganosiloxane compound comprising a polyorganosiloxane compound having the above formula (B-1) on a substrate to form a coating film. The structure represented by the structure having the liquid crystal alignment ability, and

(2) A step of irradiating radiation to at least a part of the coating film formed in the step (1).

By the formation method of this invention using this liquid crystal aligning agent, the liquid crystal aligning film which fully satisfies characteristics, such as liquid crystal orientation, voltage retention, and light resistance, which are practically required as a liquid crystal display element can be formed.

The liquid crystal aligning film formed from this liquid crystal aligning agent, and the liquid crystal display element provided with the said liquid crystal aligning film are also included in this invention suitably. The liquid crystal display element of this application equipped with the liquid crystal aligning film formed by this liquid crystal aligning agent can be used suitably, for example in a watch, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, a portable information terminal, a digital camera, etc. , mobile phones, various monitors, LCD TVs and other display devices.

In addition, the aryl group having 6 to 20 carbon atoms represented by the above R ¹ , the aralkyl group having 7 to 13 carbon atoms, the alkyl group having 1 to 6 carbon atoms represented by R ² to R ⁵ , A part or all of the hydrogen atoms of the aryl group having 6 to 12 carbon atoms and the aralkyl group having 7 to 13 carbon atoms may be substituted.

According to the present invention, it is possible to provide a liquid crystal alignment film, a method for forming the liquid crystal alignment film, and a liquid crystal alignment film suitable for practical use as a liquid crystal display element that satisfies the characteristics of liquid crystal orientation, voltage retention, and light resistance. The storage stability of a formation material is excellent, and the liquid crystal aligning agent of a liquid crystal aligning film and the liquid crystal display element equipped with a liquid crystal aligning film can be formed by the photo-alignment method. The liquid crystal display element of this application equipped with the liquid crystal aligning film formed by this liquid crystal aligning agent can be used suitably, for example in a watch, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, a portable information terminal, a digital camera, etc. , mobile phones, various monitors, LCD TVs and other display devices.

Detailed ways

Hereinafter, embodiments of the present invention will be described in detail.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention contains [A] polyorganosiloxane compound which has at least 1 sort(s) of structure selected from the group which consists of a piperidine structure, a phenol structure, or aniline structure. The storage stability of this liquid crystal aligning agent is excellent, and the liquid crystal aligning film formed from this liquid crystal aligning agent fully satisfies the properties such as liquid crystal orientation, voltage retention and light resistance required practically as a liquid crystal display element. In addition, the [A] polyorganosiloxane compound preferably has a structure having liquid crystal alignment ability, and the liquid crystal aligning agent preferably contains polymers other than the [A] polyorganosiloxane compound (hereinafter, sometimes referred to as "other polymers"). ”), Furthermore, unless the effect of this invention is impaired, this liquid crystal aligning agent may contain an optional component. Hereinafter, [A] polyorganosiloxane compound, a structure having liquid crystal alignment ability, other polymers, and optional components will be described in detail.

<[A] polyorganosiloxane compound>

[A] A polyorganosiloxane compound having at least one structure selected from the group consisting of a piperidine structure, a phenol structure, or an aniline structure. In addition, the [A] polyorganosiloxane compound preferably contains polyorganosiloxane (hereinafter, sometimes referred to as "polyorganosiloxane having an epoxy group") having a structural unit represented by the above formula (1). ), and a moiety derived from at least one compound selected from the group consisting of compounds represented by the above formula (A-1), formula (A-2) and formula (A-3). This [A] polyorganosiloxane compound can be obtained by combining a polyorganosiloxane having an epoxy group with a compound represented by the above formula (A-1), formula (A-2) or formula (A-3). obtained from the response. In this liquid crystal aligning agent, [A] the polyorganosiloxane compound is derived from the polyorganosiloxane having the structural unit represented by the above formula (1), its hydrolyzate, and the condensate of the hydrolyzate As part of at least one selected from the group formed, it is possible to easily introduce a structure having a free radical scavenging ability such as a piperidine structure into the [A] polyorganosiloxane compound, thereby improving light resistance. Hereinafter, polyorganosiloxanes having a piperidine structure, a phenol structure, an aniline structure, and an epoxy group will be described in detail.

[Piperidine structure]

The piperidine structure of the [A] polyorganosiloxane compound is preferably a structure represented by the above formula (A-1').

[A] The organopolysiloxane compound having such a piperidine structure can be obtained by reacting an organopolysiloxane having an epoxy group with a compound represented by the above formula (A-1).

The alkyl groups having 1 to 6 carbon atoms represented by R ¹ to R ⁵ above may be linear or branched, for example, methyl, ethyl, propyl, butyl, Pentyl, Hexyl, etc.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ include phenyl, naphthyl, oxybenzoic acid and the like. In addition, it is preferable that a part or all of the hydrogen atoms contained in the aromatic ring of the aryl group be substituted with a formyl group or an alkoxy group having 1 to 4 carbon atoms.

Examples of the aralkyl group having 7 to 13 carbon atoms represented by R ¹ to R ⁵ include benzyl group and phenethyl group. In addition, it is preferable that a part or all of the hydrogen atoms contained in the aromatic ring of the aralkyl group be substituted with a formyl group or an alkoxy group having 1 to 4 carbon atoms.

Examples of the aryl group having 6 to 12 carbon atoms represented by R ² to R ⁵ include phenyl, naphthyl and the like. In addition, it is preferable that a part or all of the hydrogen atoms contained in the aromatic ring of the aryl group be substituted with a formyl group or an alkoxy group having 1 to 4 carbon atoms.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ² to R ⁵ include methoxy, ethoxy, n-propoxy and the like.

Z in the above formula (A-1) is preferably a carboxyl group. For example, compounds represented by the following formulas (A-1-1) to (A-1-4) can be exemplified by the formula (A-1) preferred example of .

The proportion of the (A-1') structure in the [A] polyorganosiloxane compound is preferably 2 mol % to ⁸⁰ mol %, more preferably 5 mol % to 75 mol %, and particularly preferably It is 25 mol% to 60 mol%.

[Phenol structure]

The phenolic structure of the [A] polyorganosiloxane compound is preferably a structure represented by the above formula (A-2').

The [A] polyorganosiloxane compound having such a phenolic structure can be obtained by reacting a polyorganosiloxane having an epoxy group with a compound represented by the above formula (A-2).

The alkyl group represented by ^R6 having 1 to 16 carbon atoms may be linear or branched, such as methyl, ethyl, propyl, butyl, pentyl, Hexyl etc.

Z in the above formula (A-2) is preferably a carboxyl group. For example, compounds represented by the following formulas (A-2-1) to (A-2-7) can be exemplified by the formula (A-2) preferred example of .

The ratio of the (A-2') structure in the [A] polyorganosiloxane compound is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol% ^, and particularly preferably It is 25 mol% to 75 mol%.

[Aniline structure]

The aniline structure of the [A] polyorganosiloxane compound is preferably a structure represented by the above formula (A-3').

[A] The organopolysiloxane compound having such an aniline structure can be obtained by reacting an organopolysiloxane having an epoxy group with a compound represented by the above formula (A-3).

Examples of the alkyl group having 1 to 16 carbon atoms represented by R ⁷ and R ⁸ include the same alkyl groups as those described in the above formula (A-2).

Z in the above formula (A-3) is preferably a carboxyl group. For example, compounds represented by the following formulas (A-3-1) to (A-3-8) can be exemplified by the formula (A-3) preferred example of .

The proportion of the (A-3') structure in the [A] polyorganosiloxane compound is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol% ^, and particularly preferably It is 25 mol% to 75 mol%.

[Polyorganosiloxane having an epoxy group]

The polyorganosiloxane having an epoxy group means that in the structure of the [A] polyorganosiloxane compound, a polyorganosiloxane skeleton is included as a polymer main chain, and branches from the polyorganosiloxane The concept of the epoxy-containing backbone as the main chain of the polymer emerges.

The monovalent organic group having an epoxy group represented by X ^a in the above formula (1) is not particularly limited as long as it is a monovalent organic group having an epoxy group, and examples include glycidyl, Glycidyloxy group, epoxy cyclohexyl group, etc. Among them, X ^a is preferably a group represented by the above formula (X ^a -1) or (X ^a -2), and more preferably the above formula (X ^a -1-1) or (X ^a -2-1) represented group. By adopting the above-mentioned specific group as the above-mentioned monovalent organic group having an epoxy group, it is easy to use the compound derived from the above formula (A-1), formula (A-2) or formula (A-3) A part is introduced into [A] polyorganosiloxane compound of this liquid crystal aligning agent.

Examples of the alkoxy group having 1 to 10 carbon atoms represented by ^Ya in the above formula (1) include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. , Isobutoxy, etc.

Examples of the alkyl group having 1 to 20 carbon atoms represented by ^Ya in the above formula (1) include linear or branched methyl, ethyl, propyl, butyl, pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Lauryl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl base, nonadecyl, eicosyl, etc.

Examples of the aryl group having 6 to 20 carbon atoms represented by ^Ya in the above formula (1) include phenyl, naphthyl and the like.

[Synthesis method of polyorganosiloxane having epoxy group]

The polyorganosiloxane having an epoxy group can be obtained by preferably making a silane compound with an epoxy group or a mixture of a silane compound with an epoxy group and other silane compounds preferably in the presence of a suitable organic solvent, water and a catalyst. , to be synthesized by hydrolysis or hydrolysis·condensation.

As the silane compound having an epoxy group, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Methoxysilane, 3-Glycidoxypropylmethyldiethoxysilane, 3-Glycidoxypropyldimethylmethoxysilane, 3-Glycidoxypropyldimethylethoxy 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc. These can be used individually or in combination of 2 or more types.

Examples of other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxy Silane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, triisopropoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, Fluorotrimethoxysilane, Fluorotriethoxysilane, Fluorotri-n-propoxysilane, Fluorotriisopropoxysilane, Fluorotri-n-butoxysilane, Fluorotri-sec-butoxysilane, Methyltrichlorosilane , Methyltrimethoxysilane, Methyltriethoxysilane, Methyltri-n-propoxysilane, Methyltriisopropoxysilane, Methyltri-n-butoxysilane, Methyltri-sec-butoxy Silane, 2-(trifluoromethyl)ethyltrichlorosilane, 2-(trifluoromethyl)ethyltrimethoxysilane, 2-(trifluoromethyl)ethyltriethoxysilane, 2-( Trifluoromethyl)ethyltri-n-propoxysilane, 2-(trifluoromethyl)ethyltriisopropoxysilane, 2-(trifluoromethyl)ethyltri-n-butoxysilane, 2- (Trifluoromethyl)ethyltri-sec-butoxysilane, 2-(perfluoro-n-hexyl)ethyltrichlorosilane, 2-(perfluoro-n-hexyl)ethyltrimethoxysilane, 2-(perfluoro-n-hexyl base) ethyltriethoxysilane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxysilane, 2-(perfluoro-n-hexyl)ethyltriisopropoxysilane, 2-(perfluoro-n-hexyl base) ethyl tri-n-butoxysilane, 2-(perfluoro-n-hexyl) ethyl tri-sec-butoxysilane, 2-(perfluoro-n-octyl) ethyl trichlorosilane, 2-(perfluoro-n-octyl base) ethyltrimethoxysilane, 2-(perfluoro-n-octyl)ethyltriethoxysilane, 2-(perfluoro-n-octyl)ethyltri-n-propoxysilane, 2-(perfluoro-n-octyl) Octyl)ethyltriisopropoxysilane, 2-(perfluoro-n-octyl)ethyltri-n-butoxysilane, 2-(perfluoro-n-octyl)ethyltri-sec-butoxysilane, hydroxymethyl hydroxytrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltriisopropoxysilane, hydroxymethyltri-n-butoxysilane , Hydroxymethyltri-sec-butoxysilane, 3-(meth)acryloxypropyltrichlorosilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(methyl) Acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltri-n-propoxysilane, 3-(meth)acryloxypropyltriisopropoxysilane, 3-(meth)acryloxypropyltri-n-butoxysilane, 3-(meth)acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercapto Propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltriisopropoxysilane, 3-mercaptopropyltri-n-butyl Oxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethylsilane Oxysilane, Vinyl Tri-n-Propoxy Silane, Vinyl Triisopropoxy allyl trichlorosilane, allyl trimethoxysilane, allyl triethoxysilane, allyl tri-n-butoxysilane Propoxysilane, Allyltriisopropoxysilane, Allyltri-n-Butoxysilane, Allyltri-S-Butoxysilane, Phenyltrichlorosilane, Phenyltrimethoxysilane, Phenyl Triethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, methyldichlorosilane, methyl Dimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldiisopropoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, Dimethyldichlorosilane, Dimethyldimethoxysilane, Dimethyldiethoxysilane, Dimethyldi-n-propoxysilane, Dimethyldiisopropoxysilane, Dimethyldi-n-propoxysilane Butoxysilane, dimethyldi-sec-butoxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]dichlorosilane, (methyl)[2-(perfluoro-n-octyl) Ethyl]dimethoxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]diethoxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]di n-propoxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]diisopropoxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-butyl Oxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-sec-butoxysilane, (methyl)(3-mercaptopropyl)dichlorosilane, (methyl)(3- Mercaptopropyl)dimethoxysilane, (methyl)(3-mercaptopropyl)diethoxysilane, (methyl)(3-mercaptopropyl)di-n-propoxysilane, (methyl)( 3-mercaptopropyl) diisopropoxysilane, (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-propyl Oxysilane, (methyl)(vinyl)diisopropoxysilane, (methyl)(vinyl)di-n-butoxysilane, (methyl)(vinyl)di-sec-butoxysilane, di Vinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldiisopropoxysilane, divinyldi-n-butyl Oxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, Phenyldiisopropoxysilane, Diphenyldi-n-butoxysilane, Diphenyldi-sec-butoxysilane, Chlorodimethylsilane, Methoxydimethylsilane, Ethoxydimethylsilane , Chlorotrimethylsilane, Bromotrimethylsilane, Iodotrimethylsilane, Methoxytrimethylsilane, Ethoxytrimethylsilane, n-propoxytrimethylsilane, Isopropoxytrimethylsilane Butoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, tert-butoxytrimethylsilane, (chloro)(vinyl)dimethylsilane, (methyl Oxy)(vinyl)dimethylsilane, (ethoxy)(vinyl)dimethylsilane, (chloro)(methyl)diphenylsilane, (methoxy)(methyl)diphenyl Silane compounds having one silicon atom, such as silane and (ethoxy)(methyl)diphenylsilane, and the like. These can be used individually or in combination of 2 or more types.

Materials that can be purchased as commercial products include, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X- 21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22- 170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X- 41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, Shin-Etsu Chemical Co.);

Glass resin (Showa Denko Corporation);

SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray Dou Corning Company);

FZ3711, FZ3722 (above, Japan Unicar Corporation);

DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, チッソ company);

Methyl silicate MS51, methyl silicate MS56 (above, Mitsubishi Chemical Corporation);

Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, Colcoat Company);

Partial condensate of GR100, GR650, GR908, GR950 (above, Showa Denko Co., Ltd.).

Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxy Silane, 3-(Meth)acryloxypropyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Allyltrimethoxysilane, Allyltriethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltrimethoxysilane Ethoxysilane, Dimethyldimethoxysilane or Dimethyldiethoxysilane.

The epoxy equivalent of the polyorganosiloxane having an epoxy group is preferably 100 g/mol to 10000 g/mol, more preferably 150 g/mol to 1000 g/mol, and particularly preferably 150 g/mol to 300 g/mol. Therefore, when synthesizing a polyorganosiloxane having an epoxy group, it is preferable to set the ratio of the silane compound having an epoxy group and other silane compounds so that the epoxy equivalent of the obtained polyorganosiloxane reaches the above-mentioned scope.

As an organic solvent which can be used when synthesizing the polyorganosiloxane which has an epoxy group, a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, an alcohol compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types.

As a hydrocarbon compound, toluene, xylene, etc. are mentioned, for example.

Examples of the ketone compound include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentanone, diethyl ketone, and cyclohexanone.

Examples of the ester compound include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like.

As an ether compound, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc. are mentioned, for example.

Examples of alcohol compounds include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether. , Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Mono-N-Propyl Ether, etc.

Among them, water-insoluble substances are preferable.

As the usage-amount of an organic solvent, it is preferable that it is 10-10000 mass parts with respect to 100 mass parts of all silane compounds, and it is more preferable that it is 50-1000 mass parts.

The amount of water used when synthesizing the polyorganosiloxane having an epoxy group is preferably 0.5-fold mol to 100-fold mol, more preferably 1-fold mol to 30-fold mol, based on all silane compounds.

As a catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.

As the organic base, for example, organic primary or secondary amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole can be cited;

Organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;

Organic quaternary ammonium such as tetramethylammonium hydroxide, etc.

As a catalyst at the time of producing the polyorganosiloxane which has an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, side reactions such as ring opening of epoxy groups do not occur, and polyorganosiloxane can be obtained at a high hydrolysis/condensation rate, so the production stability is excellent.

In addition, a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and the polyorganosiloxane represented by the above formula (A-1), formula (A-2) or formula (A-3) respectively Since this liquid crystal aligning agent which is a reactant of a compound is extremely excellent in storage stability, it is very advantageous. The reason can be speculated that, as pointed out in the science of the sol-gel method (Agne Chengfengsha, 1988, pp. 154-161), when alkali metal compounds or organic bases are used as catalysts in hydrolysis and condensation reactions, whether A three-dimensional structure such as a random structure or a cage structure can be obtained, and a polyorganosiloxane with a small proportion of silanol groups can be obtained. That is to say, it can be speculated that since the polyorganosiloxane has a small proportion of silanol groups, the condensation reaction between silanol groups can be suppressed. In addition, when the liquid crystal aligning agent of the present invention contains other In the case of polymers, the condensation reaction between silanol groups and other polymers can also be suppressed, resulting in excellent storage stability.

As the catalyst, organic bases are more preferred, and organic tertiary amines and organic quaternary ammoniums are particularly preferred. The amount of the organic base used varies depending on the type of organic base and reaction conditions such as temperature. For example, it is preferably 0.01 to 3 times moles, more preferably 0.05 times to 1 times moles, based on the total silane compounds.

The hydrolysis or hydrolysis-condensation reaction when synthesizing the polyorganosiloxane having an epoxy group is preferably carried out by dissolving a silane compound having an epoxy group and, if necessary, other silane compounds in an organic solvent, and mixing the solution with an organic base and Water is mixed and carried out by heating, for example, an oil bath.

The heating temperature of the oil bath during the hydrolysis/condensation reaction is preferably 130°C or lower, more preferably 40°C to 100°C. The heating time is preferably from 0.5 hour to 12 hours, and more preferably from 1 hour to 8 hours. During heating, the liquid mixture may be stirred or refluxed.

After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. When washing, it is preferable to use water containing a small amount of salt, for example, an ammonium nitrate aqueous solution of about 0.2% by mass, in order to facilitate the washing operation. Wash until the water layer after washing is neutral, and then dry the organic solvent layer with a desiccant such as anhydrous calcium sulfate or molecular sieve if necessary, and remove the solvent, thereby obtaining the desired polyorganosiloxane having an epoxy group. alkyl.

In the present invention, commercially available items can be used as the polyorganosiloxane having an epoxy group. Examples of such commercially available items include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (above, Chisso Corporation) and the like.

The polyorganosiloxane having an epoxy structure has a polystyrene-equivalent weight average molecular weight (hereinafter, sometimes referred to as "Mw") measured by gel permeation chromatography, preferably 500 to 100,000, more preferably 1,000 to 10,000 , and particularly preferably 1000-5000. In addition, in this specification, Mw is the polystyrene conversion value measured by the gel permeation chromatography demonstrated below.

Column: Tosoh Corporation, TSKgel GRCXLII

Solvent: THF

Temperature: 40°C

Pressure: 6.8MPa

<Structure with liquid crystal alignment ability>

In this liquid crystal aligning agent, it is preferable that [A] polyorganosiloxane compound contains the structure which has liquid crystal aligning ability. [A] The polyorganosiloxane compound can further improve liquid crystal alignment ability by including a structure having liquid crystal alignment ability.

As a group which the structure which has a liquid crystal aligning ability has, it is preferable that it is the above-mentioned liquid crystal aligning group. The structure which has liquid crystal aligning ability can provide more excellent liquid crystal aligning ability to this liquid crystal aligning agent by having the said specific group.

The above-mentioned organic group having 17 to 51 carbon atoms having a steroid skeleton is preferably a monovalent organic group having 17 to 30 carbon atoms having a steroid skeleton, and examples thereof include cholestan-3-yl, cholestan-3-yl, Ste-5-en-3-yl, cholest-24-en-3-yl, cholest-5,24-dien-3-yl, lanostan-3-yl, etc.

Examples of the alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-lauryl, n-dodecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-stearyl, n-eicosyl, etc. The number of carbon atoms in the alkyl group is more preferably 4-20.

Examples of the fluoroalkyl group having 1 to 20 carbon atoms include trifluoromethyl, perfluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 3,3,4,4,5,5,5-heptafluoropentyl, etc.

Examples of the alkoxyaryl group having an alkyl group having 2 to 20 carbon atoms include n-propoxyaryl, n-butoxyaryl, n-pentyloxyaryl, n-hexyloxyaryl, n-heptyloxyaryl, n-octyloxyaryl and the like.

Examples of the alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms include n-propylcyclohexyl, n-butylcyclohexyl, n-pentylcyclohexyl, n-hexylcyclohexyl, n-heptylcyclohexyl, n- Octylcyclohexyl, etc.

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

Examples of the fluoroalkoxycyclohexyl group having a fluoroalkoxy group having 1 to 20 carbon atoms include 4,4,4-trifluorobutoxycyclohexyl, 4,4,5,5, 5-pentafluoropentyloxycyclohexyl, etc.

The structure having liquid crystal alignment ability preferably further has a structure represented by the above formula (B-1). Since the structure having the above-mentioned liquid crystal aligning ability has a specific structure, even by the photo-alignment method, a liquid crystal aligning film can be formed from this liquid crystal aligning agent.

The [A] polyorganosiloxane compound containing a structure having liquid crystal alignment ability can be obtained by reacting a polyorganosiloxane having an epoxy group with a compound having liquid crystal alignment ability represented by the following formula (B-2) And get.

R ^E -T (B-2)

In the above formula (B-2), ^RE is a group including a structure having liquid crystal alignment ability. T is carboxyl or hydroxyl.

Preferable examples of the formula (B-2) include compounds represented by the following formulas (B-2-1) to (B-2-8).

In said formula (B-2-1), R ^f is the said liquid crystal aligning group. X ^c is a single bond, oxygen atom, sulfur atom, phenylene, cyclohexylene, -COO-, -NHCO-, -CONH-, -CO-, -OCO- or a combination of two or more of them linking group. X ^d is a single bond, an oxygen atom, a phenylene group, -CO-, -OCO-, -(CH ₂ ) _a -, or a linking group combining two or more of them. a is an integer of 1-6. T is synonymous with the above formula (B-2).

In the above formula (B-2-2), R ^f , X ^d and T have the same meaning as those in the above formula (B-2-1).

^Xe is a single bond, an oxygen atom, a sulfur atom, a phenylene group, -COO-, -NHCO-, -CONH-, -CO-, -OCO-, or a linking group combining two or more of them.

In the above formula (B-2-3), R ^f and T have the same meaning as in the above formula (B-2-1).

X ^f is a single bond, an oxygen atom, -CO-, -(CH ₂ ) _a -, or a linking group combining two or more of them. a is an integer of 1-6. m is an integer of 0-4.

In the above formulas (B-2-4) to (B-2-6), R ^f and T have the same meaning as in the above formula (B-2-1).

X ^g is a single bond, an oxygen atom, a sulfur atom, -COO-, -NHCO-, -CONH-, -CO-, -OCO-, or a linking group combining two or more of them.

X ^h is a single bond, an oxygen atom, a sulfur atom, -(CH ₂ ) _a -, -CO-, or a linking group combining two or more of them. a is an integer of 1-6.

In the above formulas (B-2-7) and (B-2-8), R ^f and T have the same meaning as in the above formula (B-2-1). X ^j is a single bond, an oxygen atom, -COO-, -OCO-, -(CH ₂ ) _a -, or a linking group combining two or more of them. a is an integer of 1-6.

In addition, in the above-mentioned formulas (B-2-1) to (B-2-8), combinations of substituents forming an O—O bond or an α,β-diketone structure are not allowed.

Among the above formulas (B-2-1) to (B-2-8), compounds represented by the following formulas (B-2-1-1) to (B-2-8-2) are more preferred.

In the above formulas (B-2-1-1) to (B-2-8-2), R ^f has the same meaning as the above formula (B-2-1). a is an integer of 1-6.

When a group having a structure represented by the above-mentioned formula (B-1) is included, other preferred examples of compounds having liquid crystal alignment ability include, for example, the following formula (B-2-1-1') to formula (B -2-8-1') represented by the compound.

In the above formula, R ^f is synonymous with the above formula (B-2-1).

On the other hand, ^RE in the above formula (B-2) has an organic group having a steroid skeleton with 17 to 51 carbon atoms, an alkyl group with 2 to 20 carbon atoms, and an alkyl group with 1 carbon atom. Fluoroalkyl groups with ∼20 carbon atoms, cyclohexyl groups, alkoxyaryl groups with alkyl groups with 2 to 20 carbon atoms, alkylcyclohexyl groups with alkyl groups with 1 to 20 carbon atoms, and alkylcyclohexyl groups with At least one selected from the group consisting of a fluoroalkylcyclohexyl group having a fluoroalkyl group of 1 to 20 and a fluoroalkoxycyclohexyl group having a fluoroalkoxy group having 1 to 20 carbon atoms , but when the compound (B-2) does not contain the structure represented by the above formula (B-1), it is preferably a compound represented by the following formula (B-2-9) to formula (B-2-11), etc. .

R ^f and T in the above formula (B-2-9) to formula (B-2-11) have the same meaning as the above formula (B-2-1). X ^k is a single bond, an oxygen atom, -COO- or -OCO-.

In the above formula (B-2-11), p is 1 or 2.

Examples of compounds in which T is a carboxyl group in the above formula (B-2-9) include n-butyric acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, n-lauric acid, N-dodecanoic acid, n-tridecanoic acid, n-tetradecanoic acid, n-pentadecanoic acid, n-hexadecanoic acid, n-heptadecanoic acid, n-stearic acid, n-nonadecanoic acid, n-eicosic acid, tetrahydroabietic acid, Monocholestyl succinate, monocholestyl glutarate, compounds represented by the following formulae, and the like.

C _h F _2h+1 -C _i H _2i -COOH

In the above formula, h is an integer of 1-3. i is an integer of 3-18.

Examples of compounds in which T is a hydroxyl group in the above formula (B-2-9) include 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-undecyl alcohol, 1-dodecanol, 1-tridecyl alcohol, 1-tetradecyl alcohol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-stearyl alcohol, 1- Nonadecanol, 1-eicosanol, etc.

As a compound in which T is a carboxyl group in the above formula (B-2-10), for example, 4-methylbenzoic acid, 4-ethylbenzoic acid, 4-n-propylbenzoic acid, 4-n-butylbenzoic acid, 4-n-pentylbenzoic acid, 4-n-hexylbenzoic acid, 4-n-heptylbenzoic acid, 4-n-octylbenzoic acid, 4-n-nonylbenzoic acid, 4-n-decylbenzoic acid, 4-n- Dodecylbenzoic acid, 4-n-octadecylbenzoic acid, 4-n-methoxybenzoic acid, 4-n-ethoxybenzoic acid, 4-n-propoxybenzoic acid, 4-n-butoxy Benzoic acid, 4-n-pentyloxybenzoic acid, 4-n-hexyloxybenzoic acid, 4-n-heptyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-nonyloxybenzoic acid, 4-n- Decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-octadecyloxybenzoic acid, compounds represented by the following formulas, and the like.

In the above formula, j is an integer of 5-20. k is an integer of 1-3. ma is an integer of 0-18. n is an integer of 1-18.

Examples of compounds in which T is a carboxyl group in the above formula (B-2-11) include 4-(n-butyl)cyclohexyl carboxylic acid, 4-(n-pentyl)cyclohexyl carboxylic acid, 4-(n-butyl ) dicyclohexyl carboxylic acid, 4-(n-pentyl) dicyclohexyl carboxylic acid and the like.

<Synthesis method of compound having liquid crystal alignment ability>

The compounds represented by the above formulas (B-2-1) to (B-2-11) can be obtained as commercial products, or can be synthesized by appropriately combining ordinary methods of organic chemistry. Below, the synthesis method will be described by taking the compound where ^Rf is an alkyl group as an example, and for compounds other than ^Rf being an alkyl group, it can also be synthesized by the same operation or by referring to the synthesis method of this method, which is very important for those skilled in the art It's easy to understand.

The compound represented by the above-mentioned formula (B-2-1-1), for example, can be obtained by heating hydroxycinnamic acid and a haloalkyl group having an alkyl group corresponding to R ^f in the presence of a suitable base such as potassium carbonate, so that Its reaction is followed by hydrolysis in an appropriate alkaline aqueous solution such as sodium hydroxide.

The compound represented by the above-mentioned formula (B-2-1-2), for example, can be obtained by making hydroxycinnamic acid and an alkyl acid chloride having an alkyl group corresponding to R ^f in the presence of a suitable base such as potassium carbonate, at 0° C. It is obtained by reacting at a temperature of ~ room temperature.

The compound represented by the above-mentioned formula (B-2-1-4), for example, can be obtained by making methyl hydroxybenzoate and haloalkyl or alkyl tosylate having an alkyl corresponding to R ^f in potassium carbonate or the like. In the presence of a base, react at room temperature to 100°C, then hydrolyze it in a suitable alkaline aqueous solution such as sodium hydroxide, and further use thionyl chloride to form an acid chloride, and then make it in the presence of a suitable base such as potassium carbonate It is obtained by reacting with hydroxycinnamic acid at a temperature of 0°C to room temperature.

The compound represented by the above-mentioned formula (B-2-1-5), for example, can be obtained by making hydroxybenzoic acid and an alkyl acid chloride having an alkyl group corresponding to ^Rf in the presence of a suitable base such as triethylamine, at 0 After reacting at a temperature ranging from 0°C to room temperature, form an acid chloride with thionyl chloride, and react it with hydroxycinnamic acid at a temperature ranging from 0°C to room temperature in the presence of a suitable base such as potassium carbonate.

The compound represented by the above-mentioned formula (B-2-1-6), for example, can form acid chloride with 4-alkylbenzoic acid with thionyl chloride, and make it react with hydroxycinnamic acid in the presence of appropriate bases such as potassium carbonate. It is obtained by reacting at a temperature from 0°C to room temperature.

The compound represented by the above-mentioned formula (B-2-1-7), for example, can be prepared by making 4-hydroxycyclohexyl carboxylate methyl ester and a haloalkyl group having an alkyl group corresponding to R ^f in sodium hydride or metal sodium, etc. After reacting in the presence of a base to form an ether, hydrolyze it in an aqueous base solution such as sodium hydroxide, and further use thionyl chloride to form an acid chloride, and then make it react with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at a temperature of 0°C to room temperature. obtained by the reaction.

The compound represented by the above-mentioned formula (B-2-1-8), for example, can form an acid chloride by using thionyl chloride to have an alkyl 4-alkylcyclohexyl carboxylic acid corresponding to R ^f , and make it react in carbonic acid It is obtained by reacting hydroxycinnamic acid in the presence of a suitable base such as potassium at a temperature ranging from 0°C to room temperature.

The compound represented by the above-mentioned formula (B-2-1-9) can form an ether bond by reacting a haloalkyl group having an alkyl group corresponding to R ^f with hydroxybenzaldehyde in the presence of alkalis such as potassium carbonate, and use 4- Acetyl benzoic acid is obtained by aldol condensation in the presence of sodium hydroxide. The compounds represented by the above formula (B-2-1-10) to formula (B-2-1-15) can be obtained by referring to this method.

The compound represented by the above-mentioned formula (B-2-2-1), for example, can be reacted by using palladium and amine as a catalyst to react 4-iodophenol with an alkyl acrylate having an alkyl group corresponding to ^Rf (Heck reaction ) followed by ring-opening addition of a desired cyclic acid anhydride such as succinic anhydride or glutaric anhydride to the reaction product.

The compound represented by the above-mentioned formula (B-2-2-2) can be obtained by carrying out an alcoholic reaction between 4-alkylacetophenone and 4-formylbenzoic acid having an alkyl group corresponding to ^Rf . Formed by condensation of aldehydes. The compound represented by the above formula (B-2-2-3) can be obtained by referring to this method.

The compound represented by above-mentioned formula (B-2-2-4) can be carried out aldol by making 4-alkyl acetophenone and 4-hydroxybenzaldehyde having the alkyl corresponding to R ^f in the presence of sodium hydroxide obtained by condensation. The compound represented by the above formula (B-2-2-5) can be obtained by referring to this method.

The compound represented by the above formula (B-2-3-1) can be obtained by reacting an acrylate having an alkyl group corresponding to R ^f with 4-bromocinnamic acid using a palladium catalyst. By referring to this method, the compound represented by the above formula (B-2-3-2) can also be obtained.

The compound represented by the above-mentioned formula (B-2-4-1), for example, when R ^f is an alkyl group, can be obtained by making an alkyl succinic anhydride having an alkyl group corresponding to R ^f and 4-aminocinnamic acid Under the condition of reflux in acetic acid or under the condition of reflux in toluene or xylene in the presence of a suitable base catalyst such as triethylamine, the method can be obtained. When R ^f is a fluoroalkyl group, it can be obtained by adding maleic anhydride After being protected with an appropriate protecting group such as p-toluidine, after coupling by Grignard reaction with a fluoroalkyl iodide having a fluoroalkyl group corresponding to R ^I , deprotection by hydrolysis, and dehydration after ring closure , And 4-amino cinnamon acid reaction method obtained.

The compound represented by the above formula (B-2-4-2) can be synthesized, for example, by any of the following methods. As the first method, the method of protecting maleic anhydride with an appropriate protecting group such as p-toluidine, and reacting an alcohol having an alkyl group corresponding to R ^f with it in the presence of an appropriate base such as potassium carbonate After Michael addition, the protection is deprotected by hydrolysis, followed by dehydration and ring closure, and the product is reacted with 4-aminocinnamic acid in the same manner as in the synthesis of the compound represented by the above formula (B-2-4-1). As the second method, the following method can be cited: after reacting methyl malate with a haloalkyl group having an alkyl group corresponding to ^Rf in the presence of silver oxide to form an ether, hydrolyzing, and further dehydrating and ring-closing, and the above-mentioned The method for synthesizing the compound represented by the formula (B-2-4-1) is performed in the same manner, and the product is reacted with 4-aminocinnamic acid.

The compound represented by the above-mentioned formula (B-2-4-3), for example, except using a thiol having an alkyl corresponding to R ^f instead of an alcohol having an alkyl corresponding to R ^f , can be combined with the above-mentioned formula (B - The compound represented by 2-4-2) can be obtained in the same manner as the first method of synthesis.

The compound represented by the above formula (B-2-5-1) can be obtained, for example, by forming an acid chloride from 1,2,4-tricarboxycyclohexane anhydride with thionyl chloride, and having an alkyl corresponding to R ^f The alcohol reacts in the presence of a suitable base such as triethylamine to carry out esterification, and the synthetic method of the compound represented by the above-mentioned formula (B-2-4-1) is operated in the same way, and the product is mixed with 4-aminocinnamic acid obtained by the reaction.

The compound represented by the above formula (B-2-6-1), for example, can be synthesized as an intermediate ester compound by reacting the compound R ^f -OH corresponding to the desired compound with trimellitic anhydride halide, and then making the ester The compound is synthesized by reacting with 4-aminocinnamic acid. The synthesis of the intermediate ester compound is preferably carried out in an appropriate solvent in the presence of a basic compound. Examples of usable solvents include tetrahydrofuran and the like, and examples of basic compounds include triethylamine and the like. The reaction of ester compound and 4-aminocinnamic acid, can enumerate for example the method that makes both reflux in acetic acid, makes both in toluene or xylene in suitable catalyst (for example acid catalyst such as sulfuric acid or base catalyst such as triethylamine) ) in the presence of the reflux method, etc.

The compound represented by the above-mentioned formula (B-2-6-2) can be dehydrated and ring-closed to form an acid anhydride by refluxing 5-hydroxyphthalic acid in, for example, diethylbenzene, and then by the same method as above with 4- Aminocinnamic acid is reacted to synthesize an imide compound as a first intermediate, which is then synthesized by reacting the imide compound with a compound R ^f -H (H is a halogen atom) corresponding to the desired compound. At this time, it is preferably carried out in an appropriate solvent in the presence of a basic compound. Examples of usable solvents include amide compounds such as N,N-dimethylacetamide, and examples of basic compounds include potassium carbonate.

The compound represented by the above formula (B-2-7-1), for example, can form an ester by reacting 4-nitrocinnamic acid with a haloalkyl group having an alkyl group corresponding to ^R in the presence of potassium carbonate, and It is obtained by reducing the nitro group to form an amino group using, for example, tin chloride, and reacting the product with 1,2,4-tricarboxycyclohexylcyclohexane anhydride. The latter reaction can be carried out, for example, by refluxing the starting compound in acetic acid or by refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine. By referring to this method, the compound represented by the above formula (B-2-8-1) can be synthesized.

The compound represented by the above formula (B-2-8-2) can be obtained by using hydroxyphthalic acid instead of 1,2,4 in the synthesis of the compound represented by the above formula (B-2-7-1). -Tricarboxycyclohexylcyclohexane anhydride, obtained by reacting cinnamic acid derivatives with imide rings with succinic anhydride or glutaric anhydride.

The compound represented by the above-mentioned formula (B-2-1-1') can be obtained by reacting a haloalkyl group having an alkyl group corresponding to R ^f with 4-hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond. , In the presence of sodium hydroxide and 4-hydroxyacetophenone for aldol condensation. The compounds represented by the above formulas (B-2-1-2') to (B-2-1-7') can be obtained by referring to this method.

The compound represented by the above formula (B-2-2-1'), for example, can be obtained by reacting 4-iodophenol with an alkyl acrylate having an alkyl group corresponding to R ^f using palladium and amine as a catalyst .

The compound represented by the above-mentioned formula (B-2-2-2') can be obtained by making 4-alkylacetophenone and 4-hydroxybenzaldehyde having an alkyl group corresponding to ^R Formed by condensation of aldehydes. The compound represented by the above formula (B-2-1-3') can be obtained by referring to this method.

The compound represented by the above-mentioned formula (B-2-8-1'), for example, can form an ester by reacting with an alcohol having an alkyl corresponding to R after making 4-nitrocinnamic acid form an acid chloride with thionyl ^chloride , and use, for example, tin chloride to reduce the nitro group to form an amino group, and then react the product with hydroxyphthalic anhydride. The latter reaction can be carried out, for example, by refluxing the starting compound in acetic acid or by refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine.

Among these compounds (B-2), the above-mentioned formula (B-2-1-1), formula (B-2-1-3), formula (B-2-1-4), formula (B-2 -1-6)～Formula (B-2-1-8), Formula (B-2-1-16), Formula (B-2-1-19), Formula (B-2-1-21), Compounds represented by formula (B-2-4-1), formula (B-2-4-2), formula (B-2-5-1) and formula (B-2-7-1).

In addition, as a substance having a structure having liquid crystal alignment ability that does not contain the structure represented by the above formula (B-1), n-butyric acid, n-hexanoic acid, n-octanoic acid, n-lauric acid, n-stearic acid, 4-n-deca Octylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-octylbenzoic acid, 4-n-hexylbenzoic acid, 4-n-octadecyloxybenzoic acid, 4-n-dodecyloxybenzoic acid Benzoic acid, 4-n-octyloxybenzoic acid, 4-n-hexyloxybenzoic acid, 1-hexanethiol, 1-heptanthiol, 1-octylthiol, 1-nonanthiol, 1-decanethiol, 1-Undecanethiol, 1-Dodecanethiol, 1-Tetradecanethiol, 1-Hexadecanethiol, 1-Octadecanethiol, Monocholestylsuccinate and A compound represented by the following formula.

In this specification, the compound which does not contain the structure represented by the said formula (B-1) with the structure which has liquid-crystal aligning ability is called "another pretilt angle expressing compound". The proportion of such a polyorganosiloxane compound having a structure having liquid crystal alignment ability is preferably 10 mol % to 90 mol %, more preferably 20 mol % to 80 mol %, and particularly preferably 25 mol % to X ^a . Mole % to 75 mole %.

In the [A] polyorganosiloxane compound in the present invention, it is preferable that a part of the Si-X ^a bond in the polyorganosiloxane having an epoxy structure remains. Therefore, when carrying out the reaction, the total number of moles of compound (A-1), compound (A-2), compound (A-3) and the compound with liquid crystal alignment ability is preferably less than that of polyorganosilicon with epoxy structure The number of moles of the group ^Xa that the oxane has. At this time, when the use ratio of the compound having liquid crystal alignment ability having the group represented by the above formula (B-1) is preferably 50 mol% or more relative to the total amount of the compound, the [A] polyorganic The liquid crystal aligning agent of a siloxane compound can form the liquid crystal aligning film which shows favorable liquid crystal orientation by the photo-alignment method.

<[A] Synthesis method of polyorganosiloxane compound>

[A] The polyorganosiloxane compound can be obtained by combining a polyorganosiloxane having an epoxy group, a compound represented by the above-mentioned formula (A-1) to formula (A-3), and a polyorganosiloxane having liquid crystal alignment ability if necessary. The compound is preferably synthesized by reacting in an organic solvent in the presence of a catalyst. This manufacturing method is convenient and has a high rate of introduction of various structures, so it is suitable in these points.

The compound represented by formula (A-1) - formula (A-3) and the compound which has liquid crystal alignment ability can be used individually or in combination of 2 or more types.

Moreover, when the compound represented by a formula (A-1) - a formula (A-3) and the structure which have a liquid crystal aligning ability have a carboxyl group, it can react by substituting a part of a compound with another carboxylic acid. In this case, the proportion of the other carboxylic acid used is preferably 50 mol% or less based on the total of the compound and the other carboxylic acid.

As the catalyst, for example, an organic base or a so-called curing accelerator that accelerates the reaction of an epoxy compound and an acid anhydride can be used.

As the organic base, for example:

Organic primary or secondary amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;

Organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;

Organic quaternary ammonium such as tetramethylammonium hydroxide, etc. Among them, organic tertiary amines and organic quaternary ammoniums are preferred.

Examples of curing accelerators include:

Benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, triethanolamine and other tertiary amines;

2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-Benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-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-bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl )-2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium Trisalt, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium trimellitate 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 Oxyzine, 2-methylimidazole isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2,4-diamino-6-[2'-methylimidazolyl-(1 ')] Imidazole compounds such as isocyanuric acid adducts of ethyl-s-triazine;

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenylphosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide compound, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium, o,o-diethylphosphorodithioate, tetra-n-butylphosphonium benzotriazolium salt , Tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate and other quaternary phosphonium salts;

1,8-diazabicyclo[5.4.0]undecene-7, its organic acid salts and other diazabicycloalkenes;

Organometallic compounds such as zinc octoate, tin octoate, aluminum acetoacetate complex;

Tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride and other quaternary ammonium salts;

Boron compounds such as boron trifluoride and triphenyl borate;

Metal halides such as zinc chloride and tin chloride;

Amine addition type accelerators such as diamine diamides or adducts of amines and epoxy resins, etc., such as high melting point dispersed latent curing accelerators;

Microcapsule-type latent curing accelerators coated with polymers on the surface of curing accelerators such as imidazole compounds, organophosphorus compounds, and quaternary phosphonium salts;

Amine salt type latent curing accelerator;

Latent curing accelerators such as pyrolysis-type thermal cationic polymerization-type latent curing accelerators such as Lewis acid salts and Bronsted acid salts, etc.

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

The amount of the catalyst used is preferably 100 parts by mass or less, more preferably 0.01 parts by mass to 100 parts by mass, and particularly preferably 0.1 parts by mass to 20 parts by mass, based on 100 parts by mass of the polyorganosiloxane having an epoxy group. share.

The reaction temperature is preferably from 0°C to 200°C, and more preferably from 50°C to 150°C. The reaction time is preferably from 0.1 hour to 50 hours, and more preferably from 0.5 hour to 20 hours.

Examples of organic solvents that can be used when synthesizing the [A] polyorganosiloxane compound include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Among them, ether compounds, ester compounds, and ketone compounds are preferable from the viewpoint of solubility of raw materials and products, and ease of purification of the products. As the content of the solvent, its solid content concentration (the ratio of the total mass of components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1 mass % or more, and more preferably 5 mass % to 50 mass %.

[A] The Mw of the polyorganosiloxane compound is preferably 1,000 to 1,000,000, more preferably 2,000 to 100,000, and particularly preferably 3,000 to 50,000.

<Other polymers>

Other polymers can be used to further improve the solution properties of the liquid crystal aligning agent and the electrical properties of the obtained liquid crystal aligning film, so they can be appropriately contained in the liquid crystal aligning agent. Examples of other polymers include [B] at least one polymer selected from the group consisting of polyamic acid and polyimide, [C] other polyorganosiloxane compounds, and polyamic acid esters. , polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, etc.

Among them, [B] polymer and [C] other polyorganosiloxane compounds are preferable. By producing a liquid crystal aligning film using this liquid crystal aligning agent which further contains [B] polymer, the liquid crystal display element whose electric characteristics, such as a voltage retention rate, were further improved can be obtained. In addition, the liquid crystal aligning agent can further improve the crosslinking of the [A] polyorganosiloxane compound by further containing [C] other polyorganosiloxane compounds, thereby further improving the voltage retention of the obtained liquid crystal display element, etc. . Hereinafter, [B] polymer and [C] other polyorganosiloxane compounds will be described in detail.

<[B]polymer>

[polyamic acid]

[B] The polyamic acid which is a polymer can be obtained by making tetracarboxylic dianhydride and a diamine compound react.

As tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. In addition, tetracarboxylic dianhydrides described in Japanese Patent Application No. 2009-157556 can also be used. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types.

As aliphatic tetracarboxylic dianhydride, butane tetracarboxylic dianhydride etc. are mentioned, for example.

Examples of alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a ,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]furan-1,3-dione, 1,3 ,3a,4,5,9b-Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]furan-1,3 -diketone, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5 -Dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 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-tetraketone, etc.

As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride etc. are mentioned, for example, In addition, tetracarboxylic dianhydride as described in Japanese Patent Application No. 2009-84462 is also mentioned.

Among these tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides are preferred, and 2,3,5-tricarboxycyclopentylacetic dianhydrides or 1,2,3,4-cyclobutanetetracarboxylic dianhydrides are more preferred. anhydride, and particularly preferably 2,3,5-tricarboxycyclopentylacetic dianhydride.

As the amount of 2,3,5-tricarboxycyclopentylacetic dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride used, it is preferably 10 mol% of the total tetracarboxylic dianhydride The above, more preferably 20 mol% or more, and particularly preferably composed only of 2,3,5-tricarboxycyclopentylacetic dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

As a diamine compound, aliphatic diamine, alicyclic diamine, diaminoorganosiloxane, aromatic diamine etc. are mentioned, for example. These diamine compounds can be used alone or in combination of two or more. In addition, diamines described in Japanese Patent Application No. 2009-157556 can also be used.

Examples of the aliphatic diamine include m-xylylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, and the like.

Examples of the diaminoorganosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldicyclohexane, etc. In addition, examples include those described in Japanese Patent Application No. 2009-84462. of diamines.

Examples of aromatic diamines include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 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)bis( Aniline), 4,4'-(m-phenylenediisopropylidene)bis(aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminobenzene Oxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N- Methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-amino Phenyl)benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis(4-aminopropyl)piperazine, 3,5- Diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecane Oxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene Aminobenzene, Pentadecyloxy-2,5-diaminobenzene, Hexadecyloxy-2,5-diaminobenzene, Octadecyloxy-2,5-diaminobenzene, Cholesteryloxy -3,5-Diaminobenzene, Cholesteryloxy-3,5-Diaminobenzene, Cholesteryloxy-2,4-Diaminobenzene, Cholesteryloxy-2,4-Diaminobenzene , 3,5-diaminobenzoic acid cholestyl ester, 3,5-diaminobenzoic acid cholestyl ester, 3,5-diaminobenzoic acid lanostyl ester, 3,6-di(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, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, and the diaminobenzylamine represented by the following formula (6) Amine compounds, etc.

In the above formula (6), Za is an alkyl group having 1 to 3 carbon atoms, -O-, -COO- or -OCO-. pa is 0 or 1. q is an integer of 0-2. r is an integer of 1-20.

In the above formula (6), examples of C _r H _2r+1 groups include linear or branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. , nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosane Base etc.

As a diamine compound represented by said formula (6), the compound etc. which are represented, for example by following formula (6-1) - (6-5) are mentioned.

The usage ratio of the tetracarboxylic dianhydride and the diamine compound provided in the polyamic acid synthesis reaction is preferably 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride relative to the amino group contained in 1 equivalent of the diamine compound, More preferably, it is 0.3 equivalent - 1.2 equivalent.

Preference is given to carrying out the synthesis reaction in an organic solvent. The reaction temperature is preferably -20°C to 150°C, more preferably 0°C to 100°C. The reaction time is preferably 0.1 hours to 24 hours, more preferably 0.5 hours to 12 hours.

The organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid, and examples thereof include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide, N,N-dimethyl Aprotic polar solvents such as methyl formamide, N,N-dimethylimidazolinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphoric triamide; m-cresol , xylenol, phenol, halogenated phenol and other phenolic solvents.

The usage-amount (a) of the organic solvent is preferably 0.1% by mass to 50% with respect to the total amount (a+b) of the total amount (b) of the tetracarboxylic dianhydride and the diamine and the usage-amount (a) of the organic solvent. % by mass, more preferably 5% by mass to 30% by mass.

The polyamic acid solution obtained after the reaction can be directly supplied to the preparation of a liquid crystal aligning agent, or the polyamic acid contained in the reaction solution can be separated and then supplied to the preparation of a liquid crystal aligning agent, or the isolated polyamic acid can also be After refining, it supplies to preparation of a liquid crystal aligning agent. As a method of isolating the polyamic acid, for example, a method of pouring the reaction solution into a large amount of poor solvent and drying the obtained precipitate under reduced pressure, a method of distilling the reaction solution under reduced pressure using an evaporator, and the like may be mentioned. As the purification method of polyamic acid, the method of redissolving the separated polyamic acid in an organic solvent and precipitating it with a poor solvent, performing one or more steps of distilling off an organic solvent under reduced pressure using an evaporator, etc. method.

[Polyimide]

[B] The polyimide which is a polymer can be manufactured by dehydrating and ring-closing the amic acid structure which the said polyamic acid has, and imidating it.

Polyimide can be a complete imide formed by dehydrating and ring-closing all the amic acid structures of the polyamic acid as its precursor, or it can be a part of the amic acid structure dehydrating and ring-closing to form an amic acid structure and an imide structure. Coexisting partial imides. The imidization ratio of polyimide is preferably 30% or more, and more preferably 40% to 80%. In addition, the imidation ratio in polyimide is obtained by putting the solution of polyimide into pure water, drying the obtained precipitate under reduced pressure at room temperature, and dissolving it in deuterated dimethylmethylene Among the sulfones, ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance, and the obtained ¹ H-NMR spectrum was obtained from the formula represented by the following formula (7).

Imidization rate (%)={1-(A ¹ /A ² )×α}×100 (7)

In the above formula (7), A ¹ is the peak area (10 ppm) derived from NH group protons. ^A2 is the peak area from other protons. α is the ratio of the number of other protons to one proton of the NH group in the polyamic acid.

As a synthesis method of polyimide, for example, (i) a method of heating polyamic acid (hereinafter, sometimes referred to as "method (i)"), (ii) dissolving polyamic acid in an organic solvent, and A method of adding a dehydrating agent and a dehydration ring-closing catalyst to this solution, and heating as necessary (hereinafter, may be referred to as "method (ii)"), etc., using a method of dehydration ring-closure reaction of polyamic acid.

As the reaction temperature in the method (i), it is preferably 50°C to 200°C, and more preferably 60°C to 170°C. When the reaction temperature is lower than 50°C, the dehydration ring-closing reaction cannot proceed sufficiently, and when the reaction temperature exceeds 200°C, the molecular weight of the obtained polyimide will decrease. The reaction time is preferably 0.5 hours to 48 hours, more preferably 2 hours to 20 hours.

The polyimide obtained in the method (i) can be directly supplied to the modulation of the liquid crystal aligning agent, or the polyimide can be separated and then supplied to the modulation of the liquid crystal aligning agent, or the isolated polyimide can be refined Afterwards or after refining the obtained polyimide, it supplies to preparation of a liquid crystal aligning agent.

Examples of the dehydrating agent in the method (ii) include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride.

Although content of a dehydrating agent can be suitably selected according to the desired imidation ratio, it is preferable that it is 0.01 mol - 20 mol with respect to the amic-acid structure of 1 mol of polyamic acid.

Examples of the dehydration ring-closure catalyst in the method (ii) include pyridine, collidine, lutidine, triethylamine and the like.

The content of the dehydration ring-closing catalyst is preferably 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent contained. In addition, the higher the content of the dehydrating agent and the dehydration ring-closing catalyst, the more the imidation rate can be increased.

Examples of the organic solvent used in the method (ii) include the same organic solvents as those exemplified as the solvent used for polyamic acid synthesis.

The reaction temperature in method (ii) is preferably 0°C to 180°C, more preferably 10°C to 150°C. The reaction time is preferably 0.5 hour to 20 hours, more preferably 1 hour to 8 hours. By making reaction conditions into the said range, dehydration ring closure reaction can fully advance, and the suitable molecular weight of the obtained polyimide can be obtained.

In method (ii), a reaction solution containing polyimide can be obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal aligning agent, or can be supplied to the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and can also be supplied to the liquid crystal aligning agent after the polyimide is separated. The preparation of the liquid crystal alignment agent or the preparation of the separated polyimide after purification. As a method of removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method of solvent replacement and the like are mentioned. As the isolation method and purification method of polyimide, the method similar to the method etc. which were mentioned as the isolation method of polyamic acid, and a purification method are mentioned, for example.

<[C] Other polyorganosiloxane compounds>

In this liquid crystal aligning agent, it is preferable to further contain [C] other polyorganosiloxane compounds in addition to [A] polyorganosiloxane compounds, and [C] other polyorganosiloxane compounds are more preferably A polyorganosiloxane having a structural unit represented by the above formula (2). In addition, when the liquid crystal aligning agent contains [C] other polyorganosiloxane compounds, as long as most of [C] other polyorganosiloxane compounds exist independently of [A] polyorganosiloxane compounds, then A part thereof may exist as a condensate with a specific polyorganosiloxane compound.

In the above formula (2), X ^b is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Y ² is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Base, lauryl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc. .

Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and isobutoxy.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl and the like.

[C] The Mw of the other polyorganosiloxane compound is preferably 500 to 100,000, more preferably 500 to 10,000.

[C] Other polyorganosiloxane compounds, for example, can be selected from the group consisting of alkoxysilane and halogenated silane compounds, preferably in a suitable organic solvent, in the presence of water and a catalyst. At least one silane compound (hereinafter, sometimes referred to as "raw material silane compound") is synthesized by hydrolysis or hydrolysis-condensation.

Examples of raw material silane compounds include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert- Butoxysilane, tetrachlorosilane, etc.;

Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane , Methyltri-tert-butoxysilane, Methyltriphenoxysilane, Methyltrichlorosilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Ethyltri-n-propoxysilane, Ethyl Triisopropoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltri Ethoxysilane, phenyltrichlorosilane, etc.;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, etc.;

Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, etc.

Among them, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, Methoxysilane, Dimethyldiethoxysilane, Trimethylmethoxysilane or Trimethylethoxysilane.

Examples of organic solvents that can be used arbitrarily when synthesizing [C] other polyorganosiloxane compounds include alcohol compounds, ketone compounds, amide compounds, ester compounds, and other aprotic compounds. These can be used individually or in combination of 2 or more types.

Examples of alcohol compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isoamyl alcohol, 2-methylbutanol, S-pentanol, t-amyl alcohol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, s-hexanol, 2-ethylbutanol, s-heptanol, 3-heptanol, n-octanol, 2-Ethylhexanol, sec-octyl alcohol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decyl alcohol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecyl alcohol, sec-decyl alcohol Heptaol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and other monoalcohol compounds;

Ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4 - Heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and other polyol compounds;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol mono Partial ethers of polyol compounds such as diethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

As the ketone compound, for example, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl ketone, Methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, 2-hexanone, methyl cyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fecundity Monoketone compounds such as ketones;

Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione Ketone, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5 , β-diketone compounds such as 5,5-hexafluoro-2,4-heptanedione, etc.

As the amide compound, for example, formamide, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, acetamide, N-formamide N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine , N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc.

Examples of ester compounds include diethyl carbonate, ethylene carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, and isopropyl acetate. , n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, acetic acid 2-Ethylhexyl, Benzyl Acetate, Cyclohexyl Acetate, Methylcyclohexyl Acetate, Nonyl Acetate, Methyl Acetoacetate, Ethyl Acetoacetate, Ethylene Glycol Monomethyl Ether, Ethylene Glycol Acetate Monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono Butyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate , Di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc.

As other aprotic compounds, for example, acetonitrile, dimethylsulfoxide, N,N,N',N'-tetraethylsulfonamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylpiperazine, N-methyl Imidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, NMP, 1,3-dimethyl-2-imidazolinone, 1,3-dimethyltetrahydro- 2(1H)-pyrimidinone, etc.

Among these solvents, polyol compounds, partial ethers and ester compounds of polyol compounds are preferable.

The amount of water used when synthesizing [C] other polyorganosiloxane compounds is preferably 0.5 mol to 100 mol, more preferably 1 mol with respect to 1 mol of the total of alkoxy groups and halogen atoms contained in the raw material silane compound. mol to 30 mol, particularly preferably 1 mol to 1.5 mol.

Examples of catalysts that can be used when synthesizing [C] other polyorganosiloxane compounds include metal chelates, organic acids, inorganic acids, organic bases, alkali metal compounds, alkaline earth metal compounds, ammonia, and the like. These can be used individually or in combination of 2 or more types.

Examples of metal chelates include triethoxy mono(acetylacetonate) titanium, tri-n-propoxy mono(acetylacetonate) titanium, triisopropoxy mono(acetylacetonate) titanium, tri-n-butyl Oxygen mono(acetylacetonate)titanium, tri-sec-butoxymono(acetylacetonate)titanium, tri-tert-butoxymono(acetylacetonate)titanium, diethoxybis(acetylacetonate)titanium, di-n-butoxy Propoxy bis(acetylacetonate)titanium, diisopropoxybis(acetylacetonate)titanium, di-n-butoxybis(acetylacetonate)titanium, di-sec-butoxybis(acetylacetonate)titanium, Di-tert-butoxy·di(acetylacetonate)titanium, monoethoxy·tri(acetylacetonate)titanium, mono-n-propoxy·tri(acetylacetonate)titanium, monoisopropoxy·tri(acetylacetonate)titanium , mono-n-butoxy·tri(acetylacetonate)titanium, mono-sec-butoxy·tri(acetylacetonate)titanium, mono-tert-butoxy·tri(acetylacetonate)titanium, tetra(acetylacetonate)titanium, triethoxy Mono(ethyl acetoacetate) titanium, tri-n-propoxy mono(ethyl acetoacetate) titanium, triisopropoxy mono(ethyl acetoacetate) titanium, tri-n-butyl Oxygen mono(ethyl acetoacetate) titanium, tri-sec-butoxy mono(ethyl acetoacetate) titanium, tri-tert-butoxy mono(ethyl acetoacetate) titanium, diethyl Oxygen bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, diisopropoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-tert-butoxy bis (ethyl acetoacetate) titanium, mono Ethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, monoisopropoxy tris (ethyl acetoacetate) titanium, mono n-butoxy tri(ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-tert-butoxy tris (ethyl acetoacetate) titanium, Tetra(ethylacetoacetate) titanium, mono(acetylacetonate) tris(ethylacetoacetate) titanium, bis(acetylacetonate) bis(ethylacetoacetate) titanium, tris(acetylacetonate) mono( Titanium chelate compounds such as ethyl acetoacetate) titanium;

Triethoxy mono(acetylacetonate) zirconium, tri-n-propoxy mono(acetylacetonate) zirconium, triisopropoxy mono(acetylacetonate) zirconium, tri-n-butoxy mono(acetylacetonate) zirconium , Tri-sec-butoxy mono(acetylacetonate) zirconium, tri-tert-butoxy mono(acetylacetonate) zirconium, diethoxy bis(acetylacetonate) zirconium, di-n-propoxy bis(acetylacetonate) zirconium Zirconium, diisopropoxy bis(acetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-tert-butoxy di(acetylacetonate) zirconium, di-tert-butoxy di(acetylacetonate) zirconium Acetone) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonate) zirconium, monoisopropoxy tris (acetylacetonate) zirconium, mono-n-butoxy tris ( Zirconium acetylacetonate, mono-sec-butoxy tri(acetylacetonate) zirconium, mono-tert-butoxy tri(acetylacetonate) zirconium, tetrakis(acetylacetonate) zirconium, triethoxy mono(ethyl acetoacetate) ester) zirconium, tri-n-propoxy mono(ethyl acetoacetate) zirconium, triisopropoxy mono(ethyl acetoacetate) zirconium, tri-n-butoxy mono(ethyl acetoacetate) zirconium, tri-n-butoxy mono(ethyl acetoacetate) zirconium ester) zirconium, tri-sec-butoxy mono(ethyl acetoacetate) zirconium, tri-tert-butoxy mono(ethyl acetoacetate) zirconium, diethoxy bis(ethyl acetoacetate) zirconium ester) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, diisopropoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium Acetate) zirconium, bis-butoxy bis (ethyl acetoacetate) zirconium, di-tert-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetyl Acetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, monoisopropoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl Acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-tert-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium Zirconium, mono(acetylacetonate) tris(ethyl acetoacetate) zirconium, bis(acetylacetonate) bis(ethyl acetoacetate) zirconium, tris(acetylacetonate) mono(ethyl acetoacetate) zirconium, etc. Zirconium chelate compounds;

Aluminum chelate compounds such as tris(acetylacetonate)aluminum and tris(ethylacetoacetate)aluminum, and the like.

Examples of organic acids include acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, Sebacic acid, gallic acid, butyric acid, mellitic acid, arachidoleic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p- Aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid etc.

Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

Examples of organic bases include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, Ethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, etc.

As an alkali metal compound, sodium hydroxide, potassium hydroxide, etc. are mentioned, for example.

As an alkaline earth metal compound, barium hydroxide, calcium hydroxide, etc. are mentioned, for example.

Among them, metal chelate compounds, organic acids and inorganic acids are preferred, and titanium chelate compounds and organic acids are more preferred.

As the usage-amount of a catalyst, it is preferable that it is 0.001-10 mass parts with respect to 100 mass parts of raw material silane compounds, and it is more preferable that it is 0.001-1 mass part.

The water added when synthesizing [C] other polyorganosiloxane compounds may be added intermittently or continuously to the silane compound as a raw material or to a solution in which the silane compound is dissolved in an organic solvent. The catalyst may be added in advance to a silane compound as a raw material, or may be added to a solution in which a silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in added water.

The reaction temperature at the time of synthesizing [C] other polyorganosiloxane compounds is preferably 0°C to 100°C, and more preferably 15°C to 80°C. The reaction time is preferably 0.5 hour to 24 hours, more preferably 1 hour to 8 hours.

[Content ratio of other polymers]

When the liquid crystal aligning agent contains other polymers, the content ratio of the other polymers varies depending on the type of other polymers, but is preferably 10000 parts by mass or less with respect to 100 parts by mass of the [A] polyorganosiloxane compound. .

When this liquid crystal aligning agent contains [B] polymer, it is preferable that it is 200 mass parts - 5000 parts by mass.

When the liquid crystal aligning agent contains [C] other polyorganosiloxane, the content ratio of [C] other polyorganosiloxane compound is preferably 100 parts by mass with respect to 100 parts by mass of polyorganosiloxane ~2000 parts by mass.

When this liquid crystal aligning agent contains another polymer, as a kind of other polymer, [B] polymer or [C] other polyorganosiloxane is preferable, and [B] polymer is more preferable.

<Optional ingredients>

Examples of optional components include curing agents, curing catalysts, curing accelerators, compounds having at least one epoxy group in the molecule (hereinafter sometimes referred to as "epoxy compounds"), functional silane compounds, and surfactants. wait. Hereinafter, these optional components will be described in detail.

[Curing agent, curing catalyst and curing accelerator]

In order to make the crosslinking reaction of [A] polyorganosiloxane compound firmer, you may contain a hardening|curing agent and a hardening catalyst in this liquid crystal aligning agent. Moreover, in order to accelerate the hardening reaction controlled by a hardening|curing agent, you may contain the said hardening accelerator in this liquid crystal aligning agent.

As the curing agent, a curing agent generally used for curing a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used, such as polyamine, polycarboxylic acid anhydride, polycarboxylic acid Acid etc.

As polyhydric carboxylic acid anhydride, the anhydride of cyclohexanetricarboxylic acid, other polyhydric carboxylic acid anhydride etc. are mentioned, for example. Examples of cyclohexanetricarboxylic acid anhydride include cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, Carboxylic acid, 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-anhydride, etc.

Examples of other polyvalent carboxylic anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, Trimellitic anhydride and tetracarboxylic dianhydride commonly used in the synthesis of polyamic acid, in addition, alicyclic compounds having conjugated double bonds such as α-terpinene and allo-ocimene, and maleic anhydride Diels-Alder reaction products and their hydrides.

The usage ratio of the curing agent is preferably 100 parts by mass or less with respect to 100 parts by mass of the [A] polyorganosiloxane compound.

Examples of the curing catalyst include antimony hexafluoride compounds, phosphorus hexafluoride compounds, aluminum triacetoacetate, and the like. The usage ratio of the curing catalyst is preferably 2 parts by mass or less with respect to 100 parts by mass of the [A] polyorganosiloxane compound.

Examples of curing accelerators include

imidazole compound;

Quaternary phosphorus compounds;

Quaternary ammonium compounds;

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

Organometallic compounds such as zinc octoate, tin octoate, aluminum acetoacetate complexes;

Boron compounds such as boron trifluoride and triphenyl borate;

Metal halides such as zinc chloride and tin chloride;

High-melting-point dispersed latent curing accelerators such as amine-addition accelerators such as diamine diamides and adducts of amines and epoxy resins;

Microcapsule-type latent curing accelerators coated with polymers on the surface of quaternary phosphonium salts;

Amine salt type latent curing accelerator;

Pyrolysis-type thermal cationic polymerization-type latent curing accelerators such as Lewis acid salts and Bronsted acid salts, and the like.

The usage ratio of the curing accelerator is preferably 10 parts by mass or less with respect to 100 parts by mass of [A]polyorganosiloxane.

[epoxy compound]

In order to further improve the adhesiveness of the formed liquid crystal aligning film with respect to the board|substrate surface, you may contain an epoxy compound in this liquid crystal aligning agent.

Examples of 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 di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl ether Base-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-di(N,N-diglycidylaminomethyl) ring Hexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl Base-aminomethylcyclohexane, etc.

The content ratio of the epoxy compound is preferably 40 parts by mass or less, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total of the [A] polyorganosiloxane compound and other polymers optionally contained. Moreover, when this liquid crystal aligning agent contains an epoxy compound, in order to generate|occur|produce a crosslinking reaction efficiently, you may use together base catalysts, such as 1-benzyl-2-methylimidazole.

[Functional silane compound]

In order to improve the adhesiveness of the formed liquid crystal aligning film with respect to the board|substrate surface, the said functional silane compound can be used.

Examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane , N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane Oxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4, 7-Triazadecane, 10-Triethoxysilyl-1,4,7-Triazadecane, 9-Trimethoxysilyl-3,6-diazanonylacetic acid Esters, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyl Triethoxysilane, 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, a reaction product of tetracarboxylic dianhydride and a silane compound having an amino group, etc., other than that described in JP-A-63-291922 A reactant of a tetracarboxylic dianhydride and a silane compound having an amino group, etc.

The content ratio of the functional silane compound is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the total of the [A] polyorganosiloxane compound and other polymers optionally contained.

[Surfactant]

Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, polysiloxane surfactants, polyoxyalkylene surfactants, fluorine-containing surfactants, etc. .

As a usage ratio of surfactant, it is preferable that it is 10 mass parts or less with respect to the whole 100 mass parts of this liquid crystal aligning agent, and it is more preferable that it is 1 mass part or less.

<Preparation method of liquid crystal aligning agent>

As above-mentioned, this liquid crystal aligning agent contains [A] polyorganosiloxane compound as an essential component, and contains other components as needed, and it is preferable to prepare as the composition of the solution form which each component melt|dissolved in the organic solvent.

As an organic solvent, it is preferable that it dissolves [A] polyorganosiloxane compound and other components used arbitrarily, and does not react with them. As an organic solvent which can be preferably used for this liquid crystal aligning agent, it changes with the kind of other polymer which arbitrarily contains.

As a preferable organic solvent when this liquid crystal aligning agent contains [A] polyorganosiloxane compound and [B] polymer, the organic solvent mentioned as a solvent used for polyamic-acid synthesis is mentioned. These organic solvents may be used alone or in combination of two or more.

On the other hand, when the liquid crystal aligning agent contains only [A] polyorganosiloxane compound as a polymer, or contains [A] polyorganosiloxane compound and [C] other polyorganosiloxane compounds, it is preferred Organic solvents, such as 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 monopentyl ether, ethylene glycol mono Hexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl cellosolve Carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate , 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, acetic acid Amyl ester, isoamyl acetate, etc. Among them, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, and the like are preferable.

A preferable solvent that can be used to prepare the liquid crystal aligning agent can be obtained by using one or two or more of the above-mentioned organic solvents in combination depending on the presence or absence of other polymers and the type of the polymer. Such a solvent makes the surface tension of a liquid crystal aligning agent into the range of 25mN/m-40mN/m without depositing each component contained in a liquid crystal aligning agent in the following preferable solid content concentration.

The solid content concentration of the liquid crystal aligning agent of the present invention, that is to say the ratio of the mass of all components except the solvent in the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent, is selected in consideration of viscosity, volatility, etc., and is preferably 1% by mass ~10% by mass. When solid content concentration is less than 1 mass %, the film thickness of the liquid crystal aligning film formed from this liquid crystal aligning agent may be too small and a favorable liquid crystal aligning film may not be obtained. On the other hand, when the solid content concentration exceeds 10% by mass, the thickness of the coating film may be too large to obtain a favorable liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent may increase, resulting in insufficient coating properties. The range of preferable solid content density|concentration differs with the method used when apply|coating a liquid crystal aligning agent on a board|substrate. For example, when the spin coating method is used, the solid content concentration range is preferably 1.5% by mass to 4.5% by mass. When the printing method is used, the solid content concentration is preferably in the range of 3% by mass to 9% by mass, and thus the viscosity of the solution is in the range of 12mPa·s to 50mPa·s. When the inkjet method is used, the solid content concentration is preferably in the range of 1% by mass to 5% by mass, thereby making the solution viscosity in the range of 3mPa·s to 15mPa·s.

The temperature at the time of preparing this liquid crystal aligning agent is preferably 0°C to 200°C, and more preferably 10°C to 60°C.

<Liquid crystal aligning film and its forming method>

The liquid crystal aligning film formed from this liquid crystal aligning agent is also included in this invention suitably. As a method of forming a liquid crystal alignment film using this liquid crystal alignment agent, in [A] the polyorganosiloxane compound, [B] the structure having liquid crystal alignment ability does not contain the structural unit represented by the above formula (B-1) The case (hereinafter, the formation method in this case is referred to as "formation method (i)"), the case where the structure having liquid crystal alignment ability contains the structural unit represented by the above formula (B-1) (hereinafter, in this case The method of formation is referred to as "formation method (ii)"). Hereinafter, the formation methods (i) and (ii) will be described in detail.

[formation method (i)]

First, two substrates provided with a patterned transparent conductive film are used as a pair, and are formed on each transparent conductive film by an appropriate coating method such as roll coating, spin coating, printing, and inkjet. This liquid crystal aligning agent was coated on the surface. Next, the coated surface is preheated (prebaked), and then fired (postbaked) to form a coating film. As a prebaking condition, it is 0.1 minute - 5 minutes at 40 degreeC - 120 degreeC, for example. The post-baking conditions are preferably 120°C to 300°C, more preferably 150°C to 250°C, preferably for 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. The film thickness of the coating film after the post-baking is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

Examples of the substrate include glass substrates such as float glass and soda lime glass, plastic substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, and polycarbonate. materials such as transparent substrates.

Examples of the transparent conductive film include a NESA film containing SnO ₂ , an ITO film containing In ₂ O ₃ —SnO _{2 ,} and the like. As a patterning method of these transparent conductive films, the method of using a mask when forming a transparent conductive film, etc. are mentioned, for example.

When coating the liquid crystal aligning agent, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, a functional silane compound, titanate compound, etc. can be coated on the substrate and transparent conductive film in advance.

When the liquid crystal aligning agent is used to form a liquid crystal aligning film for a vertical alignment type liquid crystal display element, the coating film formed as described above can be directly used as a liquid crystal alignment film for a vertical alignment type liquid crystal display element, or the liquid crystal alignment film for the vertical alignment type liquid crystal display element can be used The coating surface is optionally sanded. On the other hand, when using the liquid crystal aligning agent of this invention for formation of the liquid crystal aligning film for horizontal alignment type liquid crystal display elements, a liquid crystal aligning film can be formed by giving the coating film formed above the rubbing process.

The aforementioned grinding treatment can be carried out by rubbing in a certain direction using a roller wrapped with a cloth made of fibers such as nylon, rayon, and cotton. Here, for example, as described in Japanese Patent Application Laid-Open No. 6-222366, Japanese Patent Laid-Open No. 6-281937, etc., a part of the liquid crystal aligning film can be irradiated with ultraviolet rays to change the pretilt angle of the formed liquid crystal aligning film. or as described in Japanese Patent Application Laid-Open No. 5-107544, after forming a resist film on a part of the surface of the formed liquid crystal alignment film, the polishing process is carried out in a different direction from the previous polishing process. , and then remove the resist film, so that the liquid crystal alignment film has different liquid crystal alignment energy in each area, so that the viewing field characteristics of the obtained horizontal liquid crystal display element can be improved.

[Formation method (ii)]

The formation method (ii) of the liquid crystal alignment film comprised in the present invention comprises:

(1) A process of coating a liquid crystal aligning agent comprising [A] a polyorganosiloxane compound comprising a polyorganosiloxane compound having the above formula (B-1) on a substrate to form a coating film. The structural unit represented by the structure with liquid crystal orientation ability, and

(2) A step of irradiating radiation to at least a part of the coating film formed in the step (1).

By the formation method of this invention using this liquid crystal aligning agent, the liquid crystal aligning film which fully satisfies characteristics, such as liquid crystal orientation, voltage retention, and light resistance, which are practically required as a liquid crystal display element can be formed.

As the above (1) coating film forming process, the same process as the coating film forming process described in the forming method (i) can be applied.

In the formation method (ii), the liquid crystal aligning film can be produced by (2) the step of irradiating at least a part of the coating film formed in the step (1) with radiation instead of the polishing treatment described in the formation method (i).

As the radiation, linearly polarized or partially polarized radiation or non-polarized radiation can be used, for example, ultraviolet rays and visible rays including light with a wavelength of 150nm to 800nm, preferably ultraviolet rays with a wavelength of 300nm to 400nm. When the radiation used is linearly polarized or partially polarized, it can be irradiated from a direction perpendicular to the substrate surface, and in order to impart a pretilt angle, it can also be irradiated from an oblique direction. In addition, they can also be combined. . When irradiating unpolarized radiation, the direction of irradiation must be an oblique direction.

Examples of the light source used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. Ultraviolet rays in the above-mentioned preferable wavelength region can be obtained by a method of using the above-mentioned light source in combination with, for example, a filter, a diffraction grating, or the like.

The radiation dose is preferably 1 J/m ² to less than 10000 J/m ² , more preferably 10 J/m ² to 3000 J/m ² . In addition, when imparting liquid crystal alignment ability to a coating film formed by a conventionally known liquid crystal aligning agent by a photo-alignment method, a radiation dose of 10000 J/m ² or more is required, and when using this liquid crystal aligning agent, even if the photo-alignment method When the radiation dose is 3000J/m ² or less, further 1000J/m ² or less, and especially 500J/m ² or less, good liquid crystal orientation can also be imparted, and it contributes to the reduction of the manufacturing cost of liquid crystal display elements.

<Liquid crystal display element>

The liquid crystal display element provided with this liquid crystal aligning film is also suitably included in this invention. Therefore, the liquid crystal display element of this application equipped with the liquid crystal aligning film formed by this liquid crystal aligning agent can be suitably used for a clock, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, a portable information terminal, Display devices such as digital cameras, mobile phones, various monitors, and LCD TVs.

<Manufacturing method of liquid crystal display element>

This liquid crystal display element can be manufactured as follows, for example.

As the first method, it is a conventionally known method, wherein, first, two substrates are arranged facing each other with a gap (cell gap) therebetween so that the respective liquid crystal aligning films face each other, and the two substrates are bonded together using a sealant. The peripheral parts are bonded together, and the filling liquid crystal is injected into the cell gap defined by the substrate surface and the sealant, and the injection hole is closed to manufacture a liquid crystal cell.

The second method is a method called ODF (One Drop Fill) method, in which, for example, a UV-curable sealant is applied to a predetermined part of one of the two substrates on which the liquid crystal alignment film is formed. material, and then drop liquid crystal on the surface of the liquid crystal alignment film, then stick another substrate so that the liquid crystal alignment film faces each other, and then irradiate the entire surface of the substrate with ultraviolet rays to cure the sealant, thereby manufacturing a liquid crystal cell.

In the case of either method, it is desirable to subsequently heat the liquid crystal cell to a temperature at which the liquid crystal used is in the isotropic phase, and then slowly cool it to room temperature, thereby removing the flow orientation when filling the liquid crystal. Then, the liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell.

Examples of the sealing agent include epoxy resins containing alumina balls as separators and a curing agent.

As said liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. are mentioned, for example. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferred. Examples of such liquid crystals include biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, Bicyclooctane-based liquid crystals, cubane-based liquid crystals, etc. In addition, it is also possible to further add and use cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate (Melk, "C-15", "CB-15") to the above-mentioned liquid crystals. Chiral agents for sale; ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, etc.

On the other hand, in the case of a vertical alignment type liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable. Examples of such liquid crystals include dicyanobenzene-based liquid crystals, pyridazine-based liquid crystals, Schiff-based liquid crystals, azo oxide-based liquid crystals, biphenyl-based liquid crystals, and phenylcyclohexane-based liquid crystals.

As the polarizing plate used on the outside of the liquid crystal cell, a polarizing plate or a H-film obtained by absorbing iodine while stretching and aligning polyvinyl alcohol by sandwiching cellulose acetate protective films can be cited. The film itself forms a polarizing plate.

Example

Hereinafter, although this invention is demonstrated in full detail based on an Example, this invention is not limitedly interpreted by description of this Example.

In addition, the synthesis of raw material compounds and polymers in the synthesis routes shown in the following synthesis examples was repeated as necessary to ensure the required amounts of raw material compounds and polymers used in the following examples. The epoxy equivalent is measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105. The solution viscosity (mPa·s) was measured using an E-type rotational viscometer for the solution in which the polymer concentration of the polymer solution was adjusted to 10% by mass in each synthesis example.

<Synthesis of Polyorganosiloxane Having Epoxy Group>

[Synthesis Example 1]

In a reaction vessel with a stirrer, thermometer, dropping funnel and reflux condenser, add 100.0 g of 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and mix at room temperature. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, mixed under reflux, and reacted at 80° C. for 6 hours. After the reaction, the organic layer was taken out, washed with 0.2% by mass of ammonium nitrate aqueous solution until the washed water was neutral, and then the solvent and water were distilled off under reduced pressure to obtain a viscous transparent liquid having epoxy groups. Organosiloxane (EPS-1).

As a result of ¹ H-NMR analysis of (EPS-1), an epoxy group-based peak with the same theoretical intensity was obtained near the chemical shift (δ) = 3.2ppm, confirming that no epoxy group was generated during the reaction side effects. (EPS-1) had a Mw of 2200 and an epoxy equivalent of 186 g/mol.

<Synthesis of Compound (A-1-1)>

[Synthesis Example 2]

Compound (A-1-1) was synthesized according to the following synthetic route.

In a 500 mL eggplant flask, 23.6 g of 2,2,6,6-tetramethyl-4-hydroxypiperidine, 15.0 g of succinic anhydride, and 200 mL of pyridine were added, and the reaction was stirred at 80° C. for 9 hours. After completion of the reaction, it was left standing at room temperature for 1 day to precipitate crystals, and the solvent was removed to obtain 37.1 g of white crystals of compound (A-1-1).

<Synthesis of compound having liquid crystal alignment ability>

[Synthesis Example 3]

Compound (b-1) was synthesized according to the following synthetic route.

In a 1L eggplant-shaped flask, add 82g of p-hydroxycinnamic acid, 304g of potassium carbonate and 400mL of N-methyl-2-pyrrolidone, stir at room temperature for 1 hour, add 166g of 1-bromopentane, and stir at 100°C for 5 Hour. Then, the solvent was distilled off under reduced pressure. Add 48g of sodium hydroxide and 400mL of water therein, and reflux for 3 hours to carry out the hydrolysis reaction. After the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was recovered and recrystallized with ethanol to obtain 80 g of white crystals of compound (b-1).

[Synthesis Example 4]

Compound (b-2) was synthesized according to the following synthetic route.

In a 1L eggplant-shaped flask, add 91.3g methyl 4-hydroxybenzoate, 182.4g potassium carbonate and 320mL N-methyl-2-pyrrolidone, stir at room temperature for 1 hour, add 99.7g 1-bromopentane, in Stir at 100°C for 5 hours. After the reaction was completed, reprecipitation was performed with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to perform a hydrolysis reaction. After completion of the reaction, it was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain (104 g) white crystals of compound (b-2'). 104 g of compound (b-2') was put into a reaction container, 1 L of thionyl chloride and 770 µL of N,N-dimethylformamide were added thereto, and stirred at 80°C for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with aqueous sodium bicarbonate, dried over magnesium sulfate, concentrated, and tetrahydrofuran was added to form a solution. Next, in a 5L three-necked flask different from the above, 74g of 4-hydroxycinnamic acid, 138g of potassium carbonate, 4.8g of tetrabutylammonium, 500mL of tetrahydrofuran and 1L of water were added. This aqueous solution was cooled with ice water, and a tetrahydrofuran solution containing a reactant of the above-mentioned compound (b-2') and thionyl chloride was slowly added dropwise, followed by a reaction with stirring for 2 hours. After the reaction was completed, hydrochloric acid was added to the reaction mixture for neutralization, and extracted with ethyl acetate, then the extract was dried with magnesium sulfate, concentrated, and then recrystallized with ethanol to obtain 90 g of compound (b-2). White crystals.

[Synthesis Example 5]

Compound (b-3) was synthesized according to the following synthetic route.

In a 1L eggplant-shaped flask, add 82g of methyl 4-hydroxybenzoate, 166g of potassium carbonate and 400mL of N,N-dimethylacetamide, after stirring at room temperature for 1 hour, add 95g of 4,4,4-trifluoro- 1-iodobutane, stirred at room temperature for 5 hours, and reacted. After the reaction was completed, reprecipitation was performed with water. Next, 32 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 4 hours to perform a hydrolysis reaction. After the reaction was completed, it was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized with ethanol to obtain 80 g of white crystals of compound (b-3'). 46.4 g of compound (b-3') was put into a reaction vessel, 200 mL of thionyl chloride and 0.2 mL of N,N-dimethylformamide were added thereto, and stirred at 80°C for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with aqueous sodium bicarbonate, dried over magnesium sulfate, concentrated, and tetrahydrofuran was added to form a solution. Next, in a 2L three-necked flask different from the above, add 36g of 4-hydroxycinnamic acid, 55g of potassium carbonate, 2.4g of tetrabutylammonium, 200mL of tetrahydrofuran and 400mL of water. This aqueous solution was cooled with ice water, and a tetrahydrofuran solution containing the reaction product of the above-mentioned compound (b-3') and thionyl chloride was slowly added dropwise, followed by a reaction with stirring for 2 hours. After the reaction was completed, hydrochloric acid was added to the reaction mixture for neutralization, and extracted with ethyl acetate, then the extract was dried with magnesium sulfate, concentrated, and then recrystallized with ethanol to obtain 39 g of compound (b-3). White crystals.

[Synthesis Example 6]

Compound (b-4) was synthesized according to the following synthetic route.

13 g of white crystals of compound (b-4) were obtained in the same manner as in Synthesis Example 4, except that 9.91 g of 4-pentyl-trans-cyclohexylcarboxylic acid was used instead of compound (b-2') in Synthesis Example 4.

[Synthesis Example 7]

Compound (b-5) was synthesized according to the following synthetic route.

In a 500mL three-neck flask with a reflux tube, a thermometer and a nitrogen inlet tube, add 31g of compound (b-5'), 0.23g of palladium acetate, 1.2g of tri(o-tolyl)phosphine, 56mL of triethylamine, 8.2mL of acrylic acid and 200mL N,N-dimethylacetamide, and reacted at 120°C for 3 hours under stirring. After the reaction, the reaction mixture was filtered, 1 L of ethyl acetate was added to the obtained solution, and the obtained organic layer was washed twice with dilute hydrochloric acid and three times with water. Then, the organic layer was dried over magnesium sulfate, concentrated to dryness, and recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain 15 g of compound (b-5) crystals.

[Synthesis Example 8]

Compound (b-6) was synthesized according to the following synthetic route.

16 g of compound (b-6) was obtained in the same manner as in Synthesis Example 7 above, except that 36 g of compound (b-6') was used instead of compound (b-5').

[Synthesis Example 9]

Compound (b-7) was synthesized according to the following synthetic route.

In a 200 mL eggplant-shaped flask with a reflux tube, 12 g of decylsuccinic anhydride, 8.2 g of 4-aminocinnamic acid, and 100 mL of acetic acid were added, and reacted under reflux for 2 hours. After the reaction was finished, the reaction mixture was extracted with ethyl acetate, the organic layer was washed with water, and dried with magnesium sulfate, then refined with a silicon column, and further recrystallized with a mixed solvent of ethanol and tetrahydrofuran, thus obtaining 10 g of compound (b- 7) as white crystals (purity: 98.0%).

[Synthesis Example 10]

Except in above-mentioned synthetic example 7, use the compound (b-8 ') represented by 28g following formula to replace compound (b-5 '), operate similarly with synthetic example 7, obtain the compound represented by 14g following formula ( b-8).

[Synthesis Example 11]

Compound (b-9) was synthesized according to the following synthetic route.

In a 500mL three-neck flask with a reflux tube and a nitrogen inlet tube, add 39gβ-cholesterol, 20g succinic anhydride, 1.5g N,N-dimethylaminopyridine, 200mL ethyl acetate and 17mL triethylamine, under reflux React for 8 hours. After the reaction, 200 mL of tetrahydrofuran was added to the reaction mixture, and the obtained organic layer was washed twice with 1N dilute hydrochloric acid and three times with water. After drying over magnesium sulfate, the solvent was removed under reduced pressure, and the resulting solid was recrystallized from ethyl acetate, whereby 38 g of white crystals of compound (b-9) were obtained.

<[A] Synthesis of polyorganosiloxane compound>

[Synthesis Example 12]

In a 200mL three-necked flask, add 10.0g (EPS-1), 69.5g methyl isobutyl ketone, 2.77g compound (A-1-1) (relative to the epoxy group, corresponding to 20 mol%), 4.60g of stearic acid (relative to the epoxy group of polyorganosiloxane (EPS-1), corresponding to 30 mol%), and 1.00g of tetrabutylammonium bromide, It stirred at 100 degreeC for 8 hours, and reacted. After the reaction was completed, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution, and the solution was washed with water 5 times, and then the solvent was distilled off, thus obtaining 15.8 g of [A]polyethylene as a white powder. Organosiloxane compound (S-1).

[Synthesis Example 13 to Synthesis Example 33]

The types and amounts of compounds to be blended were as shown in Table 1, and [A] polyorganosiloxane compounds (S-2) to (S-22) were synthesized in the same manner as in Synthesis Example 12.

In addition, the usage ratio of the compound in Table 1 is mol% with respect to the epoxy group which (EPS-1) has. In addition, Mw of polyorganosiloxanes (S-1) to (S-22) are shown in Table 1 together. In addition, the structures of salicylic acid and 4-diethylaminobenzoic acid are shown below in order.

[Comparative Synthesis Example 1]

In a 200mL three-necked flask, add 10.0g (EPS-1), 58.4g methyl isobutyl ketone, 4.60g stearic acid (relative to the epoxy group that polyorganosiloxane EPS-1 has, equivalent to 30 mol%) and 1.00 g of tetrabutylammonium bromide were stirred at 100° C. for 8 hours to react. After the reaction was completed, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed with water five times, and then the solvent was distilled off, thereby obtaining 12.4 g of polyorganosiloxane as a white powder. (CS-1).

[Comparative synthesis examples 2 to 4]

The types and amounts of compounds to be blended were shown in Table 1, and polyorganosiloxane compounds (CS-2) to (CS-4) were synthesized in the same manner as in Comparative Synthesis Example 1. In addition, Mw of polyorganosiloxanes (CS-1) to (CS-4) are shown in Table 1 together.

<[B] Synthesis of polymer (polyamic acid)>

[Synthesis Example 34]

196g (1.0 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, and 212g (1.0 mole) of 2,2'-dimethyl-4 , 4'-diaminobiphenyl was dissolved in 4050g NMP, and reacted for 3 hours at 40°C to obtain a polyamic acid solution (PA-1) with a solid content concentration of 10% and a solution viscosity of 170mPa·s.

[Synthesis Example 35]

86.3g (0.44 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 96.0g (0.44 mole) of pyromellitic dianhydride as tetracarboxylic dianhydride, and 191.0 g (0.90 moles) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 1490g of NMP, reacted for 4 hours at 40°C, and then further added NMP to obtain a solid concentration of 10%, A polyamic acid solution (PA-2) with a solution viscosity of 43 mPa·s.

<[B] Synthesis of polymer (polyimide)>

[Synthesis Example 36]

20.9g (0.093 moles) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 9.2g (0.085 moles) of p-phenylenediamine and 4.9g (0.009 moles) of diamine ) The compound represented by the following formula (DA) was dissolved in 140g NMP, reacted for 4 hours at 60°C, got a small amount of polyamic acid solution obtained, and added NMP to obtain a solid concentration of 10%, and a solution viscosity of 126mPa·s polyamic acid solution. Next, 325 g of NMP was added to the obtained polyamic acid solution, 7.4 g of pyridine and 9.5 g of acetic anhydride were added, and dehydration and ring closure were performed at 110° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was solvent-substituted with new NMP, and about 210 g of a solution containing 16.1% by weight of polyimide (PI-1) having an imidation rate of about 54% was obtained. A small amount of the obtained polyimide solution was taken, NMP was added to make the solid content concentration 10%, and the measured solution viscosity was 75 mPa·s.

[Synthesis Example 37]

20.0g (0.089 moles) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 6.8g (0.063 moles) of p-phenylenediamine, 3.6g (0.018 moles) of diamine ) 4,4'-diaminodiphenylmethane and 4.7g (0.0090 moles) of the compound represented by the above formula (DA), dissolved in 140g of NMP, reacted at 60°C for 4 hours to obtain a solid content concentration of 20% , The polyamic acid solution whose solution viscosity is 2200mPa·s. Next, 325 g of NMP was added to the obtained polyamic acid solution, 10.5 g of pyridine and 13.6 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110° C. for 4 hours. After the dehydration ring-closing reaction, the solution in the system was solvent-substituted with new NMP to obtain about 160 g of a polyimide (PI-2) solution with an imidization rate of about 65% (solid content concentration: 20%) .

[Synthesis Example 38]

19.2g (0.086 moles) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, and 5.2g (0.034 moles) of diamine as 3,5-diaminobenzoic acid and 25.5 g (0.052 moles) of the diamine represented by the following formula was dissolved in 200g NMP, and reacted for 4 hours at 60°C to obtain a polyamic acid solution whose solid content concentration was 20%, and the solution viscosity was 1450mPa·s. Next, 250 g of NMP was added to the obtained polyamic acid solution, 10.2 g of pyridine and 13.2 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110° C. for 4 hours. After the dehydration ring-closing reaction, the solution in the system was solvent-substituted with new NMP to obtain about 230 g of a solution containing 20% by weight of polyimide (PI-3) with an imidation rate of about 67%.

<[C] Synthesis of other polyorganosiloxane compounds>

[Synthesis Example 39]

In a 200 mL three-neck flask with a condenser, 20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol were added, heated to 60° C. and stirred. An aqueous solution of maleic anhydride obtained by dissolving 0.26 g of maleic anhydride in 10.8 g of water prepared in another 20-mL flask was added thereto, followed by stirring at 60° C. for 4 hours to perform a reaction. After the reaction was completed, the solvent was distilled off from the resulting reaction mixture, 1-ethoxy-2-propanol was added to the residue, and concentrated again to obtain a polyorganosiloxane (PS) with a solid content concentration of 10%. -1) Solution. Mw is 5100.

<Preparation of liquid crystal aligning agent>

[Example 1]

Mix 100 parts by mass of polyorganosiloxane (S-1) and a solution containing polyamic acid (PA-1) equivalent to 1000 parts by mass in terms of polyamic acid (PA-1), and add to it NMP and ethylene glycol mono-n-butyl ether were added to form a solution having a solvent composition of NMP:ethylene glycol mono-n-butyl ether=50:50 (mass ratio) and a solid content concentration of 3.0% by mass. This solution was filtered using the filter of 1 micrometer of pore diameters, and liquid crystal aligning agent (AF-1) was prepared, and this was made into Example 1.

[Examples 2 to 39 and Comparative Examples 1 to 7]

The kind and usage amount of the compounded mixture are respectively shown in Table 2 described later, and the same operation as in Example 1 was carried out to prepare liquid crystal aligning agents (AF-2) to (AF-39) and (CAF-1) to ( CAF-7), these are Examples 2-39 and Comparative Examples 1-7.

<Storage stability>

About each said liquid crystal aligning agent, storage stability was evaluated according to following (method 1) or (method 2). The results are shown in Table 2.

(method 1)

Using the spin coating method, with the rotation number as a variable, the liquid crystal alignment agents (AF-1) ~ (AF-12) and (CAF-1) ~ (CAF-3) are coated on the glass substrate, and then heated at 200 ° C Heating at lower temperature for 60 minutes forms a coating film, and investigates the thickness of the coating film after removing the solvent. number of rotations. Next, some liquid crystal aligning agents were collected and stored at -15°C for 5 weeks. The liquid crystal aligning agent after storage was visually observed, and when precipitation of an insoluble matter was observed, it evaluated as storage stability "poor". When no insoluble matter was observed after storage for 5 weeks, further pass the spin coating method, and the film thickness before storage was number of rotations, the stored liquid crystal aligning agent was coated on a glass substrate, and then heated at 200° C. for 60 minutes to form a coating film, and the film thickness after removing the solvent was measured. When the film thickness is given by When the change was 10% or more, the storage stability was evaluated as "poor", and when the change in film thickness was less than 10%, the storage stability was evaluated as "good". In addition, the measurement of the film thickness of the said coating film was performed using the stylus-type step film thickness meter manufactured by KLA-Tencor Corporation.

(method 2)

Liquid crystal aligning agent (AF-13) - (AF-39) and (CAF-4) - (CAF-7) were stored at -15 degreeC for 6 months. Before and after storage, the viscosity was measured at 25° C. using an E-type viscometer. When the change rate of the solution viscosity before and after storage was less than 10%, the storage stability was evaluated as "good", and when it was 10% or more, the storage stability was evaluated as "poor".

[Table 2]

<Manufacturing of liquid crystal display elements>

[Example 40]

Use a spin coater to coat the liquid crystal aligning agent (AF-1) on the transparent electrode face of the glass substrate with the transparent electrode formed by the ITO film, and pre-bake it on a hot plate at 80 ° C for 1 minute, and then carry out The solvent was removed by heating at 200° C. for 1 hour in an oven replaced with nitrogen, and a coating film having a film thickness of 0.1 μm was formed. This operation was repeated to produce a pair (two sheets) of substrates having a liquid crystal aligning film. By screen printing, after the epoxy resin adhesive that added the alumina balls with a diameter of 5.5 μm was coated on the outer periphery of the surface with the liquid crystal alignment film in the above-mentioned one substrate, the liquid crystal alignment film surfaces of the pair of substrates were overlapped and Press-bond and heat at 150°C for 1 hour to thermally cure the adhesive. Next, after filling the gap between the substrates with nematic liquid crystal (Melk Corporation, MLC-6608) from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy-based adhesive. In addition, in order to eliminate the flow orientation during liquid crystal injection, the It was heated at 150°C for 10 minutes and then slowly cooled to room temperature. Furthermore, polarizing plates were bonded to both outer surfaces of the substrate so that the polarization directions of the two polarizing plates were perpendicular to each other, thereby producing a vertical alignment type liquid crystal display element, which was referred to as Example 40.

[Examples 41-51, Comparative Examples 8-10]

Use liquid crystal alignment agent (AF-2)～(AF-12) and (CAF-1)～(CAF-3), operate similarly with embodiment 40, manufacture liquid crystal display element, they are as embodiment 41～51, comparative Example 8-10.

[Example 52]

Use a spin coater to coat the liquid crystal aligning agent (AF-13) on the transparent electrode face of the glass substrate with the transparent electrode formed by the ITO film, and pre-bake it on a hot plate at 80 ° C for 1 minute, and then carry out The solvent was removed by heating at 200° C. for 1 hour in an oven replaced with nitrogen, and a coating film having a film thickness of 0.1 μm was formed. Next, using a Hg-Xe lamp and a Glan-Taylor prism, the surface of the coating film was irradiated with 200 J/ ^m2 of polarized ultraviolet light containing a bright line with a wavelength of 313 nm from a direction inclined 40° relative to the normal line of the substrate to form a liquid crystal alignment film. Repeat the same operation to make a pair (two) of substrates with liquid crystal alignment films. After screen printing, the outer periphery of the surface with the liquid crystal alignment film in the above-mentioned one substrate was coated with an epoxy resin adhesive that added alumina balls with a diameter of 5.5 μm, and the liquid crystal alignment film surfaces of the pair of substrates faced each other. And carry out pressure bonding, make the projection direction of the ultraviolet optical axis of each substrate on the substrate surface be antiparallel, and heat at 150° C. for 1 hour, so that the adhesive is thermally cured. Next, after the gap between the substrates was filled with nematic liquid crystal (MLC-6608) from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy-based adhesive. In addition, in order to eliminate the flow orientation at the time of liquid crystal injection, it was heated at 150° C. for 10 minutes and then slowly cooled to room temperature. Next, stick polarizing plates on the outer sides of the substrate, make the polarization directions of the polarizing plates perpendicular to each other, and make the projection direction of the ultraviolet optical axis of the liquid crystal alignment film on the substrate surface be at an angle of 45°, thereby producing a vertical alignment A liquid crystal display element of the type is used as Example 52.

[Examples 53-78, Comparative Examples 11-14]

Use liquid crystal aligning agent (AF-13)～(AF-39) and (CAF-4)～(CAF-7), operate similarly with embodiment 52, manufacture liquid crystal display element, they are as embodiment 53～78, comparative Examples 11-14.

Table 3 shows the results of the following evaluations on the liquid crystal display elements of Examples 40 to 78 and Comparative Examples 8 to 14.

<Liquid crystal orientation>

Whether or not there is an abnormal region in which light and dark changes when a voltage of 5 V is turned on and off (applied and released) to the liquid crystal display element produced above is observed visually. When the cell light leakage was not observed when the voltage was turned off, and when the voltage was applied, the cell driving region showed white, and the liquid crystal orientation was "good" when there was no light leakage in other regions. When the cell light leakage is observed when the voltage is turned off, or light leakage is observed in a region other than the cell driving region when the voltage is turned on, the alignment of the liquid crystal is "bad".

<Voltage retention>

To the liquid crystal display element produced above, a voltage of 5 V was applied for an application time of 60 microseconds at an interval of 167 milliseconds at an ambient temperature of 60° C., and then the voltage retention rate after release of the application to 167 milliseconds was measured. As the measurement device, VHR-1 manufactured by Toyo Technica Co., Ltd. was used. When the voltage retention rate was 97% or more, the voltage retention rate was evaluated as "good".

<Lightfastness>

The initial voltage retention was measured for the liquid crystal display element manufactured above under the same conditions as the evaluation of the voltage retention. Then, it was placed at a distance of 5 cm under a 100 W type white fluorescent lamp, and after being irradiated with light for 500 hours, the voltage retention rate was again measured under the same conditions as above. When the reduction rate of the voltage retention rate compared with the initial value was 1% or less, the light resistance was evaluated as "A", when it exceeded 1% and was 2% or less, the light resistance was evaluated as "B", and when it exceeded 2% %, it was evaluated as light fastness "C".

[table 3]

As is clear from the results in Tables 2 and 3, the storage stability of the liquid crystal aligning agent of the present invention is excellent. Furthermore, it has also been found that the liquid crystal aligning film formed from this liquid crystal aligning agent sufficiently satisfies the liquid crystal orientation, voltage retention, and light resistance required practically as a liquid crystal display element.

Industrial Applicability

According to the present invention, it is possible to provide a liquid crystal alignment film that fully satisfies the characteristics of liquid crystal orientation, voltage retention and light resistance as a liquid crystal display element in practical aspects; the formation method of the liquid crystal alignment film; suitable as a liquid crystal alignment film The storage stability of a forming material is excellent, and the liquid crystal aligning agent which can form a liquid crystal aligning film by the photo-alignment method; and the liquid crystal display element equipped with a liquid crystal aligning film. The liquid crystal display element of this application equipped with the liquid crystal aligning film formed by this liquid crystal aligning agent can be used suitably, for example in a watch, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, a portable information terminal, a digital camera, etc. , mobile phones, various monitors, LCD TVs and other display devices.

Claims (15)

1. a liquid crystal aligning agent, it contains [A] and has the polyorganosiloxane compounds of aniline structure.

2. liquid crystal aligning agent as claimed in claim 1, wherein above-mentioned aniline structure is represented by following formula (A-3 '),

Formula (A-3 ') in, R ⁷and R ⁸the alkyl that is 1～16 for carbonatoms independently of one another, and, abovementioned alkyl in skeletal chain, can have Sauerstoffatom, sulphur atom, carbonyl, ester group or by the two or more groups that combine in them, the represented connecting key of * is connected with main chain or the side chain of organopolysiloxane skeleton.

3. liquid crystal aligning agent as claimed in claim 1, wherein [A] polyorganosiloxane compounds contains: come from the group that the condenses of organopolysiloxane, its hydrolyzate and this hydrolyzate forms and select at least one part, this organopolysiloxane has the represented structural unit of following formula (1); Come from the part of the compound represented by following formula (A-3),

In formula (1), X ^afor thering is 1 valency organic group of epoxy group(ing), Y ^afor hydroxyl, the carbonatoms alkoxyl group that is 1～10, alkyl that carbonatoms is 1～20 or the carbonatoms aryl that is 6～20,

In formula (A-3), R ⁷and R ⁸with above-mentioned formula (A-3 ') synonym,

Y is the alkane 2 basis that singly-bound, carbonatoms are 1～16, and above-mentioned alkane 2 basis in structure, can have Sauerstoffatom, sulphur atom, carbonyl, ester group, amide group or by the two or more groups that combine in them, Z is carboxyl or hydroxyl.

4. liquid crystal aligning agent as claimed in claim 3, the wherein X in above-mentioned formula (1) ^afor following formula (X ^a-1) or formula (X ^a-2) represented group,

Formula (X ^a-1) and formula (X ^a-2) in, the integer that s is 0～3, the integer that t is 1～6, the integer that u is 0～2, the integer that v is 0～6, the represented connecting key of * is connected with Siliciumatom.

5. liquid crystal aligning agent as claimed in claim 4, wherein above-mentioned formula (X ^a-1) or formula (X ^a-2) represented group, is respectively following formula (X ^a-1-1) or (X ^a-2-1) represented group,

Formula (X ^a-1-1) and formula (X ^a-2-1) in, the represented connecting key of * is connected with Siliciumatom.

6. the liquid crystal aligning agent as described in claim 1～5 any one, wherein [A] polyorganosiloxane compounds comprises the structure with liquid crystal aligning energy.

7. liquid crystal aligning agent as claimed in claim 6, the wherein above-mentioned structure with liquid crystal aligning energy, the organic group that to have by the carbonatoms with steroid skeleton be 17～51, carbonatoms is 2～20 alkyl, carbonatoms is 1～20 fluoro-alkyl, cyclohexyl, there is carbonatoms and is the alkoxy aryl of 2～20 alkyl, there is carbonatoms and is the alkyl-cyclohexyl of 1～20 alkyl, having carbonatoms and be the fluoro-alkyl cyclohexyl of 1～20 fluoro-alkyl and having carbonatoms is at least one group of selecting in the group that forms of the fluoroalkyl cyclohexyl of 1～20 fluoroalkyl.

8. liquid crystal aligning agent as claimed in claim 6, wherein has the structure of above-mentioned liquid crystal aligning energy by following formula (B-1) expression,

In formula (B-1), the integer that m is 0～4.

9. the liquid crystal aligning agent as described in claim 1～5 any one, it further contains at least one polymkeric substance of selecting in the group that [B] be made up of polyamic acid and polyimide.

10. the liquid crystal aligning agent as described in claim 1～5 any one, it further contains [C] and has the polyorganosiloxane compounds of the represented structural unit of following formula (2),

In formula (2), X ^bfor hydroxyl, halogen atom, the carbonatoms alkyl that is 1～20, alkoxyl group that carbonatoms is 1～6 or carbonatoms be 6～20 aryl, Y ^bfor hydroxyl or the carbonatoms alkoxyl group that is 1～10.

The formation method of 11. 1 kinds of liquid crystal orientation films, has:

(1) claim 8, claim 9 or liquid crystal aligning agent claimed in claim 10 are coated on substrate, form the operation of film, and

(2) at least a portion of film operation (1) being formed is irradiated the operation of radioactive rays.

12. 1 kinds of liquid crystal orientation films that formed by the liquid crystal aligning agent described in claim 1～10 any one.

13. 1 kinds possess the liquid crystal display device of the liquid crystal orientation film described in claim 12.

14. 1 kinds of polyorganosiloxane compounds, it has aniline structure.

15. polyorganosiloxane compounds as claimed in claim 14, wherein above-mentioned aniline structure is by the represented structure of following formula (A-3 '),

Formula (A-3 ') in, R ⁷and R ⁸the alkyl that is 1～16 for carbonatoms independently of one another, and, abovementioned alkyl in skeletal chain, can have Sauerstoffatom, sulphur atom, carbonyl, ester group or by the two or more groups that combine in them, the represented connecting key of * is connected with main chain or the side chain of organopolysiloxane skeleton.