KR101972822B1 - Liquid crystal aligning agent, liquid crystal alignment film, polymer, compound, liquid crystal display device, and manufacturing method for the liquid crystal display device - Google Patents

Abstract

(식 중, A¹은, 비페닐기, 바이사이클로헥실렌기, 나프틸렌기 등 중 어느 것이고; Y는, 단결합, -O-, ＊²-COO-, ＊²-OCO-, -OCOO- 등 중 어느 것이고; L은, 단결합, 탄소수 1∼20의 알칸디일기 등 중 어느 것이고; a 및 b는, 각각 독립적으로 0 또는 1이고, a＝b＝0이 되는 일은 없고; Z는, 중합성 불포화 결합을 갖는 기임).A liquid crystal aligning agent capable of forming a liquid crystal alignment film exhibiting a good pretilt angle at a low light irradiation dose and further capable of obtaining a liquid crystal display element having a sufficiently high response speed of liquid crystal molecules.
(Solution) The liquid crystal aligning agent contains a polymer having a group represented by the following formula (1):

(Wherein, A ¹ is a biphenyl group, a bi-cyclohexylene group, a naphthylene group, such as any of will; Y is a single bond, -O-, -COO- * ^{2, 2} * -OCO-, -OCOO- A and b each independently represent 0 or 1, and a = b = 0; Z represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, A group having a polymerizable unsaturated bond).

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a polymer, a compound, a liquid crystal display device and a manufacturing method of a liquid crystal display device }

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a method for producing the liquid crystal display element, and more particularly relates to a liquid crystal aligning agent which can be suitably used for producing a vertically aligned liquid crystal display element.

Conventionally, various driving methods have been developed as liquid crystal display devices, which have different electrode structures and physical properties of liquid crystal molecules to be used. For example, TN type, STN type, VA type, in-plane switching type (IPS type) Various liquid crystal display devices are known. These liquid crystal display devices have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of the liquid crystal alignment film, for example, polyamic acid, polyimide, polyester, polyorganosiloxane and the like are known.

Recently, as a new technique for controlling the orientation of liquid crystal molecules in liquid crystal display devices, a PSA (Polymer Sustained Aligment) technology has been proposed (see, for example, Patent Document 1). This PSA technique is a method of polymerizing a polymerizable component by incorporating a polymerizable component that polymerizes by light irradiation into a liquid crystal layer of a liquid crystal cell and irradiating the liquid crystal cell with a liquid crystal molecule while tilting the liquid crystal molecule by applying a voltage This is a technique for controlling the molecular orientation of liquid crystal molecules.

However, when the orientation of the liquid crystal molecules is controlled by the PSA technique, it is necessary to perform light irradiation at a relatively high irradiation dose. As a result, problems such as decomposition of liquid crystal molecules and deterioration of the performance of the liquid crystal alignment film occur. As a result, display unevenness of the liquid crystal display element occurs, and the long-term reliability of the panel is inferior. On the other hand, when the light irradiation amount is reduced, there is a problem that the response speed of the liquid crystal molecules with respect to the voltage change becomes slow in the formed liquid crystal display element. In view of this, conventionally, a desired pretilt angle characteristic can be imparted to a coating film formed using a liquid crystal aligning agent with as little light irradiation as possible, and at the same time, the response speed of liquid crystal molecules A technique for obtaining a fast liquid crystal display element has been proposed (for example, see Patent Document 2). In Patent Document 2, a liquid crystal aligning film is formed on a substrate by using a liquid crystal aligning agent containing a polyorganosiloxane having a (meth) acryloyl group as a polymer component and a polyamic acid or polyimide, Discloses that a liquid crystal display element is manufactured by forming a liquid crystal cell using light and irradiating the liquid crystal cell with light while applying a voltage between the substrates.

Japanese Patent Application Laid-Open No. 2003-149647 Japanese Laid-Open Patent Publication No. 2011-118358

However, in recent years, liquid crystal display devices are used not only for display terminals such as personal computers, but also for various purposes such as liquid crystal televisions, car navigation systems, mobile phones, smart phones, and information displays. With this increase in versatility, the demand for higher performance of the liquid crystal display element is further increased, and as the liquid crystal aligning agent, it is required to further improve the display quality of the liquid crystal display element. For example, in the technique of controlling the alignment of the liquid crystal molecules by light irradiation as in the method described in the above-mentioned Patent Document 2, the pretilt angle characteristics can be imparted to the coating film as the liquid crystal alignment film with a smaller amount of light irradiation , It is required that a liquid crystal display element having a sufficiently high response speed of liquid crystal molecules with respect to a voltage change can be manufactured.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a liquid crystal display device in which, when a liquid crystal cell is manufactured by irradiating a liquid crystal cell with a voltage applied between substrates after formation of the liquid crystal cell, And it is a main object of the present invention to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film capable of manifesting each property and capable of providing a liquid crystal display element with a sufficiently high response speed of liquid crystal molecules with respect to a voltage change.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to achieve the above-mentioned problems of the prior art, and as a result, they found that the above problems can be solved by including a polymer having a specific structure in a liquid crystal aligning agent. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method of manufacturing liquid crystal display element.

In one aspect, the present invention provides a liquid crystal aligning agent containing a polymer (P) having a group represented by the following formula (1): "

[In the formula (1), A ¹ represents a group represented by the following formula (1a):

(In the formula (1a), A ² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a piperidine-1,4-diyl group, a piperidine- A pyrimidine-2,5-diyl group, a pyridazine-3,6-diyl group, a pyrazine-2,5-diyl group, or a pyridine-2,5- and 2,5-diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, - (CH 2) 2 - or -C≡C- a, m is an integer from 0 to 2 Provided that when m is 1 or 2, plural A ^{2 s} may be the same or different, and when m is 2, plural X ^{4 s} may be the same or different and two "* ¹ " s Hand)

, A naphthylene group, a tetrahydronaphthalene diyl group, or a decahydronaphthalenediyl group; Y is a single bond, -O-, * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N _{3) -, -N (C 2} H 5) -, -Si (CH 3) 2 -, -S-, * 2 -COS-, * 2 -SCO- or -C≡C- (However, "* ² Quot; represents a bond with A < ¹ >); L is a divalent group in which at least one hydrogen atom of a single bond, an alkanediyl group having 1 to 20 carbon atoms or an alkanediyl group having 1 to 20 carbon atoms is substituted with a halogen atom, and the carbon- O-, -S-, and -NH-, and a part of the carbon-carbon bond may be a double bond or a triple bond; a and b are each independently 0 or 1; Provided that a = b = 0; When a = b = 1, plural Y and L may be the same or different; Z is a group represented by the following formula (2a) or (2b):

(In the formulas (2a) and (2b), X ¹ represents a hydrogen atom or a methyl group; "* ³ " represents a bond)

Lt; / RTI > "*" Indicates a combined hand).

The liquid crystal aligning agent includes, as a polymer component, a polymer having a group represented by the formula (1). According to this liquid crystal aligning agent, when a liquid crystal cell is formed by using a substrate coated with the liquid crystal aligning agent and light is irradiated to the liquid crystal cell in a state where a voltage is applied between the substrates, It is possible to impart a good pretilt angular characteristic to the coating film as the liquid crystal alignment film at a small light irradiation amount (for example, at a light irradiation amount of about 5,000 J / m 2), and to provide a liquid crystal display element having a sufficiently high response speed of liquid crystal molecules Can be obtained.

According to another aspect of the present invention, there is provided a liquid crystal display device comprising a first step of coating a liquid crystal aligning agent of the present invention on a conductive film of a pair of substrates each having a conductive film and then heating the same to form a coated film, A second step of arranging a pair of substrates provided with a pair of substrates facing each other with the liquid crystal molecules facing each other so as to oppose each other to form a liquid crystal cell; And a third step of irradiating light to the liquid crystal display element.

In addition, another aspect of the present invention provides a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention and a liquid crystal display element comprising the liquid crystal alignment film. In another aspect of the present invention, there is provided a polymer (P) having a group represented by the formula (1) and a carboxylic acid having a group represented by the formula (1).

1 is a plan view showing a pattern of a transparent electrode patterned in a slit shape.

(Mode for carrying out the invention)

Hereinafter, each component contained in the liquid crystal aligning agent of the present invention and other components arbitrarily blended as required will be described.

≪ Polymer (P) >

The liquid crystal aligning agent of the present invention comprises a polymer component and contains, as the polymer component, at least a polymer (P) having a group represented by the following formula (1).

In the above formula (1), A ¹ is a divalent group represented by the following formula (1a), a naphthylene group, a tetrahydronaphthalenediyl group, or a decahydronaphthalenediyl group:

(In the formula (1a), A ² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a piperidine-1,4-diyl group, a piperidine- A pyrimidine-2,5-diyl group, a pyridazine-3,6-diyl group, a pyrazine-2,5-diyl group, or a pyridine-2,5- and 2,5-diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, - (CH 2) 2 - or -C≡C- a, m is an integer from 0 to 2 Provided that when m is 1 or 2, plural A ^{2 s} may be the same or different, and when m is 2, plural X ^{4 s} may be the same or different and two "* ¹ " s Hand).

Examples of the divalent group represented by the formula (1a) include a 1,4-phenylene group, a 1,4-cyclohexylene group, a piperidine-1,4-diyl group, a piperidine- A pyrimidine-2,5-diyl group, a pyridazine-3,6-diyl group, a pyrazine-2,5-di A divalent group formed by connecting one to three of at least one member selected from the group consisting of a pyridine-2,5-diyl group and a bond between A ² and A ² , -O-, -COO-, - OCO-, - (CH ₂ ) ₂ - or -C≡C-, and the like.

m is preferably 1 or 2. When m is 1 or 2, it is preferable that X ⁴ is a single bond. The two "* ¹ " s in the formula (1a) may be bonded to any of two Ys in the formula (1a).

A ² is preferably a 1,4-phenylene group or a 1,4-cyclohexylene group. Specific examples of the bivalent group represented by the above formula (1a) include biphenylene group, bicyclohexylene group, terphenylene group (-C ₆ H ₄ -C ₆ H ₄ -C ₆ H ₄ -) and the following formula (1a-1) to (1a-6), and the like.

Y is a single bond, -O-, * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N _{3) -, -N (C 2} H 5) -, -Si (CH 3) 2 -, -S-, * 2 -COS-, * 2 -SCO- or -C≡C- (However, "* ² Quot; represents a binding hand with A &^lt; ¹ >). Among them, a single bond, -O-, * ² -COO-, * ² -OCO-, -OCOO- or -C≡C- is preferable, and -O-, * ² -COO-, * ² -OCO - or -C? C-.

L is a divalent group in which at least one hydrogen atom of a single bond, an alkanediyl group having 1 to 20 carbon atoms or an alkanediyl group having 1 to 20 carbon atoms is substituted with a halogen atom, and the carbon- O-, -S-, and -NH-, and a part of the carbon-carbon bond may be a double bond or a triple bond. Examples of the alkanediyl group having 1 to 20 carbon atoms in L include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, A butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, Diyl group, a decanyl-1,10-diyl group, a dodecyl-1,12-diyl group, a tetradecyl-1,14-diyl group, a hexadecyl-1,16-diyl group, , An 18-diyl group, an icosyl-1, 20-diyl group, and the like, and they may be linear or branched. However, it is preferably linear in view of liquid crystal alignability. When L is a group in which the hydrogen atom of the above-mentioned alkanediyl group is substituted with a halogen atom, the halogen atom is preferably a chlorine atom or a fluorine atom, more preferably a fluorine atom.

L may be a group containing at least one of -O-, -S-, and -NH- in the carbon-carbon bond of the alkanediyl group, and may be, for example, - (CH ₂ ) _s - X ³ - (CH ₂ ) _t - (wherein X ³ is -O-, -S- or -NH-, s and t are an integer of 1 or more satisfying s + t? 20) ^{_{2) c -X 3 - (CH}} 2) d -X 3 - (CH 2) e - "(where, X ³ are each independently -O-, and -S-, or -NH-, c, d, and e is an integer of 1 or more satisfying c + d + e? 20). In addition, L may be a group in which a part of the carbon-carbon bond of the alkanediyl group is a double bond or a triple bond, and examples thereof include a group of a propan-1-en-1,3-diyl group, 1,5-diyl group, hex-1-en-1, 6-diyl group and the like.

The number of carbon atoms is preferably from 2 to 20, and more preferably from 3 to 20 carbon atoms, from the viewpoint that the response speed of liquid crystal molecules can be made faster. Further, L is preferably from 2 to 8 carbon atoms, more preferably from 2 to 4 carbon atoms, from the viewpoint of making the pretilt angle stability better.

a and b are each independently 0 or 1, and a = b = 0. When a = b = 1, a plurality of Y and L may be the same or different. Preferably, a combination of a = 1 and b = 0, or a combination of a = 0 and b = 1, more preferably a combination of a = 0 and b = 1. When the polymer (P) is a group represented by the above formula (1), L is a relatively short chain having 2 to 4 carbon atoms, and a group represented by the formula L is a relatively long chain having 8 to 20 carbon atoms, the pretilt angle stability can be further improved, which is preferable.

Z is a group represented by the following formula (2a) or the following formula (2b);

(Formula (2a), formula (2b) of the, X ¹ is a hydrogen atom or a methyl group; "* ^3" represents a bonding hand).

Z is preferably a group represented by the above formula (2a).

When A ¹ is a naphthylene group, a tetrahydronaphthalenediyl group or a decahydronaphthalenediyl group, the bonding position of the group "Z- (LY) _a -" bonded to A ¹ and the group "- (YL) _b - For example, 1,3-position, 1,4-position, 1,5-position, 1,6-position, 1,7-position, 2,6-position, 2,7- Among them, 1,5-position or 2,6-position is preferable.

Specific preferred examples of the group represented by the formula (1) include, for example, the following groups:

(Where " * " represents a combined hand).

When the liquid crystal aligning agent of the present invention is used in the production of vertically aligned liquid crystal display elements, the polymer (P) may have a liquid crystal aligning group in order to impart good vertical alignment to the formed coating film. Examples of such vertically aligning groups include an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 40 carbon atoms, an alkoxy group having 4 to 40 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, .

Examples of the alkyl group include an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, a n-decyl group, a n-dodecyl group, Practical skills; Examples of the fluoroalkyl group include a trifluoromethylpropyl group, a trifluoromethylbutyl group, a trifluoromethylhexyl group, a trifluoromethyldecyl group, a pentafluoroethylpropyl group, a pentafluoroethylbutyl group , Pentafluoroethyloctyl group and the like; Examples of the alkoxy group include a butoxy group, a pentyloxy group, a hexyloxy group, and an octyloxy group;

Examples of the group having a steroid skeleton include a cholestanyl group, a cholestenyl group, a lanostanyl group and the like; Examples of the group having a polycyclic structure include a group consisting of 4,4'-biphenylene group, 4,4'-bicyclohexylene group and groups represented by each of the above formulas (1a-1) to (1a-6) And the like; Respectively.

Further, the polymer (P) may have a group having a polymerizable unsaturated bond separately from the group represented by the formula (1). By having this group, stability of the pretilt angle of the liquid crystal display element can be improved. The group having such a polymerizable unsaturated bond preferably contains a (meth) acryloyl group, and specifically includes, for example, a (meth) acryloyloxy group and a (meth) acryloyloxypropyl group. have. Also, in the present specification, (meth) acryloyl represents acryloyl and methacryloyl.

The main chain skeleton of the polymer (P) is not particularly limited, and examples thereof include a polyorganosiloxane skeleton, a polyester skeleton, a polyamic acid skeleton, and a polyimide skeleton. Among them, a polyorganosiloxane skeleton is preferable. That is, the liquid crystal aligning agent of the present invention preferably contains, as a polymer component, a polyorganosiloxane having a group represented by the formula (1) (hereinafter also referred to as "specific polyorganosiloxane").

≪ Specific polyorganosiloxane >

The above-mentioned specific polyorganosiloxane can be produced by appropriately combining the methods of organic chemistry. As an example thereof, for example,

(I) a method in which a hydrolyzable silane compound (a1) having a group represented by the formula (1) or a mixture of the silane compound (a1) and another silane compound is heated in an alcohol solvent under oxalic acid catalyst;

(Hereinafter referred to as " epoxy group-containing polyorganosiloxane ") obtained by hydrolyzing and condensing a hydrolyzable silane compound (a2) having an epoxy group (II) or a mixture of the silane compound (a2) And a carboxylic acid (AC) having a group represented by the formula (1);

(III) a method of hydrolyzing and condensing a hydrolyzable silane compound (a1) having a group represented by the formula (1) or a mixture of the silane compound (a1) and other silane compounds; And the like.

[About method (I)]

[Silane compound (a1)]

The silane compound (a1) includes, for example, a compound represented by the following formula (a-1), which has at least one group represented by the formula (1)

(In the formula (a-1), each X is independently a halogen atom, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, provided that at least 2 of X 3 A halogen atom or an alkoxy group having 1 to 4 carbon atoms; W ¹ represents a single bond, an oxygen atom, -OR ⁵ - * or -C≡CR ⁵ - * (wherein R ⁵ represents a hydrogen atom of a phenylene group or a phenylene group A ¹ , Y, L, Z, a, and b are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms, (1)).

Examples of the halogen atom for X in the formula (a-1) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like; Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like; Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group; Respectively. X is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, from the viewpoint of reactivity.

The phenylene group of W ¹ and R ⁵ is preferably a 1,4-phenylene group.

As for A ¹ , Y, L, Z, a and b in the formula (a1), the description in the group represented by the formula (1) can be respectively applied.

Preferable specific examples of such silane compound (a1) include compounds represented by each of the following formulas (a1-1) to (a1-33). Such a silane compound (a1) can be synthesized by appropriately combining organic chemical methods.

(Wherein Me represents a methyl group and Et represents an ethyl group).

Hereinafter, the compounds represented by each of the above formulas (a1-1) to (a1-33) are also referred to as silane compounds (a1-1) to (a1-33), respectively.

[Other silane compounds]

In the synthesis of the specific polyorganosiloxane by the method (I), the silane compound (a1) may be used alone, but other silane compounds other than the silane compound (a1) may be used in combination. Examples of the other silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hydrolyzable silane compound having a vertically aligning group (Hereafter referred to as an aromatic group-containing silane compound), a silane compound having a polymerizable unsaturated bond (excluding those corresponding to the silane compound (a1)), a hydrolyzable silane compound having an epoxy group Silane compound), and the like.

Examples of the above-mentioned oriented group-containing silane compound include hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltri Ethoxysilane, trifluoromethylhexyltriethoxysilane, octyloxytrimethoxysilane, and the like. The polyorganosiloxane having a group represented by the above formula (1) and a vertically aligning group can be produced by using these oriented group-containing silane compounds in the synthesis of a specific polyorganosiloxane.

Further, by using a silane compound having a polymerizable unsaturated bond as the other silane compound, it is possible to enhance the pretilt angle stability. Examples of the silane compound include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane and the like (Meth) acryloyl group can be preferably used.

Specific examples of the epoxy group-containing silane compound include a silane compound having a group represented by the following formula (a2-1) or (a2-2), for example:

(In the formula (a2-1), Z ¹ is a single bond or an oxygen atom, h is an integer of 1 to 3, and i is an integer of 0 to 6, provided that when i is 0, Z ¹ (A2-2), j is an integer of 1 to 6, and " * " represents a bonding bond with a silicon atom.

Specific examples of the epoxy group-containing silane compound include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Of these, at least one of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane can be particularly preferably used.

The above-mentioned other silane compounds may be used singly or in combination of two or more.

In the synthesis of the specific polyorganosiloxane, the use ratio of the silane compound (a1) is preferably 5 mol% or more, more preferably 10 to 70 mol%, based on the total amount of the silane compound used in the synthesis , And more preferably from 20 to 60 mol%.

In the above method (I), oxalic acid is added to the alcohol in advance to prepare an alcoholic solution of oxalic acid, and the solution and the silane compound are mixed and heated to obtain a solution containing the objective polyorganosiloxane.

Examples of the alcohol used in the reaction include methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and the like. .

The use ratio of the alcohol in the reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound used in the reaction. The amount of oxalic acid to be used in the reaction is preferably 0.2 to 2 mol per 1 mol of the total alkoxy groups of the silane compound. The heating temperature is preferably 50 to 180 DEG C, and the heating time can be, for example, several tens of minutes to several tens of hours.

Thus, a reaction solution containing a specific polyorganosiloxane is obtained. The reaction solution may be directly supplied to the preparation of a liquid crystal aligning agent, or may be provided in the preparation of a liquid crystal aligning agent after concentration or dilution of the reaction solution, if necessary. When the specific polyorganosiloxane obtained by the above reaction has an epoxy group, it is preferable that the specific polyorganosiloxane (the epoxy group-containing polyorganosiloxane having a group represented by the above formula (1)) further has the above-mentioned vertical orientation Group may be reacted. By this reaction, it is possible to introduce a vertically orienting group into a specific polyorganosiloxane.

Specific examples of the carbonic acid having such a vertically aligning group include long chain fatty acids such as caproic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid and stearic acid; Benzoic acid having a long chain alkyl group such as 4-n-hexylbenzoic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexadecylbenzoic acid and 4-stearylbenzoic acid; 4-n-octyloxybenzoic acid, 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, Benzoic acid having a long chain alkoxy group; Cholestanyloxybenzoic acid, cholestenyloxybenzoic acid, cholestenyloxybenzoic acid, lanostanyloxybenzoic acid, cholestanyloxycarbonylbenzoic acid, cholestenyloxycarbonylbenzoic acid, lanostannyloxycarbonylbenzoic acid, succinic acid-5? Benzoic acid having a steroid skeleton such as succinic acid -5? -Cholesten-3-yl, succinic acid-5? -Lanosan-3-yl; Benzoic acid, 4- (4-pentyl-cyclohexyl) benzoic acid, 4- (4-pentyl-cyclohexyl) Heptyl-bicyclohexyl-4-carbonic acid, 4'-pentyl-biphenyl-4-carboxylic acid, 4'-hexyl-biphenyl- 4-carboxylic acid, 4- (4-pentyl-bicyclohexyl-4-yl) benzoic acid, 4- (4-hexyl- Benzoic acid containing a polycyclic structure such as 4- (4-heptyl-bicyclohexyl-4-yl) benzoic acid and 6- (4'-cyanobiphenyl-4-yloxy) hexanoic acid; Carbonic acid containing a fluoroalkyl group such as 6,6,6-trifluorohexanoic acid and 4- (4,4,4-trifluorobutyl) benzoic acid; And the like. The above-mentioned carbonic acid having a vertically-oriented group may be used singly or in combination of two or more kinds.

In the reaction of the specific polyorganosiloxane with the carbonic acid, the carbonic acid having the vertically-oriented group may be used alone, but other carbonic acid other than the carbonic acid may be used in combination. Specific examples of such other carbonic acids include formic acid, acetic acid, propionic acid, benzoic acid, and methylbenzoic acid.

Details of the reaction between a specific polyorganosiloxane having an epoxy group and a carboxylic acid will be described in the following method (II).

[About method (II)]

Examples of the silane compound (a2) used for synthesizing the epoxy group-containing polyorganosiloxane in the method (II) include the compounds exemplified as the epoxy group-containing silane compounds in the description of the method (I) have.

In the synthesis of the epoxy group-containing polyorganosiloxane, the silane compound (a2) may be used singly or other silane compounds other than the silane compound (a2) may be used in combination. Examples of the other silane compounds include the compounds exemplified as " other silane compounds " in the description of the above method (I). As other silane compounds, it is preferable to use silane compounds having polymerizable unsaturated bonds in order to increase the pretilt angle stability. For example, the silane compounds (a1), 3- (meth) acryloyl (Meth) acryloyloxypropyltriethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, and the like can be given. Among them, it is preferable to use a silane compound having a (meth) acryloyl group.

[Hydrolysis and condensation reaction of silane compound]

The hydrolysis-condensation reaction of the silane compound can be carried out by reacting one or more silane compounds as described above with water, preferably in the presence of a suitable catalyst and an organic solvent. Here, the ratio of the silane compound (a2) used in the synthesis is preferably 70 mol% or more, more preferably 80 mol% or more, and 90 mol% or more based on the total amount of the silane compound . In the hydrolysis-condensation reaction, the use ratio of water is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, per 1 mole of the silane compound (total amount).

Examples of the catalyst include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. Specific examples of these catalysts include acids such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins and various Lewis acids;

As the alkali metal compound, for example, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like;

As organic bases, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene; Quaternary organic amines such as tetramethylammonium hydroxide; Respectively. As the organic base, a tertiary organic amine or a quaternary organic amine is preferable.

Among these catalysts, an alkali metal compound or an organic base is preferred among the above catalysts in that side reactions such as ring-opening of the epoxy group can be suppressed, the rate of hydrolysis and condensation can be increased, Organic bases are preferred.

The amount of the organic base to be used differs depending on the kind of the organic base, the reaction conditions such as the temperature, and the like, and is appropriately set. For example, it is preferably 0.01 to 3 moles per mole of the total silane compound, It is 1 mol.

Examples of the organic solvent that can be used in the hydrolysis and condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Specific examples of the hydrocarbon include, for example, toluene, xylene and the like; As the ketone, for example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and the like; As the ester, for example, ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; As the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; As the alcohol, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like; Respectively. Of these, it is preferable to use a water-insoluble organic solvent. These organic solvents may be used alone or in combination of two or more.

The use ratio of the organic solvent in the hydrolysis and condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound used in the reaction.

The hydrolysis-condensation reaction is preferably carried out by dissolving the silane compound as described above in an organic solvent, mixing the solution with an organic base and water, and heating it by, for example, an oil bath. In the hydrolysis-condensation reaction, the heating temperature is preferably 130 ° C or lower, more preferably 40 to 100 ° C. The heating time is preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During the heating, the mixed solution may be stirred or refluxed. After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of this cleaning, cleaning is preferably performed by using water containing a small amount of a salt (for example, an aqueous solution of ammonium nitrate of about 0.2 wt%) from the standpoint of facilitating the cleaning operation. The washing is carried out until the water layer after the washing becomes neutral. Thereafter, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain the objective polyorganosiloxane (Epoxy group-containing polyorganosiloxane) can be obtained.

[Carbonic acid (AC)]

The carbonic acid (AC) used in the reaction with the epoxy group-containing polyorganosiloxane may have a group represented by the formula (1) and a carboxyl group, for example, a compound represented by the following formula (AC1)

(Wherein A ¹ , Y, L, Z, a, b and W ¹ each have the same meanings as in the above formula (a-1)).

As for A ¹ , Y, L, Z, a, and b in the formula (AC1), the description in the period of the formula (1) can be applied respectively. As for W ¹ , the description of the group represented by the above formula (a-1) can be applied.

Preferred examples of the compound represented by the formula (AC1) include compounds represented by the following formulas (AC-1) to (AC-30) and (AC-33) to have.

(AC-1) to (AC-1) to (AC-1) to (AC-41) 30), (AC-33) to (AC-41).

As the carbonic acid to be reacted with the epoxy group-containing polyorganosiloxane, a carbonic acid (AC) may be used singly or other carbonic acid may be used together with a carbonic acid (AC). Examples of the other carbonic acid include carbonic acid having a polymerizable unsaturated bond (excluding those corresponding to the above carbonic acid (AC)), such as formic acid, acetic acid, propionic acid, benzoic acid, methylbenzoic acid, ), And the like can be given. It is preferable to use carbonic acid having a polymerizable unsaturated bond other than the above-mentioned carbonic acid (AC) as other carbonic acid in that it can increase stability of the pretilt angle of the obtained liquid crystal display element. The carbonic acid is preferably a carboxylic acid having a (meth) acryloyl group, and examples thereof include acrylic acid, methacrylic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2- Cyclohexane-hexahydrophthalic acid, and the like.

[Synthesis of carbonic acid]

Carbonic acid (AC) can be synthesized by appropriately combining the methods of organic chemistry. As an example thereof, first, a compound represented by the formula (AC1) can be synthesized by synthesizing a carbonic acid ester in which a carboxyl group is protected with a t-butyl group or the like, and deprotecting the resulting carboxylic acid ester .

Here, a = 0 and b = 1 which will be described for the carboxylic acid ester for example, in the case of "Y" indicates "* ² -CO-O-", for example represented by ^"1 ZA -COOH" Compound and a halide represented by "X ^h -L-COO-R ^p " (wherein X ^h is a halogen atom and R ^p is a protecting group) in the presence of a suitable catalyst, Followed by deprotection of the resulting coupling product.

When "Y" is "* ² -O-CO-", for example, a compound represented by "ZA ¹ -OH" and a halide represented by "X ^h -CO-L-COO-R ^p " , X ^h is a halogen atom, and R ^p is a protecting group) in the presence of a suitable catalyst, followed by deprotection of the coupling product obtained by the reaction.

When Y is "-O-", for example, a compound represented by "ZA ¹ -OH" and a halide represented by "X ^h -L-COO-R ^p " (wherein X ^h represents a halogen atom And R ^p is a protecting group) in the presence of a suitable catalyst, followed by deprotection of the coupling product obtained by the reaction. However, the method of synthesizing carbonic acid (AC) is not limited to the above method.

[Reaction between an epoxy group-containing polyorganosiloxane and a carboxylic acid]

The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent.

In the above reaction, the amount of the carboxylic acid (total amount) to be used is preferably at least 5 mol%, more preferably from 10 to 90 mol%, based on the epoxy group of the epoxy group-containing polyorganosiloxane And preferably 15 to 80 mol%. In the method (I), the ratio of the carboxylic acid having a vertically-oriented group is preferably 50 mol% or more, more preferably 70 mol% or more, based on the total amount of the carbonic acid used in the reaction. On the other hand, in the method (II), the use ratio of the carboxylic acid (AC) is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total amount of the carbonic acid used in the reaction.

As the catalyst to be used in the reaction, for example, known compounds such as so-called curing accelerators for promoting the reaction of organic bases and epoxy compounds can be used.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene; Quaternary organic amines such as tetramethylammonium hydroxide; And the like. As the organic base, a tertiary organic amine or a quaternary organic amine is preferable.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol;

Imidazole compounds such as 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole;

Organic phosphorus compounds such as diphenylphosphine and triphenylphosphine;

Quaternary phosphonium salts such as benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide and ethyltriphenylphosphonium bromide;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 or an organic acid salt thereof; Organometallic compounds such as zinc octylate, tin octylate, and aluminum acetyl acetone complex;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride; Boron compounds such as boron trifluoride, triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride;

A high melting point dispersed latent curing accelerator such as an amine addition type accelerator such as dicyandiamide or an adduct of an amine with an epoxy resin; A microcapsulated latent curing accelerator in which a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer; Amine salt type latent curing accelerator; Latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts; And the like. Of these, quaternary ammonium salts are preferred.

The catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the epoxy group-containing polyorganosiloxane.

Examples of the organic solvent that can be used in the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, and an alcohol compound. Of these, ether compounds, ester compounds and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of products. Specific examples of particularly preferable solvents include 2-butanone, 2-hexanone, Butyl ketone, and butyl acetate. The organic solvent is preferably used in such a ratio that the solid concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) is 0.1 wt% or more, preferably 5 to 50 wt% Is more preferable.

The reaction temperature is preferably 0 to 200 캜, more preferably 50 to 150 캜. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. Further, after completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. After washing with water, the organic solvent layer is dried, if necessary, with a suitable drying agent, and then the solvent is removed to obtain the objective polyorganosiloxane (specific polyorganosiloxane).

[About method (III)]

Examples of the silane compound used in the method (III) include the same ones as those exemplified in the above-mentioned method (I), and the other silane compounds include the epoxy group-containing silane compound, the above- And silane compounds having polymerizable unsaturated bonds. As for the details of the hydrolysis-condensation reaction in the method (III), the description of the above method (II) can be applied.

The specific polyorganosiloxane to be contained in the liquid crystal aligning agent of the present invention preferably has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 500 to 100,000, more preferably 1,000 to 30,000 Do.

The content of the polymer (P) in the liquid crystal aligning agent of the present invention is preferably such that the amount of the polymer (P) in the liquid crystal aligning agent of the present invention is preferably in the range of 5,000 J / Is preferably 1% by weight or more, more preferably 5% by weight or more, based on the total amount of the polymer component contained in the liquid crystal aligning agent, from the viewpoint that each property can be obtained and the response speed of liquid crystal molecules can be sufficiently fast desirable.

≪ Polymer (Q) >

When the liquid crystal aligning agent of the present invention contains a specific polyorganosiloxane as the polymer (P), it is preferable to use at least one kind of polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide together with the specific polyorganosiloxane (Q). The polymer (Q) may or may not have a group represented by the formula (1). Preferably, the polymer (Q) does not have a group represented by the formula (1).

In the case of containing the specific polyorganosiloxane and the polymer (Q) as the polymer component, the content of the polymer (Q) is preferably 1 to 99% by weight based on the total amount of the polymer components contained in the liquid crystal aligning agent, More preferably 10 to 95% by weight. When the content of the polymer (Q) is 1% by weight or more, the heat resistance and mechanical strength of the liquid crystal alignment film can be improved. When the content of the polymer (Q) is 99% by weight or less, the response speed of liquid crystal molecules by specific polyorganosiloxanes An improvement effect of the tilt angle characteristics can be suitably obtained.

<Polyamic acid>

The polyamic acid contained in the liquid crystal aligning agent of the present invention can be synthesized, for example, by reacting a tetracarboxylic acid dianhydride with a diamine.

[Tetracarboxylic acid dianhydride]

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid in the present invention include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride . As specific examples of these,

Examples of the aliphatic tetracarboxylic acid dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and the like;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane 2: 3,5: 6-2 anhydride, 2 , 4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6,8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- 5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride and the like;

As the aromatic tetracarboxylic acid dianhydride, for example, pyromellitic dianhydride and the like;

Tetracarboxylic acid dianhydride described in JP-A-2010-97188, and the like can be used. The tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

As the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid, it is preferable to use the alicyclic tetracarboxylic dianhydride alone or a mixture of the alicyclic tetracarboxylic dianhydride and the aromatic tetracarboxylic dianhydride Do. In the latter case, the alicyclic tetracarboxylic acid dianhydride is preferably contained in an amount of 20 mol% or more, more preferably 40 mol% or more, based on the total amount of the tetracarboxylic dianhydride used in the synthesis.

[Diamine]

Examples of the diamine used for synthesizing the polyamic acid in the present invention include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;

As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

As aromatic diamines, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl Diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9- 4,4'- (m-tert-butylphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 - diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl- , 6-diaminocarbazole, N-phenyl (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-diaminocyclohexane, N, N'- Aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1- (4-amino Phenyl) -2,3-dihydro-1,3,3-trimethyl-1 H-inden-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholesteryl Diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5- (3,5-diaminobenzoyloxy) cholestane, 3, 5-diaminobenzoyloxy cholestane, 3, 6-bis 4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) ) Cyclohexyl-3,5-di (4 - ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis Bis (4 - ((aminophenyl) methyl) phenyl) -4- (4-hydroxyphenyl) -4-heptylcyclohexane, Aminobenzylamine, and 3-aminobenzylamine represented by the following formula (D-1): &lt; EMI ID =

^Wherein X ^I and X ^II each independently represents a single bond, -O-, -COO- or OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and a (a) Is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, n is 0 or 1, provided that a and b do not become 0 at the same time)

And the like;

As the diaminoorganosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like; The diamine described in JP-A-2010-97188 can be used. These diamines may be used singly or in combination of two or more.

Examples of the divalent group represented by "-X ^I - (R ^I -X ^II ) _n -" in the above formula (D-1) include an alkanediyl group having 1 to 3 carbon atoms, * -O-, * -COO- Or * -OC ₂ H ₄ -O- (provided that a bonding hand having "*" attached thereto is bonded to a diaminophenyl group). Specific examples of the group "-C _c H _{2c +1} " include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n-heptadecyl, n-heptadecyl, n-octadecyl, n-hexadecyl, n-hexadecyl, n-nonadecyl group, and n-eicosyl group. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-3).

In addition, these tetracarboxylic acid dianhydrides and diamines have the same function in that they can obtain a polyamic acid for inclusion in the liquid crystal aligning agent for the purpose of improving various properties such as heat resistance and mechanical strength of the liquid crystal alignment film . Therefore, even those not described in the following examples can be used in the present invention.

[Molecular Weight Regulator]

In the synthesis of the polyamic acid, the endmodified polymer may be synthesized by using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and the diamine as described above. By using such a polymer having a terminal modification type, the coating property (printing property) of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention.

Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds. Specific examples thereof include acid anhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back; As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and the like; As the monoisocyanate compound, for example, phenyl isocyanate, naphthyl isocyanate and the like; Respectively.

The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride and diamine to be used.

<Synthesis of polyamic acid>

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid in the present invention is such that the ratio of the acid anhydride group of the tetracarboxylic acid dianhydride to the equivalent of 0.2 to 2 equivalents , More preferably from 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 캜 to 150 캜, more preferably 0 to 100 캜. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like.

Specific examples of these organic solvents include non-protonic polar solvents such as N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N- , N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, gamma -butyrolactone, tetramethylurea, hexamethylphosphoric triamide and the like; As the phenolic solvent, for example, phenol, m-cresol, xylenol, halogenated phenol and the like;

Examples of the alcohols include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like; Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like;

Examples of the esters include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, isoamyl propionate, isoamyl isobutyrate, Ethyl, diethyl malonate and the like;

Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether , Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Diisopentyl ether, tetrahydrofuran and the like;

As the halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like; Examples of the hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene and the like; Respectively.

Among these organic solvents, at least one kind selected from the group consisting of an aprotic polar solvent and a phenol type solvent (first group of organic solvents), or at least one kind selected from an organic solvent of the first group, It is preferable to use a mixture of at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less, relative to the total amount of the organic solvent of the first group and the organic solvent of the second group By weight, more preferably not more than 30% by weight.

The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50 wt% with respect to the total amount (a + b) of the reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or after the isolated polyamic acid is purified, . When the polyamic acid is dehydrated and cyclized to polyimide, the reaction solution may be directly supplied to the dehydration ring-closing reaction, or the polyamic acid contained in the reaction solution may be isolated and then subjected to a dehydration ring- The polyamic acid may be purified and then subjected to a dehydration ring-closing reaction. The polyamic acid can be isolated and purified by a known method.

<Polyimide>

The polyimide contained in the liquid crystal aligning agent of the present invention can be obtained, for example, by imidizing the polyamic acid synthesized as described above by dehydration ring closure.

The polyimide may be a completely imidized product obtained by dehydrating and ring closure of the entire acid structure of the polyamic acid which is a precursor of the polyimide. The polyimide may be a partially imidized product in which only a part of the acid structure is subjected to dehydration ring closure, . The imide ratio of the polyimide in the present invention is preferably 30% or more, more preferably 40 to 99%, and even more preferably 45 to 99%. The imidization rate is expressed as a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid, or a method of dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and optionally heating the polyamic acid . The latter method is preferred.

In the method of adding the dehydrating agent and the dehydrating ring-closing catalyst to the solution of the polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration cyclization reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide is obtained. The reaction solution may be directly supplied to the preparation of a liquid crystal aligning agent, may be added to the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring- The polyimide may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or may be provided in the preparation of the liquid crystal aligning agent after the isolated polyimide is purified. These purification operations can be carried out according to a known method.

<Polyamic acid ester>

The polyamic acid ester contained in the liquid crystal aligning agent of the present invention may be obtained by, for example, ring opening the tetracarboxylic acid dianhydride to give a dicarboxylic acid 2 ester, then subjecting the resulting dicarboxylic acid 2 ester and diamine to the presence of a dehydration catalyst ; [Ii] a method in which a 2-ester 2-carboxylic acid chloride is obtained by using tetracarboxylic acid dianhydride, and then the obtained 2-ester 2-carboxylic acid chloride is reacted with a diamine; [Iii] a method of esterifying the carboxyl group of the polyamic acid; And the like. Examples of tetracarboxylic acid dianhydrides and diamines that can be used in the synthesis of the polyamic acid ester include the compounds exemplified in the description of the polyamic acid.

&Lt; Solution viscosity of polymer >

The polyamic acid, polyamic acid ester and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s and a solution of 15 to 500 mPa · s It is more preferable to have a viscosity. The solution viscosity (mPa · s) of the polymer is preferably 10 to 10 mPa.s (mPa.s) prepared using a good solvent (for example,? -Butyrolactone, N-methyl- Measured at 25 캜 using an E-type rotational viscometer with respect to the weight% of the polymer solution.

&Lt; Weight average molecular weight of polymer &

The polyamic acid, the polyamic acid ester and the polyimide preferably have a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 500 to 300,000, more preferably 1,000 to 200,000.

<Other components>

The liquid crystal aligning agent of the present invention may contain other components as required. Such other components include, for example, other polymers other than those described above, a compound having at least one epoxy group in the molecule (hereinafter referred to as an &quot; epoxy group-containing compound &quot;), and a functional silane compound.

[Other Polymers]

The other polymer may be used for improving solution characteristics and electrical properties. Examples of such other polymers include polyorganosiloxanes other than the specific polyorganosiloxanes described above, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) (Meth) acrylate, and the like.

When the other polymer is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 50% by weight or less, more preferably 0.1 to 40% by weight, more preferably 0.1 to 30% by weight based on the total amount of the polymer in the composition More preferable.

[Epoxy group-containing compound]

The epoxy group-containing compound can be used for improving the adhesion to the substrate surface and electric characteristics in the liquid crystal alignment film. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Diallyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromonopentyl glycol di N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidylaminomethylcyclohexane, N-diglycidyl-cyclohexylamine, and the like. In addition, as the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.

When these epoxy compounds are added to the liquid crystal aligning agent, the blending ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-tri Methoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like, Can.

When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio thereof is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight per 100 parts by weight of the total amount of the polymers.

In addition to the above-exemplified compounds, compounds having at least one oxetanyl group in the molecule, an antioxidant, and the like may be used as the other components.

<Solvent>

The liquid crystal aligning agent of the present invention is constituted by dissolving a polymer component and optionally other optional components, if necessary, in an organic solvent.

Examples of the solvent used in the preparation of the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, Propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol diisopropyl ether, diethylene glycol diisopropyl ether, Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether There may be mentioned the lactate, dipropylene glycol monomethyl ether (DPM), di-isobutyl ketone, isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used alone or in combination of two or more.

The solid concentration of the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate as described later, and is preferably heated to form a coating film which becomes a liquid crystal alignment film or a liquid crystal alignment film. When the solid concentration is less than 1 wt% , The film thickness of the coating film becomes too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large, and it becomes difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased and the coating property is poor.

A particularly preferable range of the solid concentration is different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in accordance with the spinner method, it is particularly preferable that the solid concentration is in the range of 1.5 to 4.5% by weight. In the case of following the printing method, it is particularly preferable to set the solid content concentration in the range of 3 to 9% by weight and the solution viscosity in the range of 12 to 50 mPa · s accordingly. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and accordingly, the solution viscosity is in the range of 3 to 15 mPa · s.

The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚.

<Liquid Crystal Alignment Film and Liquid Crystal Display Device>

The liquid crystal alignment film of the present invention is formed by the liquid crystal aligning agent prepared as described above. Further, the liquid crystal display element of the present invention comprises a liquid crystal alignment film formed using the liquid crystal aligning agent. The mode of operation of the liquid crystal display element is not particularly limited, but is preferably applied in a vertically aligned mode.

A liquid crystal display element of the present invention comprises a first step of applying a liquid crystal aligning agent of the present invention onto a conductive film of a pair of substrates each having a conductive film and then heating this to form a coated film, A second step of arranging a pair of substrates so as to face each other with a coating film interposed therebetween through a layer of liquid crystal molecules to construct a liquid crystal cell; and a step of irradiating the liquid crystal cell with light And a third step of carrying out the reaction.

[First Step: Formation of Coating Film]

In this step, two substrates each having a patterned transparent conductive film are formed as a pair, and the liquid crystal aligning agent of the present invention is applied onto the surface of the transparent conductive film on the substrate, Spin coating method, roll coater method, or inkjet printing method. Examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film to be formed on one surface of the substrate, an ITO film made of NESA film (a registered trademark of PPG Corporation of the US) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) . In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a patternless transparent conductive film, a method of using a mask having a desired pattern in forming a transparent conductive film, and the like . When applying the liquid crystal aligning agent, a functional silane compound, a functional titanium compound or the like is preferably added to the surface of the substrate on which the coating film is to be formed, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film The pre-treatment for pre-coating may be carried out.

Preheating (prebaking) is preferably performed for the purpose of preventing the liquid flow of the applied liquid crystal aligning agent after application of the liquid crystal aligning agent. The prebaking temperature is preferably 30 to 200 캜, more preferably 40 to 150 캜, particularly preferably 40 to 100 캜. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the acid structure present in the polymer. The post-baking temperature is preferably 80 to 300 占 폚, and more preferably 120 to 250 占 폚. The post baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 占 퐉, and more preferably 0.005 to 0.5 占 퐉.

After the application of the liquid crystal aligning agent, the organic solvent is removed by heating, whereby a coating film to be an alignment film is formed. At this time, when the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid or an imidized polymer having an imidazole ring structure and an arboric acid structure, the dehydration ring-closure reaction is further advanced by further heating after forming the coating film, Or may be a coated film. The coating film thus formed can be used as it is as a liquid crystal alignment film, but rubbing treatment may be carried out as desired.

[Second Step: Construction of Liquid Crystal Cell]

In this step, two liquid crystal alignment films are formed as described above, and the liquid crystal is arranged between the two substrates arranged opposite to each other to manufacture a liquid crystal cell. Here, when the coating film is subjected to the rubbing treatment, the two substrates are opposed to each other such that the rubbing directions of the coating films are at a predetermined angle, for example, orthogonal or anti-parallel to each other.

In order to produce a liquid crystal cell, for example, the following two methods can be mentioned.

The first method is a conventionally known method (vacuum injection method). First, two substrates are opposed to each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded to each other using a sealant. Liquid crystal is injected and filled in the cell gap, and then the injection port is sealed to produce a liquid crystal cell.

The second method is a method called ODF (One Drop Fill) method. For example, an ultraviolet curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is further dripped onto a predetermined number of places on the liquid crystal alignment film surface, A liquid crystal cell is manufactured by joining the other substrate so that the alignment film is opposed to the substrate, spreading the liquid crystal on the entire surface of the substrate, and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealing agent.

In any method, the liquid crystal cell manufactured as described above may be further heated to a temperature at which the liquid crystal used is isotropic, and then gradually cooled to room temperature to remove the flow alignment at the time of filling the liquid crystal .

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

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Of these, nematic liquid crystals are preferable, and examples thereof include a cypher base liquid crystal, an agar watch liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane liquid crystal, , Terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, quaternary type liquid crystals and the like. Further, to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate; Chiral agents such as those sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, and the like may be added and used. The thickness of the liquid crystal molecule layer is preferably 1 to 5 mu m.

[Third step: light irradiation step]

After the formation of the liquid crystal cell, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage to be applied here may be DC or AC of 5 to 50 V, for example. As the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As the light source of the irradiation light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp and an excimer laser can be used. The ultraviolet ray in the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with, for example, a filter diffraction grating or the like.

The irradiation dose of light is preferably 1,000 J / m 2 or more and less than 100,000 J / m 2, and more preferably 1,000 to 50,000 J / m 2. For example, it has been necessary to irradiate light of about 100,000 J / m 2 at the time of manufacturing a conventionally known PSA mode liquid crystal display element. However, in the method of manufacturing a liquid crystal display element of the present invention, Or less, and even when it is 5,000 J / m &lt; 2 &gt; or less, it is possible to obtain a liquid crystal display element having the desired pretilt angle characteristics and contribute to reduction of the manufacturing cost of the liquid crystal display element. In addition, the reduction of the electric characteristics due to the irradiation of strong light and the lowering of the responsiveness of the liquid crystal molecules are suppressed.

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. As the polarizing plate, a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state is sandwiched by a cellulose acetate protective film, or a polarizing plate comprising a H film itself is exemplified.

The liquid crystal display element of the present invention can be effectively applied to various apparatuses and can be applied to various devices such as a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, Phones, various monitors, liquid crystal televisions, information displays, and the like.

(Example)

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

The weight average molecular weight, the epoxy equivalent, the solution viscosity of each polymer solution, and the imidation rate of the polyimide of each polymer in the examples and the synthesis examples were measured by the following methods.

[Weight average molecular weight]

The weight average molecular weight Mw of the polymer was determined from the results of measurement by gel permeation chromatography (GPC) under the following conditions using polystyrene as a standard substance using monodispersed polystyrene.

Measuring device: Type "8120-GPC" manufactured by Tosoh Corporation

Column: "TSKgel GRCXL II" manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Sample concentration: 5% by weight, sample injection amount: 100 μL

Column temperature: 40 占 폚, column pressure: 68 kgf / cm2

[Imidization Rate of Polyimide]

The polyimide solution was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidization ratio [%] was obtained by the equation shown by the following formula (1x): &lt; EMI ID =

Imidization rate [%] = {(1-A ¹ ) / (A ² x?)} 100 ... (1x)

(In the formula (1x), A ¹ is the peak area originating from the proton of the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from the other proton, and α is the peak area derived from the proton The ratio of the number of other protons to one proton in the NH group).

&Lt; Synthesis (1) of polymer (P) >

[Example P1]

3.2 g of oxalic acid and 39.6 g of ethanol were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser and stirred to prepare an ethanol solution of oxalic acid. Subsequently, this solution was heated to 70 캜 in a nitrogen atmosphere, and then the compound represented by the formula (a1-1) (provided that the group "-C ₆ H ₁₂ -" was a silane compound Hexane-1,6-diyl group), and further 2.2 g of tetraethoxysilane (TEOS) was added dropwise as another silane compound. After the completion of the dropwise addition, a solution containing the polyorganosiloxane (A-1) as the polymer (P) was obtained by adding 40.0 g of butyl cellosolve followed by cooling to 25 캜 after maintaining the temperature at 70 캜 for 6 hours It was prepared. The weight average molecular weight Mw of the polyorganosiloxane (A-1) contained in this solution was 12,000.

[Examples P2 to P33, Synthesis Example 1]

(A-2) to (A-2) were obtained in the same manner as in Example P1, except that the kinds and amounts of the silane compounds used as raw materials, and the amounts of oxalic acid and ethanol used were as shown in Table 1, -33) and (c-1), respectively. As the silane compound (a1), a silane compound having a group "-C _n H _2n -" is used. The weight average molecular weight Mw of each polyorganosiloxane contained in each solution is shown in Table 1 below.

In Table 1, the abbreviations of the respective compounds have the following meanings respectively.

ODES: octadecyltriethoxysilane

MPTMS: 3-methacryloyloxypropyltrimethoxysilane

In Table 1, "-" indicates that the raw material corresponding to the column was not used (the same applies to the following tables).

&Lt; Synthesis of carbonic acid (AC) >

[Example AC-1]

Carbonic acid (AC-1) was synthesized by the following Reaction Scheme 1.

22.3 g (77.5 mol) of 4- (4-methacryloyloxy-cyclohexyl) benzoic acid, 320 ml of dimethylformamide, 17.1 g (81.4 mmol) of t-butyl 6- 21.9 mg of hydroxytoluene, and 21.4 g (155 mmol) of potassium carbonate were mixed and stirred at 70 占 폚 for 7 hours. Subsequently, 700 ml of ethyl acetate and 700 ml of cyclohexane were added, and extracted and washed five times with 500 ml of distilled water. The organic layer was concentrated to obtain 28 g of a coupling product.

Then, 28 g of the obtained coupling product, 98 ml of dichloromethane, 28 mg of dibutylhydroxytoluene and 24.5 ml of trifluoroacetic acid were mixed and stirred at room temperature for 2 days. After concentrating to remove trifluoroacetic acid, 500 ml of ethyl acetate was added and extracted twice with 250 ml of distilled water. 250 mL of ethanol was added to the organic layer, and the mixture was concentrated to precipitate, followed by filtration, washing with ethanol, and drying, to obtain 23 g of a carboxylic acid (AC-1) as a target.

[Example AC-9]

Carbonic acid (AC-9) was synthesized by the following Reaction Scheme 2.

42.8 g (0.2 mol) of 4- (4-hydroxyphenyl) benzoic acid, 16 g (0.4 mol) of sodium hydroxide and 1 L of water were added to a 2 L three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, Or less. Next, 23.4 mL (0.24 mol) of methacryloyl chloride and 300 mL of methylene chloride were added to the dropping funnel, and the dropwise addition was carried out at 5 DEG C over 2 hours, and the temperature was returned to room temperature and further reacted for 3 hours. After completion of the reaction, the white precipitate recovered by filtration was dissolved in 1 L of ethyl acetate and 2 L of tetrahydrofuran, and washed once with 1 L of 1M hydrochloric acid aqueous solution and three times with 500 mL of water. Next, the organic layer is dried with magnesium sulfate, concentrated to about 500 mL, and the resulting white crystal is collected and dried to obtain the compound represented by the formula (AC2-1) (hereinafter also referred to as "compound (AC2-1)") 56.5 g of white crystals were obtained.

Subsequently, 13.59 g (48.1 mmol) of the compound (AC2-1) obtained above, 200 mL of DMF, 10 mL of 11-bromo-n-undecanoic acid-t-butyl 16.34 g (50.5 mmol) of potassium carbonate and 13.31 g (96.3 mmol) of potassium carbonate were added and reacted at 70 占 폚 for 8 hours. After completion of the reaction, 500 mL of cyclohexane and 500 mL of ethyl acetate were added and the mixture was washed with 400 mL of water three times, dried over magnesium sulfate, and concentrated to obtain a liquid compound (AC2-2) -2) &quot;).

Then, 28.62 g of the compound (AC2-2) obtained above, 100 mL of methylene chloride and 25 mL of trifluoroacetic acid were added to a 500 mL eggplant-shaped flask, and the mixture was allowed to react at room temperature for 5 hours. After completion of the reaction, 100 mL of ethanol was added thereto, and the mixture was concentrated. Further, 100 mL of ethanol was added thereto, and the mixture was concentrated. The mixture was allowed to stand overnight. The resulting crystals were filtered and washed with ethanol and dried to obtain 12.51 g of white crystals of carboxylic acid (AC-9).

[Example AC-14]

Carbonic acid (AC-14) was synthesized by the following Reaction Scheme 3.

(36.22 mmol) of hydroxybenzoic acid, 150 mL of tetrahydrofuran, 100 mL of t-butanol and 0.177 g of N, N-dimethylaminopyridine (1.45 m, ㏖). Next, 8.22 g (39.84 mmol) of dicyclohexylcarbodiimide was dissolved in 50 mL of tetrahydrofuran and added dropwise over 30 minutes to the dropping funnel, and the mixture was allowed to react for 15 hours. After the completion of the reaction, the filtrate was subjected to Celite filtration, and the resulting liquid was concentrated. To the residue was added 300 mL of ethyl acetate, and the mixture was washed with an aqueous solution of sodium hydrogencarbonate twice and three times with water, followed by concentration and vacuum drying to obtain orange viscous liquid &Lt; / RTI &gt; This viscous liquid was purified by silica column purification (developing solvent: hexane / ethyl acetate = 80/20 (weight ratio)) to obtain the compound represented by the formula (AC3-1) 3.6 g of white crystals were obtained.

Subsequently, 12.25 g (63.1 mmol) of the compound (AC3-1), 16.64 g (66.2 mmol) of 11-bromo-n-undecanol and 50 ml of N, N-dimethylaniline were placed in a 500 ml three-necked flask equipped with a thermometer and a nitrogen- Dimethylacetamide, 9.58 g (69.4 mmol) of potassium carbonate and 2.09 g (12.6 mmol) of potassium iodide were added and reacted at 100 DEG C for 2 hours. After completion of the reaction, 500 mL of ethyl acetate was added, and the mixture was washed three times with diluted hydrochloric acid and once with water. Thereafter, the product was dried with magnesium sulfate, concentrated, and dried to obtain 21.3 g of a white solid of a compound represented by the formula (AC3-2) (hereinafter also referred to as "compound (AC3-2)").

Subsequently, 16.48 g (58.4 mmol) of the compound (AC2-1), 21.3 g (58.4 mmol) of the compound (AC3-2) and 440 mL of methylene chloride were added to a 1 L three-necked flask equipped with a thermometer and a nitrogen- And ice-cooled. Next, 13.47 g (70.3 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1.43 g (11.7 mmol) of N, N-dimethylaminopyridine were added thereto and stirred for 2 hours under ice- Thereafter, the reaction was returned to room temperature and allowed to react for 16 hours. After completion of the reaction, 2 L of ethyl acetate was added, and the mixture was washed three times with water, followed by drying with magnesium sulfate. Next, the white precipitate formed by concentration was filtered and dried to obtain 26.0 g of a white crystal of the compound represented by the formula (AC3-3) (hereinafter also referred to as "compound (AC3-3)").

Subsequently, 26.0 g (41.3 mmol) of the compound (AC3-3), 55 mL of trifluoroacetic acid and 110 mL of methylene chloride were added to a 500 mL eggplant type flask and reacted at room temperature for 5 hours. After completion of the reaction, the solvent was removed by an aspirator, 2 L of ethyl acetate and 2 L of tetrahydrofuran were added, washed with water three times, and then dried with magnesium sulfate. Next, the precipitate formed by concentration was filtered and dried to obtain 20.64 g of a white crystal of carbonic acid (AC-14).

[Example AC-33]

Carbonic acid (AC-33) was synthesized in the same manner as in Example AC-14 except that 6-bromo-n-hexanol was used instead of 11-bromo-n-undecanol.

[Example AC-34]

Carbonic acid (AC-34) was synthesized in the same manner as in Example AC-14 except that 3-bromo-n-propanol was used instead of 11-bromo-n-undecanol.

[Example AC-35]

Carbonic acid (AC-35) was synthesized according to Reaction Scheme 4 below.

(144 mmol) of potassium hydroxide, 24 mL of water, 0.51 g (3 mmol) of potassium iodide and 11.58 g (54 m) of 4- (4-hydroxyphenyl) benzoic acid were added to a 300 mL eggplant- shaped flask equipped with a reflux condenser, ㏖) and 36 mL of ethanol were added and dissolved homogeneously. Subsequently, 15.9 g (60 mmol) of 12-bromo-n-dodecanol was added and the mixture was refluxed for 2 hours. After completion of the reaction, the precipitate obtained by filtration was washed with water, suspended in 300 ml of 1M hydrochloric acid, collected by filtration, and washed with acetone. Subsequently, 15.6 g of a white powder of a compound represented by the formula (AC6-1) (hereinafter also referred to as "compound (AC6-1)") was obtained by recrystallization from 150 mL of methoxyethanol.

Subsequently, 3.98 g (10 mmol) of the compound (AC6-1) obtained above, 0.74 g (6.7 mmol) of hydroquinone, 100 mL of toluene and 100 mL of toluene were placed in a 100 mL three-necked flask equipped with a Dean- 0.57 g (3.3 mmol) of p-toluenesulfonic acid and 8.61 g (100 mmol) of methacrylic acid were added and refluxed for 11 hours. After completion of the reaction, 100 mL of tetrahydrofuran was added, and the mixture was divided into three portions of 50 mL of water, followed by drying with magnesium sulfate, followed by concentration and drying. The resulting solid was recrystallized from 65 mL of ethanol to obtain 2.15 g of a light brown solid of carbonic acid (AC-35).

[Example AC-36]

Carbonic acid (AC-36) was synthesized in the same manner as in Example AC-35 except that 4-hydroxybenzoic acid was used instead of 4- (4-hydroxyphenyl) benzoic acid.

[Example AC-37]

Carbonic acid (AC-37) was synthesized by the following Reaction Scheme 5.

12.4 g (50 mmol) of 4-iodobenzoic acid, 1.85 g (7.5 mmol) of N, N-dimethylaminopyridine, 200 mL of tetrahydrofuran, and 1 mL of tetrahydrofuran were placed in a 500 mL three-necked flask equipped with a reflux condenser, 16.35 g (75 mmol) of di-t-butyl dicarbonate was added and the mixture was reacted at 50 ° C for 5 hours. After completion of the reaction, the solution was concentrated to about 50 mL, and 100 mL of hexane was added to perform filtration. Next, the filtrate was washed three times with 50 mL of a saturated aqueous sodium carbonate solution and 10 times with 50 mL of water, dried over magnesium sulfate, concentrated, and vacuum-dried to obtain a compound represented by the formula (AC8-1) Quot; compound (AC8-1) &quot;) as a pale yellow oil.

Subsequently, 7.5 g (24.7 mmol) of the compound (AC8-1) obtained above, 0.433 g (0.62 mmol) of dichlorobistriphenylphosphine palladium, and 100 ml of a toluene solution were added to a 100 ml three-necked flask equipped with a thermometer and a nitrogen- 0.236 g (1.24 mmol) of copper iodide and 24.7 mL of triethylamine were added, and then 2.66 g (27.1 mmol) of 5-hexyn-1-ol was added thereto, followed by reaction at room temperature for 4 hours. After completion of the reaction, filtration was performed. Ethyl acetate was added to the resulting filtrate, and the filtrate was subjected to liquid separation eight times with water. Subsequently, the product was dried with magnesium sulfate and concentrated to obtain a brown oil. Next, this oil was purified by silica column (developing solvent: hexane / ethyl acetate = 2: 1 (weight ratio)) and concentrated and vacuum dried to obtain the compound represented by the formula (AC8-2) -2) &quot;) as a pale yellow oil.

Then, 0.55 g (1.93 mmol) of the compound (AC2-1), 0.53 g (1.93 mmol) of the compound (AC8-2) and 10 mL of methylene chloride were added to a 100 mL three-necked flask equipped with a thermometer and a nitrogen- And ice-cooled to 0 deg. Then, 0.445 g (2.32 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.047 g (0.386 mmol) of N, N-dimethyl- Lt; / RTI &gt; After completion of the reaction, ethyl acetate was added and the mixture was washed three times with water, followed by drying with magnesium sulfate, followed by concentration and filtration of the white precipitate formed by ethanol addition and drying to obtain the compound represented by the formula (AC8-3) (Hereinafter also referred to as &quot; compound (AC8-3) &quot;).

Subsequently, 3.8 g (7.05 mmol) of the compound (AC8-3) was added to a 100 mL eggplant-shaped flask equipped with a nitrogen inlet tube, 20 mL of methylene chloride and 10 mL of trifluoroacetic acid were added and the reaction was allowed to proceed at room temperature for 1 hour. After completion of the reaction, 150 mL of ethyl acetate and 150 mL of tetrahydrofuran were added, and the mixture was washed with water for 8 times. The solution was washed with water and dried with magnesium sulfate, concentrated and ethanol was added thereto. The precipitated crystals were collected by filtration and dried to obtain carboxylic acid (AC- Of white crystals.

[Example AC-38]

Carbonic acid (AC-38) was synthesized in the same manner as in Example AC-37 except that 9-nonyn-1-ol was used instead of 5-hexyn-1-ol.

[Example AC-39]

Carbonic acid (AC-39) was synthesized by the following Reaction Scheme 6.

(0.1 mol) of 4-hydroxybenzoic acid-t-butyl, 15.2 g (0.11 mol) of potassium carbonate and 3.22 g (0.02 mol) of potassium iodide were placed in a 500 mL three-necked flask equipped with a reflux condenser, ), 200 mL of N, N-dimethylacetamide and 12.2 g (0.105 mol) of 5-hexynechloride were added, followed by reaction at 100 占 폚 for 4 hours. After completion of the reaction, 400 mL of ethyl acetate was added, and the mixture was washed three times with water, followed by drying with magnesium sulfate, followed by filtration and concentration. The resulting solution was purified by silica column (developing solvent: hexane: ethyl acetate = 20: 1 (weight ratio)) to obtain a compound represented by the formula (AC10-1) g.

Then, 11.0 g (50 mmol) of 4-iodophenol, 25 mL of tetrahydrofuran, and 6.1 g (60 mmol) of tetraethylamine were added to a 100 mL three-necked flask equipped with a thermometer, a dropping funnel and a nitrogen- . On the other hand, 5.75 g (55 mmol) of methacryloyl chloride and 10 mL of tetrahydrofuran were added to the dropping funnel, and the dropwise addition was carried out over 30 minutes, followed by returning to room temperature for 1 hour. After completion of the reaction, 50 mL of ethyl acetate was added, and the mixture was washed once with dilute hydrochloric acid, once with sodium carbonate aqueous solution and three times with water, dried with magnesium sulfate, concentrated and dried to obtain the compound represented by the formula (AC10-2) (Hereinafter also referred to as &quot; compound (AC10-2) &quot;).

Subsequently, 8.4 g of the compound (AC10-2), 0.52 g of dichlorobistriphenylphosphine palladium, 0.28 g of cuprous iodide and 29 mL of triethylamine were added to a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube , 8.8 g of the compound (AC10-1) was added, and the mixture was allowed to react at room temperature for 4 hours. After completion of the reaction, the filtrate was subjected to Celite filtration. To the filtrate was added 200 mL of ethyl acetate, and the filtrate was washed with water three times and then dried with magnesium sulfate. The filtrate was concentrated using a silica column (eluent: hexane: 1 (weight ratio)) to obtain 7.5 g of an oil of the compound represented by the formula (AC10-3) (hereinafter also referred to as "compound (AC10-3)").

Subsequently, 7.5 g of the compound (AC10-3), 40 mL of methylene chloride and 20 mL of trifluoroacetic acid were added to a 200 mL eggplant-shaped flask equipped with a nitrogen inlet tube, and the reaction was allowed to proceed at room temperature for 4 hours. After completion of the reaction, methylene chloride and trifluoroacetic acid were distilled off, and then 100 mL of ethyl acetate and 100 mL of tetrahydrofuran were added, and the mixture was washed 10 times with water. Next, the reaction mixture was dried with magnesium sulfate, filtered, concentrated and dried, and then recrystallized with ethanol to obtain 4.7 g of white crystals of carboxylic acid (AC-39).

&Lt; Synthesis (2) of polymer (P) >

[Synthesis Example S1]

8.4 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) as the silane compound (a2) was added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 42 g of ketone and 0.85 g of triethylamine as a catalyst were put and mixed at room temperature. Subsequently, 8.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out for 6 hours while stirring under reflux at 80 ° C. After completion of the reaction, the organic layer was taken out, washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group Quot; polysiloxane (S-1) &quot;) was obtained as a viscous transparent liquid. With respect to the polysiloxane (S-1), the weight average molecular weight Mw in terms of polystyrene measured by GPC was 2,200. As a result of ¹ H-NMR analysis of the polysiloxane (S-1), it was found that a peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm in accordance with the theoretical strength and no side reaction of the epoxy group occurred during the reaction Confirmed.

[Example P34]

6 g of the polysiloxane (S-1) obtained above, 85 g of methyl isobutyl ketone as a solvent and 1.9 g of 4- (4-n-pentyl-cyclohexyl) benzoic acid (PCHBA) as a carbonic acid (polysiloxane 7.1 g (corresponding to 50 mol% based on the epoxy group of the polysiloxane (S-1)) of the carboxylic acid (AC-1) and 20 mol% And 0.10 g of UCAT 18X (trade name, a curing accelerator of an epoxy compound manufactured by San A Pro Co., Ltd.), and the reaction was carried out at 90 캜 for 48 hours with stirring. As the carbonic acid (AC-1), a hexanediyl group was used in a linear form. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the resulting organic layer was washed with water three times, dried over magnesium sulfate and then the solvent was distilled off to obtain a polyorganosiloxane (A-34) as a polymer (P). With respect to the polyorganosiloxane (A-34), the weight average molecular weight Mw in terms of polystyrene measured by GPC was 9,200.

[Examples P35 to P67, Synthesis Example 2]

The polyorganosiloxane (A-35) was obtained in the same manner as in Example P34, except that the kind and amount of the silane compound used as the raw material, and the kind and amount of the used carbonic acid were changed as shown in Table 2, To (A-67) and (c-2), respectively. In Example P65, Example P66, and Synthesis Example 2, two kinds of silane compounds were used each, and in Example P66, two kinds of other carbon acids were used. In Example P67, two kinds of carbonic acid (AC) were used. As the carbonic acid (AC), a compound in which the group -C _n H _2n - is linear is used. Table 2 shows the weight average molecular weights Mw of these polyorganosiloxanes in terms of polystyrene measured by GPC.

In Table 2, the abbreviations of the respective compounds have the following meanings.

GPTMS: 3-glycidoxypropyltrimethoxysilane

OCTBA: 4-n-octyloxybenzoic acid

PCHBA: 4- (4-n-pentyl-cyclohexyl) benzoic acid

[Synthesis Example S2]

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 6.3 g of ECETS as the silane compound (a2) and 2.1 g of methacryloxypropyltrimethoxysilane, 42 g of methyl isobutyl ketone as a solvent, And 0.85 g of ethylamine were added and mixed at room temperature. Subsequently, 8.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out for 6 hours while stirring under reflux at 80 ° C. After completion of the reaction, the organic layer was taken out, washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group Quot; polysiloxane (S-2) &quot;) was obtained as a viscous transparent liquid. With respect to the polysiloxane (S-2), the weight average molecular weight Mw in terms of polystyrene measured by GPC was 2,100.

[Synthesis Example S3]

A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 5.9 g of ECETS as the silane compound (a2) and 2.8 g of methacryloxyoxytitrimethoxysilane, 42 g of cyclopentanone as a solvent, And 0.85 g of amine were added and mixed at room temperature. Subsequently, 8.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out for 6 hours while stirring under reflux at 80 ° C. After completion of the reaction, the organic layer was taken out, washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group Quot; polysiloxane (S-3) &quot;) was obtained as a viscous transparent liquid. With respect to the polysiloxane (S-3), the weight average molecular weight Mw in terms of polystyrene measured by GPC was 2,400.

[Example S4]

2.9 g of ECETS as the silane compound (a2), 5.7 g of the silane compound (a1-33) as the silane compound (a1) and 42 g of methyl isobutyl ketone as the solvent were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube. And 0.85 g of triethylamine as a catalyst were added and mixed at room temperature. Subsequently, 8.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out for 6 hours while stirring under reflux at 80 ° C. After completion of the reaction, the organic layer was taken out, washed with a 0.2 wt% aqueous ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain an epoxy group and a group represented by the formula (1) (Hereinafter also referred to as &quot; polysiloxane (S-4) &quot;) was obtained as a viscous transparent liquid. With respect to the polysiloxane (S-4), the weight average molecular weight Mw in terms of polystyrene measured by GPC was 2,800.

[Examples P77 to P93]

A polyorganosiloxane (A) was obtained in the same manner as in Example P34, except that the kind and amount of the epoxy group-containing polyorganosiloxane used as the raw material, and the kind and amount of the used carbonic acid were changed as shown in Table 3, -77) to (A-93) were synthesized, respectively. As the carbonic acid (AC), a compound in which the group -C _n H _2n - is linear is used. Table 3 shows the weight average molecular weights Mw of these polyorganosiloxanes in terms of polystyrene measured by GPC.

&Lt; Synthesis (3) of polymer (P) >

[Example P68]

5.6 g of oxalic acid and 106 g of ethanol were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and stirred to prepare an ethanol solution of oxalic acid. Subsequently, this solution was heated to 70 deg. C in a nitrogen atmosphere, and then a mixture consisting of 9.9 g of the compound represented by the above formula (a1-1) and 4.9 g of ECETS was added as a raw material silane compound to the mixture, For six hours. Thereafter, the solution was cooled to 25 占 폚, and then 100 g of butyl cellosolve was added to prepare a solution containing the polyorganosiloxane (A-68). The weight average molecular weight Mw of the polyorganosiloxane (A-68) contained in this solution was 9,200.

[Examples P69 to P71]

(A-69) to (A-69) were prepared in the same manner as in Example P1, except that the kind and amount of the silane compound used as the raw material, and the amount of oxalic acid and ethanol used were changed as shown in Table 4, A-71) was prepared. The weight average molecular weight Mw of each polyorganosiloxane contained in each solution is shown in Table 4 below.

[Example P72]

12.7 g of the polyorganosiloxane (A-68) obtained in Example P68, 85 g of methyl isobutyl ketone as a solvent and 2.3 g of PCHBA as a carbonic acid (polyorganosiloxane (A-68) Equivalent to 20 mol% based on the epoxy group) and 0.10 g of "UCAT 18X" as a catalyst, and the reaction was carried out at 90 ° C for 48 hours under stirring. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed three times with water, dried over magnesium sulfate and then the solvent was distilled off to obtain a polyorganosiloxane (A-72) as the polymer (P). With respect to this polyorganosiloxane (A-72), the weight average molecular weight Mw in terms of polystyrene measured by GPC was 11,200.

[Examples P73 to P75]

(P) was obtained in the same manner as in Example P72, except that the type and amount of the polyorganosiloxane used as the raw material, and the kind and amount of the used carbonic acid were changed as shown in Table 5, respectively. (A-73) to (A-75) were obtained, respectively. The weight average molecular weight Mw of the polyorganosiloxane in terms of polystyrene measured by GPC is shown in Table 5 below.

&Lt; Synthesis of Polymer (Q) >

[Synthesis Example 3]

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride and 11 g (0.10 mole) of p-phenylenediamine as diamine and 15 g (0.10 mole) of 3,5-diaminobenzoic acid 53 g (0.20 mol) of 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine and 3- (3,5-diaminobenzoyloxy (0.10 mol) of cholestan were dissolved in 830 g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at 60 DEG C for 6 hours. A small amount of the obtained polyamic acid solution was collected and NMP was added to obtain a solution having a polyamic acid concentration of 10% by weight. The solution viscosity measured at 25 캜 using an E-type rotational viscometer was 52 mPa · s. The weight average molecular weight Mw of the obtained polyamic acid in terms of polystyrene measured by GPC was 160,500.

Next, 1,900 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a fresh NMP solvent to obtain a solution containing about 15% by weight of a polyimide (PI-1) having an imidization rate of about 50%. A small amount of the obtained polyimide solution was collected, and NMP was added thereto to measure the solution as a solution having a polyimide concentration of 10% by weight. The solution viscosity measured at 25 캜 using an E-type rotational viscometer was 35 mPa · s. The weight average molecular weight Mw of the obtained polyimide in terms of polystyrene measured by GPC was 135,000.

[Example 1]

&Lt; Preparation of liquid crystal aligning agent &

As a polymer, butyl cellosolve was added to the solution containing the polyorganosiloxane (A-1) obtained in Example P1 to prepare a solution having a solid concentration of 5% by weight. This solution was filtered using a filter having a pore diameter of 1 mu m to prepare a liquid crystal aligning agent.

&Lt; Production and evaluation of VA type liquid crystal display element >

Using the liquid crystal aligning agent prepared above, the presence or absence of the pattern of the transparent electrode and the ultraviolet ray irradiation amount (three levels) were changed to produce a total of six liquid crystal display elements. Various characteristics were evaluated for the liquid crystal display device manufactured thereby.

[Production of liquid crystal display element having transparent electrode without pattern]

Each of the liquid crystal aligning agents prepared above was coated on the transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film by using a liquid crystal alignment film printing machine (manufactured by Japan Photographic Print Co., Ltd.) (Post-baking) for 10 minutes on a hot plate at 150 DEG C to form a coating film having an average thickness of 600 ANGSTROM. The coating film was subjected to a rubbing treatment at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair pressing indentation length of 0.1 mm by a rubbing machine having rolls wrapped with rayon fabric. Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, and then the substrate was dried in a 100 占 폚 clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the respective outer edges of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces were superimposed on each other, . Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection port was sealed with an acrylic photo-curable adhesive to produce a liquid crystal display device. These operations were repeated to produce three liquid crystal display elements each having a pattern-free transparent electrode. One of them was provided for evaluation of the pretilt angle described later. The remaining two liquid crystal display elements were irradiated with light in a state in which a voltage was applied between the conductive films by the following methods, and then the initial pretilt angle, pretilt angle stability and heat resistance were evaluated.

Two of the liquid crystal display elements obtained above were irradiated with an alternating current of 10 V at a frequency of 60 Hz between the electrodes and irradiated with ultraviolet rays of 5,000 J in the state where the liquid crystal was driven using an ultraviolet irradiation apparatus using a metal halide lamp as the light source / M &lt; 2 &gt; or 10,000 J / m &lt; 2 &gt;. This irradiation dose is a value measured using a photometer which is measured based on a wavelength of 365 nm.

[Evaluation of Initial Pretilt Angle]

Non-Patent Document 1 (TJ Scheffe et al., J. Appl. Phys. Vo.48, p. 1783 (1977)) and Non-Patent Document 2 (F. Nakano et al., JPN , The tilt angle of the liquid crystal molecules from the substrate surface was measured by a crystal rotation method using He-Ne laser light in accordance with the method described in J. Appl. Phys. Vol. 19, p. , And the measured value was set as an initial pretilt angle. Table 8 shows the results of measurement of the initial pretilt angles of the liquid crystal display elements not irradiated with light, the liquid crystal display elements having a dose of 5,000 J / m 2, and the liquid crystal display elements having a dose of 10,000 J /

[Evaluation of Pretilt Angle Stability]

Of the liquid crystal display elements after the measurement of the initial pretilt angle, the liquid crystal display element with a dose of 10,000 J / m 2 was aged for 20 hours under the condition of applying an alternating voltage of 60 V and a voltage of 20 Vp-p under the fluorescent lamp illumination, Was measured by the above method. Further, the amount of change in the pretilt angle before and after aging was determined, and the pretilt angle stability was evaluated based on the amount of change. The evaluation was carried out with the pretilt angle stability "good" when the pretilt angle change amount was 2 ° or less and the pretilt angle stability "poor" when the pretilt angle change amount was larger than 2 °. The results are shown in Table 8 below.

[Evaluation of heat resistance (evaluation of thermal stability of voltage holding ratio)] [

A voltage of 5 V was applied at 23 캜 for an application time of 60 microseconds and a span of 167 milliseconds in the liquid crystal display device manufactured by the above-described ultraviolet light irradiation, and the voltage maintenance rate after 167 milliseconds ) Were measured. As the measuring device, VHR-1 manufactured by Toyotecnica Co., Ltd. was used. Subsequently, the liquid crystal display elements after the measurement of the initial VHR were left in an oven set at a temperature of 120 占 폚 for 5,000 hours. Thereafter, the voltage holding ratio was measured in the same manner as described above. The results of measurement of each of the voltage holding ratios are shown in Table 8 below.

[Production of liquid crystal display element having patterned transparent electrode]

The liquid crystal aligning agent prepared above was patterned into slits as shown in Fig. 1, and on each electrode surface of glass substrates A and B having ITO electrodes partitioned into a plurality of areas, a liquid crystal alignment film printer (Japan (Post-baking) on a hot plate at 150 DEG C for 10 minutes to obtain an average film thickness A coating film having a thickness of 600 Å was formed. This coating film was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film. The pattern of the electrode used is a pattern similar to that of the electrode pattern in the PSA mode.

Subsequently, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 占 퐉 was applied to the outer edges of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces were superimposed on each other and pressed to cure the adhesive. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled between a pair of substrates from the liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to manufacture a liquid crystal cell.

The above operation was repeated to produce three liquid crystal cells having patterned transparent electrodes. One of them was provided for evaluation of the response speed of the liquid crystal molecule described later. The remaining two liquid crystal cells were irradiated with a dose of 5,000 J / m 2 or 10,000 J / m 2 in the same manner as in the case of producing a liquid crystal display element having a patternless transparent electrode, After irradiation with light, it was provided for evaluation of the response speed of liquid crystal molecules.

[Evaluation of response speed of liquid crystal molecules]

For each of the liquid crystal display devices manufactured as described above, the luminance of light transmitted through the liquid crystal display device was measured with a photomultimeter by irradiating a visible light lamp without applying a voltage at first, and this value was regarded as 0% relative transmittance. Next, the transmittance when an AC voltage of 60 V was applied for 5 seconds between the electrodes of the liquid crystal display element was measured in the same manner as described above, and this value was set as a relative transmittance of 100%. The time from when the relative transmittance changes from 10% to 90% when the alternating current of 60 V is applied to each liquid crystal display element is measured, and this time is defined as the response speed, and the change from the voltage off to the voltage on The responsiveness of the liquid crystal molecules was evaluated.

Table 8 shows the measurement results of the response speeds of each of the liquid crystal display elements not irradiated with light, the liquid crystal display element having a dose of 5,000 J / m 2, and the liquid crystal display element having an irradiation dose of 10,000 J / m 2.

[Examples 2 to 71 and Comparative Examples 1 and 2]

A liquid crystal aligning agent was prepared in the same manner as in Example 1, except that the kinds and amounts of the polyorganosiloxane used in the preparation of the liquid crystal aligning agent were as shown in Tables 6 and 7, respectively. Using these liquid crystal aligning agents, liquid crystal display devices were manufactured in the same manner as in Example 1, and the liquid crystal display devices were evaluated. The evaluation results are shown in Tables 8 and 9 below.

[Example 72]

The polyimide (PI-1) obtained in the above Synthesis Example 3 was added to a solution containing the polyorganosiloxane (A-34) obtained in the above Example P34 and 10 weight% of the polyorganosiloxane (A-34) (NMP) and butyl cellosolve (BC) were further added to obtain a solution of NMP: BC = 50: 50 (weight%) and a solid concentration of 5% by weight. This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal display element was produced and evaluated in the same manner as in Example 1 above. The evaluation results are shown in Table 11 below.

[Examples 73 to 109, Comparative Examples 3 and 4]

A liquid crystal aligning agent was prepared in the same manner as in Example 72 except that the kind and amount of the polymer used were changed as shown in Table 10, respectively, and a liquid crystal display device was produced and evaluated. The evaluation results are shown in Table 11 below.

[Examples 110 and 111]

The types and amounts of the other polymers other than the polymer (P) and the polymer (Q) were the same as those described in Table 10, A liquid crystal aligning agent was prepared in the same manner as in Example 72, and a liquid crystal display element was produced and evaluated. The evaluation results are shown in Table 11 above. The abbreviations of the other components in Table 10 are as follows.

GA-80: Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.)

MBOMA: 4,4'-methylenebis [N, N-bis (oxiranylmethyl) aniline]

[Examples 112 to 128]

A liquid crystal aligning agent was prepared in the same manner as in Example 72 except that the type and amount of the polymer used were changed as shown in Table 12 below, and a liquid crystal display device was produced and evaluated. The evaluation results are shown in Table 13 below.

As shown in Tables 8, 9, 11 and 13, in Examples 1 to 128, the initial pretilt angle was good at a low ultraviolet radiation dose of about 5,000 J / m 2. Also, even with such a low ultraviolet radiation dose, the response speed of the liquid crystal molecules to the voltage change was sufficiently fast. In Examples 1 to 128, the voltage-holding characteristics and heat resistance were also excellent. On the other hand, in the comparative example, the initial pretilt angle was not good when the ultraviolet radiation dose was 5,000 J / m 2 and 10,000 J / m 2, and the response speed of the liquid crystal molecules to the voltage change was also slow.

Claims (9)

A liquid crystal aligning agent comprising a polymer (P) having a group represented by the following formula (1)

[In the formula (1), A ¹ represents a group represented by the following formula (1a):

(In the formula (1a), A ² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a piperidine-1,4-diyl group, a piperidine- A pyrimidine-2,5-diyl group, a pyridazine-3,6-diyl group, a pyrazine-2,5-diyl group, or a pyridine-2,5- and 2,5-diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, - (CH 2) 2 - or -C≡C- a, m is an integer from 0 to 2 Provided that when m is 1 or 2, plural A ^{2 s} may be the same or different, and when m is 2, plural X ^{4 s} may be the same or different and two "* ¹ " s Hand)
, A naphthylene group, a tetrahydronaphthalene diyl group, or a decahydronaphthalenediyl group; Y is a single bond, -O-, * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N _{3) -, -N (C 2} H 5) -, -Si (CH 3) 2 -, -S-, * 2 -COS-, * 2 -SCO- or -C≡C- (However, "* ² Quot; represents a bond with A &lt; ¹ &gt;); L is a divalent group in which at least one hydrogen atom of an alkanediyl group having 2 to 20 carbon atoms or an alkanediyl group having 2 to 20 carbon atoms is substituted with a halogen atom and between the carbon- -S- and -NH-, and a part of the carbon-carbon bond may be a double bond or a triple bond; a is 0, b is 1; Z is a group represented by the following formula (2a) or (2b):

(In the formulas (2a) and (2b), X ¹ represents a hydrogen atom or a methyl group; "* ³ " represents a bond)
Lt; / RTI &gt;"*" Indicates a combined hand). delete The method according to claim 1,
The polymer (P) is a liquid crystal aligning agent having a polyorganosiloxane skeleton. The method of claim 3,
And at least one polymer (Q) selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. A liquid crystal aligning agent according to any one of claims 1 to 3, wherein the liquid crystal aligning agent is applied onto the conductive film of a pair of substrates each having a conductive film and then heated to form a coating film and,
A second step of constructing a liquid crystal cell by disposing a pair of substrates on which the coating film is formed so that the coating films face each other with the liquid crystal molecules interposed therebetween;
A third step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films of the pair of substrates
Wherein the liquid crystal display element is a liquid crystal display element.  A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1, 3, and 4. A liquid crystal display element comprising the liquid crystal alignment film according to claim 6. A polymer having a group represented by the following formula (1):

[In the formula (1), A ¹ represents a group represented by the following formula (1a):

(In the formula (1a), A ² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a piperidine-1,4-diyl group, a piperidine- A pyrimidine-2,5-diyl group, a pyridazine-3,6-diyl group, a pyrazine-2,5-diyl group, or a pyridine-2,5- and 2,5-diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, - (CH 2) 2 - or -C≡C- a, m is an integer from 0 to 2 Provided that when m is 1 or 2, plural A ^{2 s} may be the same or different, and when m is 2, plural X ^{4 s} may be the same or different and two "* ¹ " s Hand)
, A naphthylene group, a tetrahydronaphthalene diyl group, or a decahydronaphthalenediyl group; Y is a single bond, -O-, * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N _{3) -, -N (C 2} H 5) -, -Si (CH 3) 2 -, -S-, * 2 -COS-, * 2 -SCO- or -C≡C- (However, "* ² Quot; represents a bond with A &lt; ¹ &gt;); L is a divalent group in which at least one hydrogen atom of an alkanediyl group having 2 to 20 carbon atoms or an alkanediyl group having 2 to 20 carbon atoms is substituted with a halogen atom and between the carbon- -S- and -NH-, and a part of the carbon-carbon bond may be a double bond or a triple bond; a is 0, b is 1; Z is a group represented by the following formula (2a) or (2b):

(Formula (2a), formula (2b) of the, X ¹ is a hydrogen atom or a methyl group; "* ^3" represents a bonding hand).
Lt; / RTI &gt;"*" Indicates a combined hand). A carboxylic acid having a group represented by the following formula (1):

[In the formula (1), A ¹ represents a group represented by the following formula (1a):

(In the formula (1a), A ² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a piperidine-1,4-diyl group, a piperidine- A pyrimidine-2,5-diyl group, a pyridazine-3,6-diyl group, a pyrazine-2,5-diyl group, or a pyridine-2,5- and 2,5-diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, - (CH 2) 2 - or -C≡C- a, m is an integer from 0 to 2 Provided that when m is 1 or 2, plural A ^{2 s} may be the same or different, and when m is 2, plural X ^{4 s} may be the same or different and two "* ¹ " s Hand)
, A naphthylene group, a tetrahydronaphthalene diyl group, or a decahydronaphthalenediyl group; Y is a single bond, -O-, * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N _{3) -, -N (C 2} H 5) -, -Si (CH 3) 2 -, -S-, * 2 -COS-, * 2 -SCO- or -C≡C- (However, "* ² Quot; represents a bond with A &lt; ¹ &gt;); L is a divalent group in which at least one hydrogen atom of an alkanediyl group having 2 to 20 carbon atoms or an alkanediyl group having 2 to 20 carbon atoms is substituted with a halogen atom and between the carbon- -S- and -NH-, and a part of the carbon-carbon bond may be a double bond or a triple bond; a is 0, b is 1; Z is a group represented by the following formula (2a) or (2b):

(In the formulas (2a) and (2b), X ¹ represents a hydrogen atom or a methyl group; "* ³ " represents a bond)
Lt; / RTI &gt;"*" Indicates a combined hand).

Images