KR102014819B1 - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and manufacturing method for the liquid crystal display device - Google Patents

Abstract

(Problem) The liquid crystal aligning agent which can provide the desired pretilt angle characteristic to a coating film with a comparatively small light irradiation amount, and can obtain the liquid crystal display element excellent in heat resistance.
(Solution means) The liquid crystal aligning agent has an epoxy group and a polymerizable unsaturated bond, and has the compound [E] which has a molecular weight of 2,000 or less, and the compound [D] which has two or more polymerizable unsaturated bonds (However, to the said compound [E]. Except where applicable).

Description

A liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, and a manufacturing method of a liquid crystal display element

TECHNICAL FIELD This invention relates to the manufacturing method of a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, and a liquid crystal display element, and especially relates to the liquid crystal aligning agent etc. which can be used suitably when manufacturing a vertical alignment type liquid crystal display element.

Conventionally, as a liquid crystal display element, various drive systems with different electrode structures and physical properties of liquid crystal molecules to be used have been developed. For example, TN type, STN type, VA type, in-plane switching type (IPS type), etc. Various liquid crystal display elements of are known. These liquid crystal display elements have a liquid crystal aligning film for orienting liquid crystal molecules. As a material of a liquid crystal aligning film, polyamic acid, a polyimide, polyester, a polyorganosiloxane, etc. are known, for example.

In recent years, PSA (Polymer Sustained Alignment) technology, photo-alignment technology, etc. have been proposed as a new technology for imparting pretilt angle characteristics to a coating film formed using a liquid crystal aligning agent (for example, a patent document). 1 or Patent Document 2). PSA technology polymerizes a polymerizable component by mixing the polymerizable component which superposes | polymerizes by light irradiation to the liquid crystal layer of a liquid crystal cell, and irradiates light to the liquid crystal cell in the state which inclined liquid crystal molecule by voltage application, and superposes | polymerizes a polymerizable component It is a technique to control the molecular orientation of molecules. Moreover, photo-alignment technique is a technique which expresses a pretilt angle characteristic to a film | membrane by irradiating light to the polymer thin film which has photofunctional groups, such as a cinnamoyl group.

In the case of using the PSA technique, in order to express desired pretilt angle characteristics in the coating film, it is necessary to perform light irradiation at a relatively high irradiation dose. In addition, when the amount of light irradiation is increased, generation of display irregularity of the liquid crystal display element, inferior long-term reliability of the panel, etc. may be caused by decomposition of the liquid crystal molecules and deterioration of the performance of the liquid crystal alignment film. On the other hand, when the amount of light irradiation is reduced, a problem arises in that the response speed of liquid crystal molecules with respect to a voltage change becomes slow in the formed liquid crystal display element. In view of such a point, a desired pretilt angle characteristic can be imparted to a coating film formed by using a liquid crystal aligning agent in a small amount of light as much as possible in recent years, and the response speed of liquid crystal molecules to voltage changes is sufficiently sufficient. The technique for obtaining a quick liquid crystal display element is proposed (for example, refer patent document 3). This patent document 3 forms a coating film on a board | substrate using the polyorganosiloxane which has a (meth) acryloyl group as a polymer component, and the liquid crystal aligning agent containing a polyamic acid or a polyimide, It is disclosed to form a liquid crystal cell by using the same, and to manufacture a liquid crystal display device by irradiating a liquid crystal cell with light while a voltage is applied between the substrates.

Japanese Laid-Open Patent Publication No. 2003-149647 Japanese Laid-Open Patent Publication No. 2009-36966 Japanese Patent Laid-Open No. 2011-118358

By the way, in recent years, the liquid crystal display element is not only used for display terminals, such as a personal computer, but is used for various uses, such as a liquid crystal television, a car navigation system, a mobile telephone, a smart phone, and an information display, for example. With such versatility, the liquid crystal display element may be used under harsher conditions than the prior art, for example, may be used for a long time or may be used under a high temperature environment. Moreover, in recent years, the demand for the high performance of a liquid crystal display element is increasing, and as a liquid crystal display element, what is able to maintain a display quality favorable under such severe conditions is calculated | required.

This invention is made | formed in view of the said subject, The liquid crystal aligning agent which can provide the desired pretilt angle characteristic to a coating film with a comparatively small amount of light irradiation, and can obtain the liquid crystal display element excellent in heat resistance (especially long-term heat resistance). Main purpose is to provide.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the subject of the said prior art, the present inventors discovered that the said subject can be solved by containing a specific compound in a liquid crystal aligning agent, and came to complete this invention. Specifically, the following liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, and the manufacturing method of a liquid crystal display element are provided by this invention.

In one aspect, the present invention corresponds to a compound [E] having an epoxy group and a polymerizable unsaturated bond and having a molecular weight of 2,000 or less, and a compound [D] having two or more polymerizable unsaturated bonds, provided that the compound is a compound [E] To provide a liquid crystal aligning agent).

According to the liquid crystal aligning agent of this invention, by including the said compound [D] and the said compound [E] as a structural component of a liquid crystal aligning agent, a desired pretilt angle characteristic can be provided with respect to a coating film even with a comparatively small light irradiation amount. Therefore, the performance degradation accompanying light irradiation can be minimized. In addition, even when exposed to a high temperature environment for a long time, good voltage integrity characteristics can be preserved and a liquid crystal display element excellent in heat resistance, in particular, long-term heat resistance can be manufactured.

Moreover, it is preferable that the said compound [E] has group represented by following formula (2) as group which has the said polymerizable unsaturated bond, and said compound [D] is group which has the said polymerizable unsaturated bond, It is preferable to have two or more groups represented by following formula (3):

(In Formula (2), R ² is a hydrogen atom or a methyl group, Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom; “*” represents a bond);

(In formula (3), R <^3> is a hydrogen atom or a methyl group, Y <^3> and Y <^4> are respectively independently an oxygen atom or a sulfur atom; "*" represents a bond.).

It is preferable that the liquid crystal aligning agent of this invention further contains at least 1 sort (s) of polymer [A] chosen from the group which consists of a polyamic acid, a polyamic acid ester, a polyimide, and a polyorganosiloxane. By containing the said polymer [A], various characteristics, such as liquid crystal orientation, voltage holding ratio, heat resistance, and mechanical strength of the formed coating film, can be improved.

This invention is another one side WHEREIN: The 1st process of apply | coating the liquid crystal aligning agent of the said base material on the said electrically conductive film of a pair of board | substrates which have a electrically conductive film, and then heating this to form a coating film, and the said coating film A second step of forming a liquid crystal cell by arranging a pair of substrates on which a film is formed so as to face the coating film via a layer of liquid crystal molecules, and a liquid crystal cell in a state where a voltage is applied between a conductive film of the pair of substrates; It provides the manufacturing method of the liquid crystal display element containing the 3rd process of irradiating to light.

When manufacturing a liquid crystal display element using the liquid crystal aligning agent of this invention, by employ | adopting the said method, desired pretilt angle characteristic can be provided with respect to a coating film even with comparatively small light irradiation amount, and heat resistance, especially long-term heat resistance The effect of manufacturing this excellent liquid crystal display element can be acquired suitably.

This invention provides the liquid crystal aligning film formed using the liquid crystal aligning agent of above in one aspect. Moreover, in another aspect, this invention provides the liquid crystal display element provided with the said liquid crystal aligning film.

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

(Form to carry out invention)

Below, the liquid crystal aligning agent of this invention is demonstrated in detail. The liquid crystal aligning agent of this invention contains two compound [D] and compound [E] which have a polymerizable unsaturated bond. In addition, the liquid crystal aligning agent of this invention contains a polymer component. The polymer component includes compound [D] as a polymer, at least one polymer [A] selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane, or both of them. It is preferable. In addition, polymer [A] is a polymer different from compound [D], does not have a polymerizable unsaturated bond, or has one polymerizable unsaturated bond. Hereinafter, each component contained in the liquid crystal aligning agent of this invention, and the other component arbitrarily mix | blended as needed is demonstrated.

Polymer [A]

<Polyamic acid>

The polyamic acid as the polymer [A] in the present invention can be synthesized by, for example, reacting tetracarboxylic dianhydride and diamine. By containing polyamic acid in the said liquid crystal aligning agent, various characteristics, such as liquid crystal aligning property, voltage preservation characteristic, heat resistance, and mechanical strength, can be improved and it is suitable.

[Tetracarboxylic dianhydride]

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

As aliphatic tetracarboxylic dianhydride, For example, 1,2,3, 4- butane tetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 1,3,3a, 4 , 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3 Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro- 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid 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- 3,5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride, and the like;

As aromatic tetracarboxylic dianhydride, For example, pyromellitic dianhydride etc .;

In addition to each of them, tetracarboxylic dianhydride and the like described in JP 2010-97188 A can be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

As tetracarboxylic dianhydride used for synthesize | combining a polyamic acid, it is preferable to use only alicyclic tetracarboxylic dianhydride, or to use the mixture of alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride. In the latter case, it is preferable to contain 20 mol% or more of alicyclic tetracarboxylic dianhydride with respect to the total amount of tetracarboxylic dianhydride used for synthesis | combination, and it is more preferable to contain 40 mol% or more.

[Diamine]

Examples of the diamine used to synthesize the polyamic acid in the present invention include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. As these specific examples, As aliphatic diamine, For example, metaxylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

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

As aromatic diamine, for example, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1,5- diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) biphenyl-4-4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'- Diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-( m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3 , 4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl -3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1 , 4-bis- (4-aminophenyl) -piperazine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1- ( 4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene , Cholesteryloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl , 3,5-diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3- (3,5-diaminobenzoyloxy) Cholestan, 3,6-bis (4-aminophenoxy) cholestan, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-tri Fluoromethylbenzoyloxy) cyclohexyl-3 , 5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl)- 4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4 -(4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, and the following formula (A-1):

(In formula, ^XI and ^XII are each independently a single bond, -O-, -COO-, or -OCO-, R <^1> is a C1-C3 alkanediyl group and a is 0 or 1 B is an integer from 0 to 2, c is an integer from 1 to 20, n is 0 or 1, provided that a and b do not become 0 at the same time.

Compounds represented by these;

As diamino organosiloxane, For example, 1, 3-bis (3-aminopropyl)-tetramethylsiloxane etc .;

In addition to each of them, the diamines described in JP 2010-97188 A can be used. As other diamine, these can be used individually by 1 type or in combination of 2 or more types.

In the formula (A-1) ^{"-X Ⅰ - (R Ⅰ -X Ⅱ} ) n - " As the divalent group represented by, alkanediyl group having a carbon number of 1~3, * -O-, * -COO- Or * -OC ₂ H ₄ -O-, provided that the bond to which "*" is attached is combined with a diaminophenyl group. Specific examples of the group "-C _c H _{2c +1",} for example, methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, n- octyl, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group , n-nonadecyl group, n-eicosyl group and the like. It is preferable that two amino groups in a diaminophenyl group exist in 2, 4-position or 3, 5-position with respect to another group.

As a specific example of a compound represented by said Formula (A-1), the compound etc. which are represented by each of following formula (A-1-1) (A-1-3) are mentioned, for example.

[Molecular Weight Control Agent]

When synthesize | combining a polyamic acid, you may make it synthesize | combine the terminal-modified polymer using a suitable molecular weight modifier with tetracarboxylic dianhydride and diamine as mentioned above. By setting it as such a terminal modified polymer, the coating property (printability) of a liquid crystal aligning agent can be improved further, without impairing the effect of this invention.

As a molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. As these specific examples, as an acid anhydride, maleic anhydride, a phthalic anhydride, itaconic acid anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. are mentioned, for example. of;

As a monoamine compound, For example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc .;

As a monoisocyanate compound, For example, phenyl isocyanate, naphthyl isocyanate, etc .; Each can be mentioned.

It is preferable to set it as 20 weight part or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine to use, and, as for the usage ratio of a molecular weight modifier, it is more preferable to set it as 10 weight part or less.

<Synthesis of polyamic acid>

The use ratio of tetracarboxylic dianhydride and diamine provided in the synthesis reaction of polyamic acid in this invention is a ratio which the acid anhydride group of tetracarboxylic dianhydride becomes 0.2-2 equivalent with respect to 1 equivalent of amino group of diamine. This is preferable and the ratio used as 0.3-1.2 equivalent is more preferable.

The synthesis reaction of polyamic acid is preferably performed in an organic solvent. -20 degreeC-150 degreeC is preferable, and, as for reaction temperature at this time, 0-100 degreeC is more preferable. Moreover, 0.1-24 hours are preferable and, as for reaction time, 0.5-12 hours are more preferable.

Here, as an organic solvent used for reaction, a non-protic polar solvent, a phenol solvent, alcohol, a ketone, ester, an ether, a halogenated hydrocarbon, a hydrocarbon, etc. are mentioned, for example.

Specific examples of these organic solvents include, for example, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N-ethyl-2-pyrrolidone as the aprotic polar solvent. , N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphotriamide and the like; As said phenolic solvent, For example, phenol, m-cresol, xylenol, a halogenated phenol etc .;

As said alcohol, For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4- butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc .; As said ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanol, etc .; As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methylmethoxypropionate, ethylethoxypropionate, diethyl oxalate, diethyl malonic acid, isoamylpropionate Isoamyl isobutyrate and the like;

As said ether, for example, 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, Tetrahydrofuran, diisopentyl ether and the like;

Examples of the halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like; As said hydrocarbon, For example, hexane, heptane, octane, benzene, toluene, xylene, etc .; Each can be mentioned.

Among these organic solvents, at least one selected from the group consisting of aprotic polar solvents and phenolic solvents (first group of organic solvents), or at least one selected from the first group of organic solvents, alcohols, Preference is given to using mixtures with at least one 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 second group of organic solvents is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total amount of the organic solvent of the first group and the organic solvent of the second group. More preferably, it is 30 weight% or less. It is preferable that the usage-amount (a) of an organic solvent sets it as the amount which the total amount (b) of tetracarboxylic dianhydride and diamine becomes 0.1-50 weight% with respect to the total amount (a + b) of a reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after isolating the polyamic acid contained in a reaction solution, or after refine | purifying the isolated polyamic acid, preparation of a liquid crystal aligning agent You may provide to. When polyamic acid is dehydrated and closed, and it is set as polyimide, the said reaction solution may be used for a dehydration ring-closure reaction as it is, may be used for dehydration ring-closure reaction after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid After purification, the dehydration ring-closure reaction may be used. Isolation and purification of polyamic acid can be performed according to a well-known method.

<Polyamic acid ester>

The polyamic acid ester as the polymer [A] contained in the liquid crystal aligning agent of the present invention is synthesized by, for example, esterifying the polyamic acid obtained by the above-described synthesis reaction using a hydroxyl group-containing compound or an ether compound. It can obtain by the method and the method of making [II] a tetracarboxylic-acid diester compound and diamine react. Here, as tetracarboxylic acid diester compound in method [II], the diester compound of tetracarboxylic acid which is a precursor of the said tetracarboxylic dianhydride is mentioned, Specifically, for example, tetracarboxylic acid di Ester dichloride, the tetracarboxylic acid diester which has two carboxyl groups, etc. are mentioned. Moreover, as diamine used in method [II], the diamine illustrated by description of the synthesis of the said polyamic acid is mentioned. In addition, the polyamic acid ester as polymer [A] may have only the dark acid ester structure, and the partial esterified product in which the dark acid structure and the dark acid ester structure coexist.

<Synthesis of Polyimide and Polyimide>

The polyimide contained in the liquid crystal aligning agent of this invention can be obtained by dehydrating and ring-closing the polyamic acid synthesize | combined as mentioned above, for example, and imidizing. By containing polyimide in the said liquid crystal aligning agent, various characteristics, such as liquid crystal aligning property, voltage preservation characteristic, heat resistance, and mechanical strength, can be improved.

The said polyimide may be a complete imide which dehydrated and closed all the dark acid structures which the polyamic acid which is the precursor has, and dehydrated and closed only a part of the dark acid structure, and the partial imide which the dark acid structure and the imide ring structure coexist. It may be. It is preferable that the imidation ratio of the polyimide in this invention is 30% or more, It is more preferable that it is 50 to 99%, It is further more preferable that it is 60 to 99%. This imidation ratio shows the ratio which the number of the imide ring structure to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage. Here, 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 by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating it as necessary. . Among these, it is preferable by the latter method.

In the method of adding a dehydrating agent and a dehydrating ring-closure catalyst in the solution of the polyamic acid, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the dark acid structure of polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing a polyimide is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, and may be provided to preparation of a liquid crystal aligning agent after isolating polyimide. You may provide it to the preparation of a liquid crystal aligning agent after refine | purifying an isolated polyimide. These purification operations can be performed according to a well-known method.

When the polyamic acid, the polyamic acid ester, and the polyimide obtained as described above have a solution having a concentration of 10% by weight, preferably have a solution viscosity of 10 to 800 mPa · s, and a solution viscosity of 15 to 500 mPa · s. It is more preferable to have. In addition, the solution viscosity (mPa * s) of the said polymer is the density | concentration 10weight prepared using the quantity solvent (for example, (gamma) -butyrolactone, N-methyl- 2-pyrrolidone, etc.) of the said polymer. It is the value measured at 25 degreeC using the E-type rotational viscometer about% polymer solution.

It is preferable that it is 1,000-500,000, and, as for the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography about polyamic acid, polyamic acid ester, and polyimide, it is more preferable that it is 2,000-300,000.

<Polyorganosiloxane>

The polyorganosiloxane as the polymer [A] contained in the liquid crystal aligning agent of the present invention, for example, hydrolyzes one or two or more of the hydrolyzable silane compounds, preferably in the presence of an organic solvent and a catalyst. It can obtain by the method of condensation. As a silane compound used for the said synthesis, the silane compound (si-3) etc. which are shown below are mentioned, for example. In addition, description of the hydrolysis-condensation reaction of the silane compound demonstrated by compound [D] is applicable about the organic solvent, catalyst, reaction conditions, etc. which are used for the said synthesis | combination.

It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography with respect to the said polyorganosiloxane is 500-100,000, It is more preferable that it is 1,000-50,000, It is further more preferable that it is 1,000-30,000.

The liquid crystal aligning agent of this invention is a polymer [A], The polymer selected from the group which consists of said polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane can be used individually by 1 type or in combination of 2 or more types You may contain it. In the liquid crystal aligning agent of this invention, although the content rate of each polymer with respect to the total amount of polymer [A] can be suitably selected according to the use and environment to be used, such as heat resistance of a coating film formed, mechanical strength, liquid crystal aligning property, etc. From a viewpoint, it is preferable that polymer [A] contains at least 1 sort (s) chosen from the group which consists of polyamic acid, polyamic acid ester, and polyimide, and contains at least 1 sort (s) chosen from the group which consists of polyamic acid and polyimide. More preferably, it is still more preferable that the polymer [A] is at least one selected from the group consisting of polyamic acid and polyimide.

When it contains at least any one of polyamic acid and a polyimide as polymer [A], it is preferable that content of the total is 1-100 weight% with respect to the total amount of polymer [A] contained in a liquid crystal aligning agent, It is more preferable that it is 5-100 weight%. In addition, as polymer [A], 1 type of the polymer shown above may be used independently, and may be used in combination of 2 or more type. Moreover, when using in combination of 2 or more type, the combination of a polymer with the same main skeleton may be sufficient, and the combination of a polymer from which a main skeleton is different.

Compound [D]

Compound [D] used in the present invention has two or more polymerizable unsaturated bonds in the molecule. In addition, a compound [D] means the thing which does not correspond to the compound [E] mentioned below among the compounds which have two or more polymerizable unsaturated bonds. Although the structure in the polymerizable unsaturated bond part of the said compound [D] is not specifically limited, As group which has a polymerizable unsaturated bond, group represented by following formula (3) (henceforth a specific group (g1)) is mentioned. It is preferable to have at least one, and it is more preferable to have two or more:

(In formula (3), R <^3> is a hydrogen atom or a methyl group, Y <^3> and Y <^4> are respectively independently an oxygen atom or a sulfur atom; "*" represents a bond.).

As Y <^3> and Y <^4> in said Formula (3), it is preferable that it is an oxygen atom from a viewpoint of expressing a desired pretilt angle characteristic with less light irradiation amount, respectively.

The compound [D] may be a monomer or a polymer, and specific examples thereof include a compound having, as a monomer, two or more polymerizable unsaturated bonds and a ring structure of at least one of a benzene ring and a cyclohexane ring (hereinafter, "specifically," Monomer ");

As the polymer, a compound having polyorganosiloxane, polyester, polyamic acid, polyimide and the like as a main skeleton, and having at least two polymerizable unsaturated bonds in the side chain; Each can be mentioned.

<Specific monomer>

The specific monomer is not particularly limited as long as it has two or more polymerizable unsaturated bonds and has a ring structure of at least one of a benzene ring and a cyclohexane ring. As a preferable specific example of the said specific monomer, the compound etc. which have two or more polymerizable unsaturated bonds, and the group represented by following formula (4) are mentioned, for example:

(Formula (4) of, Ac ¹ and Ac ² are, each independently, a benzene ring or a cyclohexane ring, which may have a substituent; X ^a is a single bond, a divalent hydrocarbon group having 1 to 4 carbon atoms, An oxygen atom, a sulfur atom or -COO-; "*" represents a bond.).

In said Formula (4), although Ac <^1> and Ac <^2> may be same or different, it is preferable that they are a benzene ring, respectively. In addition, each ring of Ac ¹ and Ac ² may have a substituent. As said substituent, For example, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a C1-C4 alkyl group, a C1-C4 fluoroalkyl group, a C1-C4 alkoxy group, a hydroxyl group, a cyan Anger etc. are mentioned.

The C1-C4 divalent hydrocarbon group for X ^a may be saturated or unsaturated, or may be linear or branched. As a specific example of the said hydrocarbon group, for example, a methylene group, an ethylene group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a propane-2,2-di Diary, butane-1,3-diyl group, butane-1,4-diyl group, butane-2,3-diyl group, vinylene group, and the like.

As a specific example of group represented by said Formula (4), the group etc. which are represented by each of following formula (4-1)-(4-6) etc. are mentioned, for example:

(In the formula, "*" represents a bonding hand.).

As said specific monomer, it is preferable that it is di (meth) acrylate which has two acryloyl group or a methacryloyl group as a polymerizable unsaturated bond, and it is especially preferable that it is a compound represented by following formula (D-1). .

(In formula (D-1), R <^2> is a hydrogen atom or a methyl group each independently, r1 and r2 are each independently 1 or 2, and s1 and s2 are the integers of 0-4 each independently; Ac ¹ , Ac ² and X ^a each have the same meaning as in Formula (4)).

As a specific example of the di (meth) acrylate represented by said formula (D-1), it is a di (meth) acrylate which has a biphenyl structure (group represented by said formula (4-1)), for example, 4'- (Meth) acryloyloxy-biphenyl-4-yl- (meth) acrylate, 2- [4 '-(2- (meth) acryloyloxy-ethoxy) -biphenyl-4-yloxy] -Ethyl (meth) acrylate, bishydroxyethoxybiphenyldi (meth) acrylate, 2- (2- {4 '-[2- (2- (meth) acryloyloxy-ethoxy)- Methoxy] -biphenyl-4-yloxy} -ethoxy) -ethyl (meth) acrylate, 2- (4'-acryloyloxy-biphenyl-4-yloxy) -ethyl (meth) acrylate, etc. of;

As di (meth) acrylate which has a phenyl-cyclohexyl structure (group represented by said formula (4-2)), for example, 4- (4- (meth) acryloyl ox-phenyl) -cyclohexyl (meth) Acrylate, 2- {4- [4- (2- (meth) acryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethyl (meth) acrylate, 2- [2- (4- {4- [2- (2- (meth) acryloyloxy-ethoxy) -ethoxy] -phenyl} -cyclohexyloxy) -ethoxy] -ethyl (meth) acrylate;

As di (meth) acrylate which has a 2, 2- diphenyl propane structure (group represented by said formula (4-3)), for example, 4- [1- (4- (meth) acryloyloxy-phenyl ) -1-methyl-ethyl] -phenyl (meth) acrylate, 2- (4- {1- [4- (2- (meth) acryloyloxy-ethoxy) -phenyl] -1-methyl-ethyl } -Phenoxy) -ethyl (meth) acrylate, bishydroxyethoxy-bisphenol A di (meth) acrylate, 2- {2- [4- (1- {4- [2- (2- (meth) ) Acryloyloxy-ethoxy) -ethoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -ethoxy} -ethyl (meth) acrylate, 2- (4- {1- [4- (2- (meth) acryloyloxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -1-methyl-ethyl (meth) acrylate, 2- {2- [4- (1 -{4- [2- (2- (Meta) acryloyloxy-propoxy) -propoxy] -phenyl} -1-methyl-1-ethyl) -phenoxy] -1-methyl-ethoxy}- 1-Methyl-ethyl (meth) acrylate, 3- {4- [1- (3- {1- [4- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-e Tyl} -phenyl) -1-methyl-ethylphenoxy-2-hydroxy-propyl (meth) acrylate, 3- (4- {1- [4- (3- (meth) acryloyloxy-2- Hydroxy-propoxy) -3-cyclohexyl-phenyl] -1-methyl-ethyl} -2-cyclohexyl-phenoxy) -2-hydroxy-2-propyl (meth) acrylate, 3- (5- {1- [6- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -biphenyl-3-yl] -1-methyl-ethyl} -biphenyl-2-yloxy)- 2-hydroxy-propyl (meth) acrylate, 3- {4- [1- (4- {1- [4- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -3 -Methyl-phenyl] -1-methyl-ethyl} -phenyl) -1-methyl-ethyl] -2-methyl-phenoxy} -2-hydroxy-propyl (meth) acrylate, 3- (4- {1 -[4- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -2-hydroxy-propyl (meth) acrylate, 3- [4- (1- {4- [3- (4- {1- [4- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl- Ethyl} -phenoxy) -2 -Hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -2-hydroxy-propyl (meth) acrylate, 3- {4- [1- (4- {3- [4 -(1- {4- [3- (4- {1- [4- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy C) -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy} -2 -Hydroxy-propyl (meth) acrylate, 1- (2- {4- [1- (4- {2- [2-hydroxy-3- (1-methylene-allyloxy) -propoxy] -prop Foxy} -phenyl) -1-methyl-ethyl] -phenoxy} -1-methyl-ethoxy) -3- (1-methylene-allyloxy) -propan-2-ol and the like;

As di (meth) acrylate which has a diphenylmethane structure (group represented by said formula (4-4)), for example, 4- (4- (meth) acryloyloxy-benzyl) -phenyl (meth) acryl Rate, 2- {4- [4- (2- (meth) acryloyloxy-ethoxy) -benzyl] -phenyl} -ethyl (meth) acrylate, 2- [2- (4- {4- [ 2- (2- (meth) acryloyloxy-ethoxy) -ethoxy] -benzyl} -phenoxy) -ethoxy] -ethyl (meth) acrylate, 2- {4- [4- (2- (Meth) acryloyloxy-propoxy) -benzyl-phenoxy} -1-methyl-ethyl (meth) acrylate, 2- [2- (4- {4- [2- (2- (meth) acrylic) Loyloxy-propoxy) -propoxy] -benzyl} -phenoxy) -1-methyl-ethoxy] -1-methyl-ethylethyl (meth) acrylate, formula (D-1-1) or formula (D-1-2):

(In formula, R <^2> is respectively independently a hydrogen atom or a methyl group.)

Compounds represented by each of;

As di (meth) acrylate which has a diphenylthioether structure (group represented by said formula (4-5)), for example, 4- (4-thio (meth) acryloylsulfanyl-phenylsulfanyl) -phenyl Dithio (meth) acrylate, bis (4-methacryloylthiophenyl) sulfide, etc .;

As other di (meth) acrylate, For example, 2, 5-bis {4- (3-acryloyloxy-propoxy)-benzoic acid} toluene, etc .; Each can be mentioned. In addition, in this specification, "(meth) acrylate" means "acrylate" and "methacrylate", and "(meth) acryloyloxy" means "acryloyloxy" and "methacryl" Iloxy ”.

The said di (meth) acrylate can be synthesize | combined by combining suitably the method of organic chemistry, and can obtain it as a commercial item. As di (meth) acrylate, said thing can be used individually by 1 type or in combination of 2 or more types.

On the other hand, when the said compound (D) is a polymer, the compound (henceforth "specific polyorganosiloxane" hereafter) which makes polyorganosiloxane the main skeleton can be used preferably.

<Specific polyorganosiloxane>

The specific polyorganosiloxane as the compound [D] in the present invention has two or more groups having a polymerizable unsaturated bond in the side chain of the polyorganosiloxane skeleton. As group which has the said polymerizable unsaturated bond, it is preferable that it is group represented by said formula (3), and it is especially preferable that it is acryloyl group or methacryloyl group.

It is preferable that the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) is 500-100,000, as for specific polyorganosiloxane, it is more preferable that it is 1,000-50,000, and it is more preferable that it is 1,000-10,000. Do.

The specific polyorganosiloxane is, for example,

(1a) a method of hydrolytically condensing a hydrolyzable silane compound (si-1) having a polymerizable unsaturated bond or a mixture of the silane compound (si-1) with another silane compound;

(2a) a polymer (epoxy group-containing polyorganosiloxane) obtained by hydrolytically condensing a hydrolyzable silane compound (si-2) containing an epoxy group or a mixture of the silane compound (si-2) with another silane compound; And a method of reacting carboxylic acid (C-1) having a polymerizable unsaturated bond; Etc. can be obtained.

[Silane compound (si-1)]

The silane compound (si-1) may have at least one polymerizable unsaturated bond, and examples thereof include a compound represented by the following formula (s-1):

(In formula (s-1), X is a halogen atom, a C1-C4 alkoxy group, or a C1-C4 alkyl group each independently. However, two or more X of three X which exists in a molecule | numerator is , A halogen atom or an alkoxy group having 1 to 4 carbon atoms, n is an integer of 1 to 6, and R ³ , Y ³ and Y ⁴ each have the same meaning as in Formula (3).

In the formula (s-1), the divalent group "-C _n H _2n- " may be linear or branched, for example, methylene group, ethylene group, propane-1,1-diyl group, propane- 1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, butane-2,3-di Diary, pentane-1,5-diyl group, pentane-2,4-diyl group, heptane-1,6-diyl group, etc. are mentioned. Among these, n is preferably an integer of 1 to 5, and more preferably linear such as ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, and the like.

As X, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example; As a C1-C4 alkoxy group, For example, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc .; 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; Each can be mentioned.

Two or more of X in a molecule | numerator should just be a halogen atom or a C1-C4 alkoxy group, but it is preferable that all three are a halogen atom or a C1-C4 alkoxy group. In addition, three X which exists in a molecule may respectively be same or different.

As a preferable specific example of a silane compound (si-1), 3- (meth) acryloxypropyl trimethoxysilane, 1- (meth) acryloxymethyl trimethoxysilane, 2- (meth) acryloxyethyl tree, for example Methoxysilane, 4- (meth) acryloxybutyl trimethoxysilane, 5- (meth) acryloxypentyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 1- (meth) acryloxy Methyltriethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, 5- (meth) acryloxypentyltriethoxysilane, (meth) acrylic acid- 2-hydroxy-5- (trimethoxysilanyl) -pentyl ester, (meth) acrylic acid-1-hydroxymethyl-4- (trimethoxysilanyl) -butyl ester, etc. are mentioned.

In the synthesis | combination of specific polyorganosiloxane, especially among these, 3-methacryloxypropyl trimethoxysilane and 3-acryloxypropyl trimethoxysilane can be used preferably. In addition, as a silane compound (si-1), it can be used individually by 1 type or in combination of 2 or more types.

In the above, "(meth) acryloxy" includes both "acryloxy" and "methacryloxy".

[Silane compound (si-2)]

Although the structure is not specifically limited as long as it has an epoxy group, It is preferable that a silane compound (si-2) has group represented by a following formula (ep-1) or a formula (ep-2). Moreover, as group represented by said Formula (ep-1) or Formula (ep-2), 3-epoxypropyl group, 3-glycidyloxypropyl group, and 2- (3, 4- epoxycyclohexyl) ethyl group are especially mentioned. desirable:

(In formula (ep-1), A is a single bond or an oxygen atom, h is an integer of 1 to 3, i is an integer of 0 to 6; provided that when i is 0, A is J is an integer of 1-6 in formula (ep-2); "*" represents a bond with a silicon atom.

As a preferable specific example of a silane compound (si-2), for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane , 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. are mentioned. Among these, at least any of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane can be particularly preferably used. In addition, as a silane compound (si-2), it can be used individually by 1 type or in combination of 2 or more types.

[Other Silane Compounds (si-3)]

In the synthesis | combination of specific polyorganosiloxane, the silane compound (other silane compound (si-3)) of that excepting the above can also be used. As said other silane compound (si-3), what is necessary is just a hydrolyzable silane compound which does not have a polymerizable unsaturated bond and an epoxy group, As a specific example, tetramethoxysilane, tetraethoxysilane, methyltrimeth Methoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mer Captomethyl triethoxysilane, dimethyldimethoxysilane, dimethyl diethoxysilane, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

[Hydrolytic Condensation Reaction of Silane Compounds]

The hydrolytic condensation reaction of the silane compound in the present invention can be carried out by reacting one or two or more kinds of the above silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent.

When synthesize | combining specific polyorganosiloxane by the said method (1a), the silane compound used for synthesis may use compound (si-1) independently, and other silane compound with compound (si-1) As a silane compound (si-2) and another silane compound (si-3), you may use together at least. The use ratio of the silane compound (si-1) is preferably 5 mol% or more, more preferably 10 to 70 mol%, and more preferably 20 to 50 mol, based on the total amount of the silane compound used for the reaction. It is more preferable to set it as%.

When synthesize | combining specific polyorganosiloxane by the said method (2a), the silane compound used for synthesis may use compound (si-2) independently, and with other compound (si-2), another silane compound As a silane compound (si-1) and another silane compound (si-3), you may use together at least. The use ratio of the silane compound (si-2) 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 used for the reaction. More preferably.

The use ratio of water used at the time of a hydrolysis condensation reaction becomes like this. Preferably it is 0.5-100 mol with respect to 1 mol of total of a silane compound, More preferably, it is 1-30 mol.

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. are mentioned, for example. Specific examples of these catalysts include, for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids, and the like;

As an alkali metal compound, For example, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc .;

As the organic base, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole:

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene:

Quaternary organic amines such as tetramethylammonium hydroxide and the like; Each can be mentioned. As an organic base, tertiary organic amine or quaternary organic amine is preferable among these.

As said catalyst, an alkali metal compound or the like can be suppressed from the viewpoint of suppressing side reactions such as ring-opening of an epoxy group, increasing the rate of hydrolysis condensation, and excellent storage stability. Organic bases are preferred, especially organic bases.

Although the usage-amount of an organic base differs according to reaction conditions, such as a kind of organic base, temperature, etc., it should be set suitably, For example, with respect to all the silane compounds, Preferably it is 0.01-3 times mole, More preferably, it is 0.05- 1 mole.

As an organic solvent which can be used at the time of a hydrolysis condensation reaction, a hydrocarbon, a ketone, ester, an ether, alcohol, etc. are mentioned, for example.

As the specific example, As a hydrocarbon, For example, toluene, xylene, etc .;

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

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

As the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;

Examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like; Each can be mentioned.

It is preferable to use a water-insoluble organic solvent among these. In addition, these organic solvents can be used individually by 1 type or in mixture of 2 or more types.

The use ratio of the organic solvent in a hydrolysis condensation reaction becomes like this. Preferably it is 10-10,000 weight part with respect to 100 weight part of all silane compounds, More preferably, it is 50-1,000 weight part.

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 with, for example, an oil bath.

At the time of a hydrolysis condensation reaction, heating temperature becomes like this. Preferably it is 130 degrees C or less, More preferably, it is 40-100 degreeC, Preferably it is 0.5 to 12 hours, More preferably, it is preferable to heat 1 to 8 hours. During the heating, the mixed liquid may be stirred or placed under reflux.

It is preferable to wash | clean the organic solvent layer fractionated from the reaction liquid after completion | finish of reaction with water. At the time of this washing | cleaning, it wash | cleans using water containing a small amount of salts, for example about 0.2 weight% of ammonium nitrate aqueous solution, etc., and is preferable at the point which a washing operation becomes easy. Washing is performed until the water layer after washing | cleaning becomes neutral, and after drying an organic solvent layer with drying agents, such as anhydrous calcium sulfate and molecular sieves as needed, and then removing a solvent, the target polyorganosiloxane is carried out. (In the case of method (1a), a specific polyorganosiloxane, and in the case of method (2a), an epoxy-group containing polyorganosiloxane) can be obtained.

[Carbonic Acid (C-1)]

When obtaining compound [D] in this invention by the said method (2a), as long as it has a polymerizable unsaturated bond as carbonic acid (C-1) used for reaction with an epoxy-group containing polyorganosiloxane, The structure is not particularly limited. As a preferable specific example of such a carbonic acid (C-1), For example, acrylic acid, methacrylic acid, 2-acryloxyethyl-2-hydroxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, The compound etc. which are represented by each of following formula (c-1)-(c-20) are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

[Reaction of Epoxy-containing Polyorganosiloxane with Carbonic Acid (C-1)]

The reaction between the epoxy group-containing polyorganosiloxane and the carbonic acid (C-1) is preferably carried out in the presence of a catalyst and an organic solvent.

As carbonic acid used for reaction of an epoxy-group containing polyorganosiloxane and carbonic acid (C-1), carbonic acid (C-1) can be used individually or in combination with other carbonic acid. As other carbonic acid which can be used here, formic acid, acetic acid, propionic acid, benzoic acid, methyl benzoic acid, etc. are mentioned, for example.

It is preferable that it is 30 mol% or more with respect to the total amount of carboxylic acid used for reaction, and, as for the usage ratio of carbonic acid (C-1), it is more preferable to set it as 35 mol% or more.

In addition, the usage ratio of the carbonic acid (total amount) is preferably 5 mol% or more, more preferably 10 to 80 mol%, and even more preferably 15 to the epoxy group of the epoxy group-containing polyorganosiloxane. It is -60 mol%, Especially preferably, it is 20-40 mol%.

Moreover, compound [D] can be made into the polyorganosiloxane which further has an epoxy group by making the use ratio of carbonic acid less than the epoxy group which an epoxy group containing polyorganosiloxane has.

As a catalyst used for reaction, a well-known compound etc. can be used as a so-called hardening accelerator which accelerates | stimulates the reaction of an organic base and an epoxy compound, for example.

Here, as said organic base, Primary and secondary organic amines, such as ethylamine, diethylamine, piperazine, a piperidine, a pyrrolidine, a pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;

Quaternary organic amines such as tetramethylammonium hydroxide; Etc. can be mentioned. As an organic base, tertiary organic amine or quaternary organic amine is preferable among these.

Moreover, as said hardening accelerator, For example, tertiary amines, such as benzyl dimethylamine 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, ethyltriphenylphosphonium bromide;

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

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;

Boron compounds such as boron trifluoride and triphenyl borate;

Metal halide compounds such as zinc chloride and tin tin;

High-melting-point dispersion | distribution type latent hardening accelerators, such as an amine addition type | mold promoter, such as an adduct of dicyandiamide, an amine, and an epoxy resin; Microcapsule-type latent curing accelerators in which a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer; Amine salt type latent curing accelerators; Latent curing accelerators such as high-temperature dissociation-type thermocationic polymerization-type latent curing accelerators such as Lewis salts and Brönstedates; Etc. can be mentioned. Among them, quaternary ammonium salts are preferable.

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

As an organic solvent which can be used in reaction of an epoxy-group containing polyorganosiloxane and carbonic acid (C-1), a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound etc. are mentioned, for example. have. Among them, ether compounds, ester compounds, ketone compounds are preferable from the viewpoint of solubility of raw materials and products and purification of products, and as examples of particularly preferred solvents, 2-butanone, 2-hexanone, methyliso Butyl ketone, butyl acetate, etc. are mentioned.

As for an organic solvent, it is preferable to use it in the ratio which solid content concentration (the ratio which the total weight of components other than the solvent in a reaction solution occupies for the total weight of a solution) becomes 0.1 weight% or more, and the ratio which becomes 5-50 weight% It is more preferable to use as.

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

[Vertical Orientation Group]

When applying the liquid crystal aligning agent of this invention to the liquid crystal display element of a vertical alignment type, the specific polyorganosiloxane as compound [D] may have a vertical alignment group for providing favorable vertical alignment property with respect to a coating film. Examples of such a vertically oriented group 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, a group having a polycyclic structure, and the like. Can be mentioned.

Here, as said alkyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, n-octade, for example Practical skills;

Examples of the fluoroalkyl group include trifluoromethylpropyl group, trifluoromethylbutyl group, trifluoromethylhexyl group, trifluoromethyldecyl group, pentafluoroethylpropyl group, and pentafluoroethylbutyl group. And pentafluoroethyloctyl group;

As said alkoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a hexyloxy group, an octyloxy group etc. are mentioned, for example;

Examples of the group having a steroid skeleton include a cholestanyl group, a cholesteryl group, a lanostanyl group, and the like;

As a group which has a polycyclic structure, it is a 4,4'-biphenylene group, a 4,4'-bicyclohexylene group, and a following formula, for example.

A group having at least one selected from the group consisting of; Each can be mentioned.

As a method of introducing a perpendicular alignment group into specific polyorganosiloxane, for example,

(1b) a method of reacting a polyorganosiloxane having a polymerizable unsaturated bond and an epoxy group with a carbonic acid (C-2) having the vertically oriented group;

(2b) a method of reacting an epoxy group-containing polyorganosiloxane with the carbonic acid (C-1) and the carbonic acid (C-2);

(3b) A method of reacting a polyorganosiloxane having a polymerizable unsaturated bond with at least one nucleophilic compound (r1) selected from the group consisting of a thiol compound having the vertically oriented group and an amine compound having the vertically oriented group. ;

Etc. can be obtained.

[Carbonic Acid (C-2)]

In the case where the introduction of the vertically aligned group into the specific polyorganosiloxane is carried out by the method (1b) or the method (2b), as the carbonic acid (C-2) to react with the epoxy group of the polyorganosiloxane, the liquid crystal aligning group As long as it has, the structure is not specifically limited. As a preferable specific example of such a carbonic acid (C-2), it is, for example,

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, 4-stearylbenzoic acid;

4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-hexadecyloxybenzoic acid, 4-stearyloxybenzoic acid, etc. Benzoic acid having a long chain alkoxy group;

Cholestanyloxybenzoic acid, cholestenyloxybenzoic acid, ranostanyloxybenzoic acid, cholestanyloxycarbonylbenzoic acid, cholestenyloxycarbonyl benzoic acid, ranostanyloxycarbonylbenzoic acid, succinic acid-5ξ-cholestane-3 Benzoic acid having a steroid backbone such as -yl, succinic acid-5ξ-cholester-3-yl, and succinic acid-5ξ-lanostane-3-yl;

4- (4-pentyl-cyclohexyl) benzoic acid, 4- (4-hexyl-cyclohexyl) benzoic acid, 4- (4-heptyl-cyclohexyl) benzoic acid, 4'-pentyl-bicyclohexyl-4-carboxylic acid, 4'-hexyl-bicyclohexyl-4-carboxylic acid, 4'-heptyl-bicyclohexyl-4-carboxylic acid, 4'-pentyl-biphenyl-4-carboxylic acid, 4'-hexyl-biphenyl-4 -Carboxylic acid, 4'-heptyl-biphenyl-4-carboxylic acid, 4- (4-pentyl-bicyclohexyl-4-yl) benzoic acid, 4- (4-hexyl-bicyclohexyl-4-yl) benzoic acid Benzoic acid containing polycyclic structures, such as 4- (4-heptyl-bicyclohexyl-4-yl) benzoic acid and 6- (4'-cyanobiphenyl-4-yloxy) hexanoic acid;

Carbonic acid containing fluoroalkyl groups such as 6,6,6-trifluorohexanoic acid and 4- (4,4,4-trifluorobutyl) benzoic acid; Etc. can be mentioned respectively. These can be used individually by 1 type or in combination of 2 or more types.

In addition, when a vertically oriented group is introduce | transduced by the method (2b), carbonic acid (C-2) is contained in "other carbonic acid" in the said method (2a).

In the reaction of the epoxy group of the polyorganosiloxane with the carbonic acid (C-2), when the method (1b) is used, the proportion of the carbonic acid (C-2) used is the total amount of the carbonic acid used for the reaction. It is preferable to set it as 75 mol% or more with respect to it, and it is more preferable to set it as 90 mol% or more.

On the other hand, the use ratio of the carbonic acid (C-2) in the case of using the method (2b) is preferably 40 to 70 mol%, and 50 to 65 mol% based on the total amount of the carbonic acid used for the reaction. It is more preferable to set it as.

In addition, each condition, such as the catalyst and organic solvent which can be used for reaction, reaction temperature, reaction time, is the catalyst, organic solvent, reaction demonstrated in reaction of the said epoxy group containing polyorganosiloxane and carbonic acid (C-1). Description of each condition, such as temperature and reaction time, is applicable.

[Nucleophilic Compound (r1)]

On the other hand, when the introduction of the vertically oriented group into a specific polyorganosiloxane by the method of the above (3b), as the nucleophilic compound (r1), a mercapto group or -NHR (where R is a hydrogen atom or The structure is not limited as long as it has a C1-C6 alkyl group) and the said vertically oriented group. As such a nucleophilic compound (r1),

As the amine compound, for example, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, hepta Primary amines such as decylamine, octadecylamine, nonadecylamine, 4- (4-pentylcyclohexyl) -phenylamine, and 4-octyloxyphenylamine;

For example, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, Secondary amines such as dipentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, dinonadecylamine; Etc. can be mentioned.

As the thiol compound, butane thiol, pentane thiol, hexane thiol, heptane thiol, octane thiol, nonane thiol, decanthiol, undecane thiol, dodecane thiol, tridecane thiol, tetradecane thiol, pentadecane thiol , Hexadecanethiol, heptadecanthiol, octadecanethiol, nonadecanthiol, 4-butylbenzenethiol, 4-pentylbenzenethiol, 4-hexylbenzenethiol, 4-heptylbenzenethiol, 4-octylbenzenethiol, 4-decyl Benzenethiol, 4-dodecylbenzenethiol, 4-tetradecylbenzenethiol, 4-hexadecylbenzenethiol, 4-butoxybenzenethiol, 4-hexyloxybenzenethiol, 4-octyloxybenzenethiol, 4-dodecyloxy Benzenethiol, 4- (4'-butylcyclohexyl) benzenethiol, 4- (4'-hexylcyclohexyl) benzenethiol and the like; Can be mentioned.

[Reaction of Polyorganosiloxane Having Polymeric Unsaturation Bond with Nucleophilic Compound (r1)]

The reaction between the polyorganosiloxane having a polymerizable unsaturated bond and the nucleophilic compound (r1) is preferably carried out in the presence of a catalyst and an organic solvent.

When introducing a perpendicular alignment group into a specific polyorganosiloxane by the method (3b), as an amino compound or thiol compound used for reaction, you may use a nucleophilic compound (r1) independently, Together, at least any of other amino compounds and other thiol compounds may be used. Specifically, as other amino compounds, For example, amino acid derivatives, such as glycine and alanine, 4-aminobenzoic acid, sarcosine, etc .; Examples of other thiol compounds include thioglycolic acid, mercaptopropionic acid, mercaptobutanoic acid, 4-mercaptobenzoic acid, N-acetylcysteine, and the like; Can be mentioned.

It is preferable that it is 1 mol% or more with respect to the polymerizable unsaturated bond group which specific polyorganosiloxane has, and, as for the usage ratio of the nucleophilic compound (r1) in the said reaction, it is more preferable that it is 3-50 mol% or more, 5 It is more preferable that it is-30 mol%.

As said organic solvent, a polar compound can be used preferably, For example, a nitrile, a sulfoxide, an ether, ester, etc. are mentioned. As these specific examples, As a nitrile, For example, acetonitrile etc .; As sulfoxide, For example, dimethyl sulfoxide etc .; As the ether, for example, diethyl ether, dipropyl ether and the like; As ester, For example, ethyl acetate, butyl acetate, etc .; Each can be mentioned. Moreover, when a nucleophilic compound (r1) is an amine, alcohol can also be used as an organic solvent. As a specific example of the said alcohol, trifluoro ethanol, hexafluoro ethanol, etc. are mentioned, for example.

It is preferable to use the solvent in the ratio which solid content concentration (the ratio which the total weight of components other than the solvent in a reaction solution occupies for the total weight of a solution) becomes 40 weight% or more from a viewpoint of reaction rate, 50-90 It is more preferable to use it in the ratio used as weight%.

As a catalyst used for reaction, when a nucleophilic compound (r1) is an amine, aluminum chloride, formic acid, etc. are mentioned, for example. Moreover, when a nucleophilic compound (r1) is thiol, organic base etc. are mentioned, for example, 3, such as trimethylamine, diethylmethylamine, ethyldimethylamine, triethylamine, tripropylamine, etc. are mentioned. A tertiary amine can be used preferably.

Reaction temperature becomes like this. Preferably it is 10-100 degreeC, More preferably, it is 40-80 degreeC. The reaction time is preferably 0.5 to 8 hours, more preferably 1 to 6 hours.

In addition, when using specific polyorganosiloxane as a compound [D], you may use what is marketed as polyorganosiloxane which has a (meth) acryloyl group. As such a commercial item, AC-SQ, MAC-SQ (above, Toagosei Co., Ltd. make), PSS- (1-propyl methacrylate) -heptaisobutyl substituent (Sigma-Aldrich Japan Co., Ltd. make) ); Etc. can be mentioned.

When the polymer [A] is contained in the said liquid crystal aligning agent, the use ratio of the compound [D] in the liquid crystal aligning agent of this invention is 1-100 weight part with respect to 100 weight part of polymer [A]. Do. By setting it as 1 weight part or more, even the comparatively small light irradiation amount can provide favorable pretilt angle characteristic with respect to a coating film, and can speed up the response speed of liquid crystal molecule sufficiently. Moreover, by setting it as 100 weight part or less, the content rate of a polymer [A] can be increased, and the liquid crystal aligning property and electrical property of the coating film formed by this can be made favorable. As said usage ratio, it is more preferable that it is 1-70 weight part, and it is still more preferable that it is 3-50 weight part.

Compound [E]

Compound [E] is a compound having a molecular weight of 2,000 or less having an epoxy group and a polymerizable unsaturated bond, and examples thereof include a compound represented by the following formula (1):

(In formula (1), Z is an epoxy group, W is a group which has a polymerizable unsaturated bond, R <^1> is a (m + n) valent organic group; m and n are each independently an integer of 1-8.).

Although it does not specifically limit as a bivalent organic group of R <^1> in said Formula (1), For example, a C1-C20 hydrocarbon group etc. are mentioned. The hydrocarbon group may be any of a linear hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Here, a chain hydrocarbon group means the saturated hydrocarbon group and unsaturated hydrocarbon group comprised only with a chain structure, without including a cyclic structure in a principal chain. However, both linear and branched forms are included. In addition, an alicyclic hydrocarbon group means a hydrocarbon group which contains only the structure of an alicyclic hydrocarbon as a ring structure, and does not contain an aromatic ring structure. However, it does not need to consist only of the structure of an alicyclic hydrocarbon, but includes the thing which has a linear structure in one part. An aromatic hydrocarbon means the hydrocarbon group which contains an aromatic ring structure as ring structure. However, it is not necessary to be comprised only with an aromatic ring structure, and the structure of a linear structure and an alicyclic hydrocarbon may be included in the one part. In addition, the divalent organic group of R ¹ may have -O-, -COO-, -CO-, -NH-, -NH-CO-, etc. between the carbon-carbon bonds in the said hydrocarbon group, and is a halogen atom Or an alkoxy group, hydroxyl group, cyano group or the like.

The integer of 1-5 is preferable, and, as for m and n, the integer of 1-3 is more preferable.

As W, it is good if it is a group which has a polymerizable unsaturated bond, and the structure is not specifically limited, It is preferable that at least 1 is group represented by following formula (2) (henceforth a specific group (g2)).

(In Formula (2), R <^2> is a hydrogen atom or a methyl group, Y <^1> and Y <^2> are an oxygen atom or a sulfur atom each independently; "*" represents a bond.

It is preferable that Y <^3> and Y <^4> in said Formula (2) are oxygen atoms, respectively.

The molecular weight of compound [E] is 2,000 or less, It is preferable that it is 1,500 or less from a viewpoint of uniform dispersibility in a solution, and it is more preferable that it is 1,000 or less.

Compound [E] is, for example,

(1c) A compound having a polymerizable unsaturated bond is introduced into a part of the epoxy group of the compound (ex-1) by reacting a compound (ex-1) having two or more epoxy groups with a carboxylic acid having a polymerizable unsaturated bond. Way;

(2c) at least one nucleophilic compound (ex-3) selected from the group consisting of a compound (ex-2) having two or more polymerizable unsaturated bonds, an amino compound having an epoxy group and a thiol compound having an epoxy group; A method of introducing an epoxy structure into a part of the polymerizable unsaturated bonds of the compound (ex-2) by reacting;

Etc. can be obtained.

In addition, a compound [E] can use the compound obtained by the said method (1c) or (2c) individually by 1 type or in combination of 2 or more types.

About method (1c)

[Compound (ex-1)]

If the compound (ex-1) has two or more epoxy groups, the structure thereof is not particularly limited, but for example, a compound represented by the following formula (e1-1) can be used:

(In formula (e1-1), Z is an epoxy group and R <^5> is a m-valent organic group; m is an integer of 2-6.).

In formula (e1-1), R <^5> is a m-valent organic group. In addition, the description of R <^1> in said Formula (1) is applicable to the specific example of the said organic group.

It is preferable that it is 2-4, and, as for m, it is more preferable that it is 2 or 4.

As a preferable specific example of a compound (ex-1), for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-p-phenylenediamine, N, N, N', N ' Tetraglycidyl-m-phenylenediamine, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N, N', N'-tetragly Cydyl-4,4'-diaminodiphenylether, N, N, N ', N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, trimethylolpropanetriglycol Cydylether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-digle Cydylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-di Glycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, N, N, N ', N'-tetraglycidyl-1,2-diaminocyclohexane, N, N, N ', N'- tetraglycidyl-1,3-diaminocyclohexane, N, N, N', N'-tetraglycidyl-1,4-diaminocyclohexane, bis (N, N- Diglycidyl-4-aminocyclohexyl) methane, bis (N, N-diglycidyl-2-methyl-4-aminocyclohexyl) methane, bis (N, N-diglycidyl-3-methyl 4-aminocyclohexyl) methane, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane, 1 , 3-bis (N, N-diglycidylaminomethyl) benzene, 1,4-bis (N, N-diglycidylaminomethyl) benzene, 1,3,5-tris (N, N-di Glycidylaminomethyl) cyclohexane, 1,3,5-tris (N, N-digle Sidil aminomethyl) benzene, the following formula (e1-1-1) ~ (e1-1-3):

The compound etc. which are represented by each of these are mentioned.

[Carboxylic Acids Having Polymeric Unsaturation]

As carbonic acid which has a polymerizable unsaturated bond which can be used by the said method (1c), what was illustrated as a specific example of the said carbonic acid (C-1), etc. are mentioned, for example. In addition, as said carbonic acid, said thing can be used individually by 1 type or in mixture of 2 or more types.

[Reaction of Compound (ex-1) with Carbonic Acid]

The reaction between the compound (ex-1) and the carboxylic acid having a polymerizable unsaturated bond is preferably performed in the presence of a catalyst and an organic solvent.

The use ratio of the carboxylic acid having a polymerizable unsaturated bond in the reaction is 0.01 to 10 equivalents, preferably 0.1 to 3 equivalents, and 0.2 to 1 to 1 equivalent of the epoxy group of the compound (ex-1). It is more preferable that it is equivalent.

Reaction temperature becomes like this. Preferably it is 10-200 degreeC, More preferably, it is 50-120 degreeC, More preferably, it is 70-110 degreeC. The reaction time is preferably 0.5 to 20 hours, more preferably 1 to 10 hours.

The organic solvent is not particularly limited as long as the compound (ex-1) and the carboxylic acid having a polymerizable unsaturated bond can be dissolved. As a preferable specific example of the said organic solvent, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, N, N- dimethylformamide, N, N- dimethylacetamide, etc. are mentioned, for example.

As for the said organic solvent, it is preferable to use solid content concentration (the ratio which the total weight of components other than the solvent in a reaction solution occupies for the total weight of a solution) from 1 to 50 weight% from a reaction rate viewpoint, and is 3-40 It is more preferable to use by weight%, and it is still more preferable to use by 5-20 weight%. Moreover, as said catalyst, the compound illustrated as a catalyst which can be used for reaction of the said epoxy group containing polyorganosiloxane and carbonic acid (C-1) is mentioned. As a catalyst used for reaction, quaternary ammonium salt is especially preferable.

In addition, at the time of the said reaction, in order to prevent gelation, you may add a commercial polymerization inhibitor, for example.

About method (2c)

[Compound (ex-2)]

As a compound which has a polymerizable unsaturated bond used by the said method (2c), the compound which has two or more said specific groups (g2) can be used preferably, for example. As the specific example, the compound etc. which were illustrated as a specific example of the di (meth) acrylate in the said specific monomer are mentioned, for example. In addition, as a compound (ex-2), said thing can be used individually by 1 type or in mixture of 2 or more types.

[Nucleophilic Compound (ex-3)]

The nucleophilic compound (ex-3) is a compound having a mercapto group or -NHR (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and an epoxy group, and the rest of the structure is not particularly limited. . As a preferable specific example of a nucleophilic compound (ex-3), it is an amino compound which has an epoxy group, for example, 1, 2- epoxy ethylamine, 2, 3- epoxy propylamine, 3, 4- epoxy butylamine, N-methyl. -1,2-epoxyethylamine, N-ethyl-2,3-epoxypropylamine, N-methyl-2,3-epoxypropylamine, N-ethyl-2,3-epoxypropylamine, etc .; As the thiol compound having an epoxy group, for example, 2,3-epoxypropane-1-mercaptan, 3,4-epoxybutane-1-mercaptan, 4,5-epoxy-n-pentane-1-mercaptan, 5 , 6-epoxy-n-hexane-1-mercaptan and the like; Each can be mentioned.

[Reaction of Compound (ex-2) with Nucleophilic Compound (ex-3)]

The reaction between the compound (ex-2) having two or more polymerizable unsaturated bonds and the nucleophilic compound (ex-3) is preferably carried out in the presence of a catalyst and an organic solvent.

The use rate of a nucleophilic compound (ex-3) is 0.01-10 equivalent, 0.1-3 equivalent, with respect to 1 equivalent of the polymerizable unsaturated bond group which compound (ex-2) has, and 0.2-1 equivalent It is more preferable that is.

Regarding the conditions that can be used in the reaction, such as a catalyst, an organic solvent, and a reaction temperature, each of the catalyst, organic solvent, reaction temperature, and the like described in the reaction of the specific polyorganosiloxane with the nucleophilic compound (r1) The description of the condition is applicable.

When the polymer [A] is contained in the said liquid crystal aligning agent, the use ratio of the compound [E] in the liquid crystal aligning agent of this invention is 1-100 weight part with respect to 100 weight part of polymer [A]. Do. By setting it as 1 weight part or more, the long-term heat resistance of the liquid crystal aligning film formed can be made more favorable, and by setting it as 100 weight part or less, the content rate of a polymer component can be increased, and, thereby, the mechanical strength and liquid crystal alignability of a coating film And electrical characteristics can be made favorable. As said usage ratio, it is more preferable that it is 1-70 weight part, and it is still more preferable that it is 3-50 weight part.

On the other hand, in the said liquid crystal aligning agent, when it contains a specific polyorganosiloxane (compound [D]) without containing a polymer [A] as a polymer component, it is 1 with respect to 100 weight part of specific polyorganosiloxanes. It is preferable that it is -100 weight part, It is more preferable that it is 1-50 weight part, It is still more preferable that it is 3-20 weight part.

As the polymer component in the liquid crystal aligning agent of the present invention, the compound [D], that is, the specific polyorganosiloxane may be contained alone, but the polymer [A] is contained alone or in combination with the specific polyorganosiloxane. desirable. By including a polymer [A] in a liquid crystal aligning agent, various characteristics, such as liquid crystal aligning property of a coating film formed, voltage retention, heat resistance, and mechanical strength, can be improved.

Here, in the liquid crystal aligning agent containing a polymer [A] and a specific polyorganosiloxane as the said polymer component, although a desired pretilt angle characteristic can be provided to a coating film with comparatively small light irradiation amount, coating unevenness in a coating film This may become easy to express. This is assumed to be due to the low viscosity of polyorganosiloxane. In this and the mixed system of a polymer [A] and a specific polyorganosiloxane, coating nonuniformity in the coating film formed using the said liquid crystal aligning agent by containing compound [E] as a structural component of a liquid crystal aligning agent. Can be suppressed suitably.

<< other ingredients >>

The liquid crystal aligning agent of this invention may contain other components as needed. As such other components, the compound which has at least 1 epoxy group in a molecule other than the said polymer [A], other polymers other than a specific polyorganosiloxane, and the said compound [E] (henceforth "epoxy group containing Compound ", and a functional silane compound.

<Other polymer>

The said other polymer can be used for the improvement of a solution characteristic and an electrical property. Examples of such other polymers include polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates.

When adding another polymer to a liquid crystal aligning agent, 50 weight% or less is preferable with respect to the total polymer amount in the said composition, as for the compounding ratio, 0.1-40 weight% is more preferable, 0.1-30 weight% is further desirable.

<Epoxy group-containing compound>

An epoxy group containing compound can be used in order to improve adhesiveness and electrical characteristics with the board | substrate surface in a liquid crystal aligning film. Here, as an epoxy group containing compound, For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglyci Dyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol di Glycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N- diglycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane, N, N- diglycidyl cyclohexylamine etc. are mentioned as a preferable thing.

In addition, as an example of an epoxy group containing compound, the epoxy group containing polyorganosiloxane as described in international publication 2009/096598 can also be used.

When adding these epoxy compounds to a liquid crystal aligning agent, 40 weight part or less is preferable with respect to a total of 100 weight part of polymers contained in a liquid crystal aligning agent, and 0.1-30 weight part is more preferable.

<Functional silane compound>

The said functional silane compound can be used for the purpose of the improvement of the printability of a liquid crystal aligning agent. As such a functional silane compound, for example, 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-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 9-tri Methoxysilyl-3,6-diazanyl acetate, 9-trimethoxysilyl-3,6-methyl diazanonanate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. Can.

When adding these functional silane compounds to a liquid crystal aligning agent, 2 weight part or less is preferable with respect to a total of 100 weight part of polymers, and, as for the compounding ratio, 0.02-0.2 weight part is more preferable.

Moreover, as another component, the compound, antioxidant, etc. which have at least 1 oxetanyl group in a molecule | numerator can be used in addition to the above.

"menstruum"

The said compound [D], the compound [E], and the other component arbitrarily mix | blended as needed, the liquid crystal aligning agent of this invention, Preferably melt | dissolve in an organic solvent, and are comprised.

Here, as a solvent used for preparation of the liquid crystal aligning agent of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol Methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, di 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 can be used individually or in mixture of 2 or more types.

Solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is selected suitably in consideration of viscosity, volatility, etc., Preferably It is the range of 1-10 weight%. That is, although the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate as mentioned later, Preferably it heats, the coating film which becomes a coating film which is a liquid crystal aligning film, or a liquid crystal aligning film is formed, At this time, when solid content concentration is less than 1 weight% The film thickness of this coating film becomes too small and a favorable liquid crystal aligning film cannot be obtained. On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and a favorable liquid crystal aligning film cannot be obtained, and the viscosity of a liquid crystal aligning agent increases and it becomes inferior to coating property.

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% of solid content concentration is especially preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC.

<< liquid crystal aligning film and liquid crystal display element >>

The liquid crystal aligning film of this invention is formed of the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed using the said liquid crystal aligning agent. Although the operation mode of the said liquid crystal display element is not specifically limited, It is especially preferable that it is a vertical alignment type. While the manufacturing method of the liquid crystal display element of this invention is demonstrated below, the manufacturing method of the liquid crystal aligning film of this invention is demonstrated also in the description. In addition, below, the manufacturing method of a vertically-aligned liquid crystal display element is given and demonstrated as an example.

[First Step: Formation of Coating Film]

First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and then a coating film is formed on a board | substrate by heating a coating surface.

First, two board | substrates with which the patterned transparent conductive film is formed are made into a pair, and the liquid crystal aligning agent of this invention is respectively preferably formed on the formation surface of the transparent conductive film in these board | substrates, Preferably the offset printing method and spin coating are carried out. It apply | coats respectively by the method, the roll coater method, or the inkjet printing method. Here, as a board | substrate, For example, glass, such as float glass and a 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 formed on one surface of the substrate, an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. Can be. In order to obtain a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photo-etching, a method using a mask having a desired pattern when forming a transparent conductive film, or the like can be employed. . At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, etc. The pretreatment applied in advance may be performed.

After apply | coating a liquid crystal aligning agent, preheating (prebaking) is preferably performed for the purpose of liquid flow prevention of the apply | coated liquid crystal aligning agent. Prebaking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. Prebaking time becomes like this. Preferably it is 0.25-10 minutes, More preferably, it is 0.5-5 minutes. Thereafter, the solvent is completely removed and a firing (postbaking) step is performed for the purpose of thermally imidizing the dark acid structure present in the polymer as necessary. Post-baking temperature becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Post-baking time becomes like this. Preferably it is 5-200 minutes, More preferably, it is 10-100 minutes. Thus, the film thickness of the film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

The coating film used as an oriented film is formed by removing an organic solvent by the heating after apply | coating a liquid crystal aligning agent. At this time, when the polymer contained in the liquid crystal aligning agent of this invention is a polyamic acid, a polyamic acid ester, or the imidation polymer which has an imide ring structure and a dark acid structure, dehydration ring-closure reaction is advanced by further heating after coating film formation. It is good also as a coating film which was imidated more.

Although the coating film formed as mentioned above can be used as a liquid crystal aligning film as it is, you may perform a rubbing process as needed.

Second Process: Construction of Liquid Crystal Cell

The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as mentioned above, and arrange | positioning a liquid crystal between two board | substrates which oppose. Here, when the rubbing process is performed with respect to a coating film, two board | substrates are mutually arrange | positioned so that the rubbing direction in each coating film may mutually become a predetermined angle, for example, orthogonal or antiparallel.

In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method (vacuum injection method). First, two substrates are disposed to face each other via a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealing agent and partitioned by the substrate surface and the sealing agent. After injecting and filling a liquid crystal in a cell gap, a liquid crystal cell is manufactured by sealing an injection hole. The second method is a method called an ODF (One Drop Fill) method. After apply | coating an ultraviolet-ray curable sealing compound, for example to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, and further dropping liquid crystal in predetermined several places on the liquid crystal aligning film surface, a liquid crystal aligning film is A liquid crystal cell is manufactured by bonding another board | substrate so that it opposes, spreading a liquid crystal on the whole surface of a board | substrate, then irradiating ultraviolet light to the whole surface of a board | substrate, and hardening a sealing compound. In any case, the liquid crystal cell produced as described above is preferably further heated to a temperature at which the used liquid crystal takes an isotropic phase, and then gradually cooled to room temperature to remove the flow orientation during liquid crystal filling. Do.

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

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferable, and for example, a sieve base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal and an ester liquid crystal , Terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, and cuban-based liquid crystals. Moreover, for these liquid crystals, For example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agent sold as brand names "C-15" and "CB-15" (made by Merck); Strong dielectric liquid crystals, such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate; You may add and use.

It is preferable that the thickness of the layer of liquid crystal molecules shall be 1-5 micrometers.

[3rd process: light irradiation process]

After construction 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 applied here can be, for example, 5 to 50 V DC or alternating current.

As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used, for example. In addition, the ultraviolet-ray of the said preferable wavelength range can be obtained by means of using a light source together with a filter, a diffraction grating, etc., for example.

As an irradiation amount of light, Preferably it is 1,000 J / m <2> or less than 100,000 J / m <2>, More preferably, it is 1,000-50,000 J / m <2>. For example, in the manufacture of the liquid crystal display element of the conventionally known PSA mode, although it was necessary to irradiate about 100,000 J / m <2> light, in the manufacturing method of the liquid crystal display element in this invention, the amount of light irradiation is 50,000 J. Even if it is / m <2> or less, Furthermore, even when it is set to 10,000 J / m <2> or less, the liquid crystal display element which has a desired pretilt angle characteristic can be obtained, and it contributes to the reduction of the manufacturing cost of a liquid crystal display element. Moreover, the fall of the electrical characteristic resulting from strong light irradiation, and the fall of the response of the liquid crystal molecule with respect to a voltage change can be suppressed.

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

As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which consists of a polarizing plate called "H film" which absorbed iodine while extending | stretching polyvinyl alcohol, and sandwiched between the cellulose acetate protective films, or the H film itself is mentioned. .

The liquid crystal display element of the present invention can be effectively applied to various devices, and includes, for example, a clock, a portable game, a word processor, a notebook PC, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, It can be used for various display devices, such as a smart phone, various monitors, a liquid crystal television, and an information display.

EXAMPLE

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

The solution viscosity of each polymer solution in a synthesis example, the imidation ratio of polyimide, and the weight average molecular weight of the polymer were measured by the following method.

[Solution Viscosity of Polymer Solution]

The solution viscosity [mPa * s] of a polymer solution was measured at 25 degreeC using the E-type rotational viscometer about the solution prepared at 10 weight% of polymer concentration using the predetermined solvent.

[Imidation Rate of Polyimide]

The solution of polyimide was put into pure water, the obtained precipitate was dried under reduced pressure sufficiently at room temperature, dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the formula represented by the following formula (1x):

Imidation ratio [%] = {(1-A ¹ ) / (A ² × α)} × 100. (1x)

(In Formula (1x), A <^1> is the peak area derived from the proton of the NH group which shows around 10 ppm of chemical shifts, A <^2> is the peak area derived from other protons, and (alpha) is a precursor (polyamic acid) of a polymer. Number ratio of other protons to one proton of NH group).

[Weight Average Molecular Weight of Polymer]

The weight average molecular weight Mw of a polymer is a polystyrene conversion value measured by the gel permeation chromatography on the following conditions.

Column: Tosoh Corporation, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf / ㎠

In addition, epoxy equivalent is the value measured according to the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

The following synthesis examples were repeated on the following synthesis scale as needed, and the product of the required amount used by the following synthesis example, the Example, and the comparative example was ensured.

<Synthesis of Polymer [A]>

Synthesis Example 1

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 43 g (0.40 mol) of p-phenylenediamine and 3- (3,5-diaminobenzoyloxy) as diamine 52 g (0.10 mol) of cholesterol was dissolved in 830 g of N-methyl-2-pyrrolidone (NMP), and reaction was performed at 60 degreeC for 6 hours. A small amount of the obtained polyamic acid (PA-1) solution was aliquoted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration by adding NMP was 60 mPa * s.

Subsequently, 1,900 g of NMP were added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring reaction, the solvent in the system was substituted with fresh NMP (pyridine and acetic anhydride used in the dehydration ring reaction in this operation were removed to the outside of the system) to thereby remove polyimide (PI-1) having an imidization rate of about 50%. A solution containing about 15% by weight was obtained. The obtained polyimide solution was fractionated and the solution viscosity measured as a solution of 10 weight% of polyimide concentration by adding NMP was 47 mPa * s.

<Synthesis of Compound [D]>

Synthesis Example 2

To a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 378 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 375 g of 3-methacryloxypropyltrimethoxysilane, and methyl isobutyl 753 g of ketone and 75 g of triethylamine were added and mixed at room temperature. Subsequently, 602.3 g of deionized water was dripped over 30 minutes from the dropping funnel, and it reacted at 60 degreeC for 6 hours, mixing under reflux. After completion | finish of reaction, the organic layer was taken out and washed with the 0.2 weight% ammonium nitrate aqueous solution until the water after washing became neutral. Thereafter, the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane (EPS-1) as a viscous transparent liquid. The weight average molecular weight Mw of this polyorganosiloxane (EPS-1) was 2,900.

Synthesis Example 3

In a 200 mL three-necked flask, 10.0 g of polyorganosiloxane (EPS-1), 74.10 g of methyl isobutyl ketone, 3.08 g of 4- (trans-4-N-pentylcyclohexyl) benzoic acid (polyorganosiloxane (EPS- It corresponded to 20 mol% with respect to the silicon atom which 1) has, and 0.10 g of brand names "UCAT 18X" (the hardening accelerator of an epoxy compound, the San Afro Corporation make) were added, and it reacted at 90 degreeC, stirring for 72 hours. After the completion of the reaction, methanol was added to the reaction mixture to form a precipitate. The solution obtained by dissolving the precipitate in ethyl acetate was washed three times with water, and then the solvent was distilled off to give white color of the polyorganosiloxane (D-1). 7.8 g of powder were obtained. The weight average molecular weight Mw of the polyorganosiloxane (D-1) was 3,800.

Synthesis Example 4

To a 200 mL three-necked flask equipped with a thermometer, a brand name "AC-SQ TA100" (hydrolysis condensate of 3-acryloxypropyltrimethoxysilane, manufactured by Toagosei Co., Ltd.) 33.0 g, 1-octadecane thiol 5.73 g (corresponding to 10 mol% of the silicon atoms of AC-SQ TA100), 6.37 g of mercaptopropionic acid (corresponding to 30 mol% of the silicon atoms of AC-SQ TA100), 45.1 g of acetonitrile, and 16.2 g of triethylamine were added thereto. Was reacted at 50 ° C for 1 hour. After the reaction was completed, polyorganosiloxane (D-2) was obtained by distilling acetonitrile and triethylamine off under reduced pressure. The weight average molecular weight Mw of the polyorganosiloxane (D-2) was 3,300.

<Synthesis of Compound [E]>

Synthesis Example 5

In a 100 mL three-necked flask equipped with a reflux tube, a nitrogen introduction tube and a thermometer, 4.2 g of N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 38.5 g and tetrabutylammonium bromide were added 0.42g and methacrylic acid 2.58g, and it was made to react at 90 degreeC for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed three times with 100 mL of water. Next, after adding 68 g of butyl cellosolves and concentrating to 45 g, again, 68 g of butyl cellosolves were added and concentrated to 45 g, and the solution of compound (E-1) having a solid content concentration of 10% by adding butyl cellosolve. Got.

Synthesis Example 6

In a 100 mL three-necked flask equipped with a reflux tube, a nitrogen introduction tube and a thermometer, 4.2 g of N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 33.5 of NMP 0.42 g of tetrabutylammonium bromide and 1.71 g of methacrylic acid were added, and it was made to react at 90 degreeC for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed three times with 100 mL of water. Next, after adding 68 g of butyl cellosolves and concentrating to 45 g, again, 68 g of butyl cellosolves were added and concentrated to 45 g, and the solution of compound (E-2) having a solid content concentration of 10% by adding butyl cellosolve. Got.

Synthesis Example 7

In a 100 mL three-necked flask equipped with a reflux tube, nitrogen introduction tube and thermometer, 4.2 g of N, N, N ', N'-tetraglycidyl-m-xylenediamine, 35.2 g of NMP, and tetrabutylammonium bromide 0.42g and 2.01g of methacrylic acid were added, and it was made to react at 90 degreeC for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed three times with 100 mL of water. Next, after adding 68 g of butyl cellosolves and concentrating to 45 g, again, 68 g of butyl cellosolves were added and concentrated to 45 g, and the solution of compound (E-3) having a solid content concentration of 10% by adding butyl cellosolve. Got.

Synthesis Example 8

In a 100 mL three-necked flask equipped with a reflux tube, nitrogen introduction tube, and thermometer, 4.2 g of N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 31.9 NMP were used. 0.42 g of tetrabutylammonium bromide and 1.43 g of acrylic acid were added, and it was made to react at 90 degreeC for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed three times with 100 mL of water. Next, 68 g of butyl cellosolves were added and concentrated to 45 g. Then, 68 g of butyl cellosolves were added and concentrated to 45 g. Then, a solution of compound (E-4) having a solid content concentration of 10% was added. Got.

Synthesis Example 9

In a 100 mL three-necked flask equipped with a reflux tube, nitrogen introduction tube and thermometer, 4.2 g of N, N, N ', N'-tetraglycidyl-m-xylenediamine, 33.3 g of NMP, and tetrabutylammonium 0.42g of bromide and 1.68g of acrylic acid were added, and it was made to react at 90 degreeC for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed three times with 100 mL of water. Next, after adding 68 g of butyl cellosolves and concentrating to 45 g, again, 68 g of butyl cellosolves were added and concentrated to 45 g, and the solution of compound (E-5) having a solid content concentration of 10% by adding butyl cellosolve. Got.

<Preparation of liquid crystal aligning agent>

Example 1

To the solution containing polyimide (PI-1) as a polymer, NMP and butyl cellosolve (BC) are added as an organic solvent, and compound (E-1) as compound [E] and compound as compound [D] (D-1) was added so that the content ratio of polyimide (PI-1), compound (E-1) and compound (D-1) contained in the polymer solution was 100: 10: 10 (weight ratio), and the solvent The composition was made into the solution of NMP: BC = 50: 50 (weight ratio), and solid content concentration 8.0 weight%. The liquid crystal aligning agent was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

<Manufacturing and Evaluation of Liquid Crystal Display Element>

The pattern (two types) and ultraviolet irradiation amount (three levels) of the transparent electrode were changed using the liquid crystal aligning agent prepared above, and six liquid crystal display elements were produced in total. In addition, various characteristics were evaluated about the manufactured liquid crystal display element.

[Production of Liquid Crystal Cell Having Patternless Transparent Electrode]

The liquid crystal aligning agent prepared above was apply | coated on the transparent electrode surface of the glass substrate which has a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printing machine (made by Nippon Shashin Inc.), and for 1 minute on an 80 degreeC hotplate After heating (prebaking) to remove the solvent, it was heated (postbaking) for 10 minutes on a 150 ° C hot plate to form a coating film having an average film thickness of 600 kPa.

About this coating film, the rubbing process was performed by the rubbing machine which has the roll which wound the rayon cloth at roll rotation speed 400rpm, stage movement speed of 3 cm / sec, and hair pressing indentation length of 0.1 mm. Thereafter, ultrasonic cleaning was performed 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 and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to each outer edge which has the liquid crystal aligning film of the said pair of board | substrates, it overlaps and crimps | bonds so that a liquid crystal aligning film surface may face, and an adhesive agent Was cured. Next, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a transparent electrode without a pattern. One of them was used for evaluation of the pretilt angle mentioned later as it was. Each of the remaining two liquid crystal cells was irradiated with light while a voltage was applied between the conductive films by the following method.

To two of the liquid crystal cells obtained above, an alternating current of 10 Hz at a frequency of 60 Hz is applied between the electrodes, respectively, and in the state where the liquid crystal is driven, the ultraviolet light is 10,000 J / using an ultraviolet irradiation device using a metal halide lamp as the light source. Irradiation was carried out at an irradiation dose of 2 m 2 or 100,000 J / m 2. In addition, this irradiation amount is the value measured using the photometer measured with the wavelength 365nm reference. Light irradiation amount 100,000J / m <2> is the value normally employ | adopted in PSA mode.

<Evaluation of Liquid Crystal Display Element>

[Evaluation of Pretilt Angle]

For each liquid crystal display device manufactured above, Non-Patent Document 1 (TJ Scheme et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)) and Non-Patent Document 2 (F. Nakano, et al., In accordance with the method described in JPN.J.Appl.Phys.vol. 19, p.2013 (1980)), the tilt angle from the substrate surface of the liquid crystal molecules was measured by a crystal rotation method using a He-Ne laser beam. . This measured value was made into the pretilt angle. The pretilt angles of the non-irradiated liquid crystal display element, the liquid crystal display element of irradiation amount 10,000J / m <2>, and the liquid crystal display element of irradiation amount 100,000J / m <2> are shown in following Table 2, respectively.

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

Among the liquid crystal display elements manufactured above, after applying ultraviolet rays to the liquid crystal cell, a voltage holding ratio of 167 milliseconds after the release of application was applied after applying a voltage of 5 V at 23 ° C. with an application time of 60 microseconds and a 167 millisecond span. (Initial VHR) was measured.

Next, the liquid crystal display element after the measurement of initial stage VHR was left still for 5,000 hours in oven set to the temperature of 120 degreeC, respectively. Then, the voltage holding ratio (VHR after heat stress) was measured similarly to the above. Each of these voltage holding ratios (%) is shown in Table 2 below.

In addition, VHR-1 by Toyo Technica Co., Ltd. was used as a measuring apparatus.

[Production of Liquid Crystal Display Device Having Patterned Transparent Electrode]

Liquid crystal aligning agent of Example 1 prepared above was patterned in the slit shape as shown in FIG. Apply using an alignment film printing machine (manufactured by Nippon Shashin Insatsu Co., Ltd.), and remove the solvent by heating (prebaking) on a hot plate at 80 ° C. for 1 minute, and then heating it on a hot plate at 150 ° C. for 10 minutes (postbaking) To form a coating film having an average film thickness of 600 kPa. About this coating film, after performing ultrasonic cleaning in ultrapure water for 1 minute, it dried in a 100 degreeC clean oven for 10 minutes, and obtained the board | substrate which has a liquid crystal aligning film. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained. In addition, the pattern of the used electrode is a pattern similar to the electrode pattern in PSA mode.

Subsequently, after apply | coating the aluminum-oxide oxide containing epoxy resin adhesive of 5.5 micrometers in diameter to each outer edge which has the liquid crystal aligning film of the said pair of board | substrates, it overlapped and crimp | bonded so that the liquid crystal aligning film surface could face and hardened the adhesive agent. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a patterned transparent electrode. One of them was used for evaluation of the response speed of the liquid crystal molecule mentioned later as it was. For the remaining two liquid crystal cells, light was emitted at an irradiation amount of 10,000 J / m 2 or 100,000 J / m 2 in a state where a voltage was applied between the conductive films by the same method as in the case of manufacturing a liquid crystal display element having a transparent electrode without a pattern. After the investigation, the response speed of the liquid crystal molecules was evaluated.

[Evaluation of Response Rate of Liquid Crystal Molecules]

About each liquid crystal display element manufactured above, the brightness of the light which permeate | transmitted the liquid crystal display element by irradiating a visible light lamp first without applying a voltage was measured with the photomultimeter, and this value was made into 0% of the relative transmittance | permeability. Next, the transmittance | permeability when AC 60V was applied for 5 second between electrodes of a liquid crystal display element was measured similarly to the above, and this value was made into 100% of the relative transmittance | permeability. When AC 60V is applied to each liquid crystal display element, the time until the relative transmittance transitions from 10% to 90% is measured, and this time is defined as the response speed, and the change from voltage off to voltage on The response of the liquid crystal molecule was evaluated. The response speeds of the liquid crystal display element of unexposed light, the liquid crystal display element of irradiation amount 10,000J / m <2>, and the liquid crystal display element of irradiation amount 100,000J / m <2> are shown in following Table 2, respectively.

[Examples 2 to 43 and Comparative Examples 1 and 2]

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the types and amounts of the polymer [A], the compound [D], and the compound [E] to be contained in the liquid crystal aligning agent were changed as shown in Table 1 below. did. In addition, using these liquid crystal aligning agents, the liquid crystal display element was produced like Example 1, and the produced liquid crystal display element was evaluated. The evaluation results are shown in Table 2.

In Table 1, the abbreviated-name of a compound is as follows.

<Compound [D]>

Compound (D-3); A mixture of compounds in which n is an integer of 2 to 4 in the formula (d-1):

(N is an integer of 2-4 each independently in formula (d-1).).

Compound (D-4); "AC-SQ TA100" (Toagose Corporation)

<Other components>

Compound (F-1); 2,4,6-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene

Compound (F-2); N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

As shown in Table 2, in Examples 1-43, even when light irradiation was performed at a comparatively low irradiation amount at 10,000 J / m <2>, while showing favorable pretilt angle, the response speed of liquid crystal molecules was also fast enough. In this regard, in Examples 1 to 43, it was found that the desired pretilt angle characteristic can be imparted to the coating film with a smaller light irradiation amount.

Moreover, in Examples 1-43, even after giving high temperature stress for a long time, it turned out that high voltage retention is maintained and it is excellent in long-term heat resistance.

On the other hand, in the comparative example 1 which does not contain compound [D], even if light irradiation was performed at 100,000 J / m <2>, the pretilt angle and response speed hardly changed with the case of light unirradiation. Moreover, in the comparative example 2 which does not contain compound [E], the fall amount of the voltage retention after high temperature stress provision was large, and long-term heat resistance was inferior.

Claims (12)

Compound [E] which has an epoxy group and a polymerizable unsaturated bond, and has a molecular weight of 2,000 or less,
Containing compound [D] having two or more polymerizable unsaturated bonds (excluding those corresponding to compound [E]),
The compound [D] includes a polyorganosiloxane having two or more groups having a polymerizable unsaturated bond in the side chain of the polyorganosiloxane skeleton,
The said polyorganosiloxane is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC), 1,000-100,000, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 1,
The said compound [E] is a liquid crystal aligning agent represented by following formula (1):

(In formula (1), Z is an epoxy group, W is a group which has a polymerizable unsaturated bond, R <^1> is a (m + n) valent organic group; m and n are each independently an integer of 1-8.). The method according to claim 1 or 2,
The said compound [E] is a group which has the said polymerizable unsaturated bond, The liquid crystal aligning agent which has group represented by following formula (2):

(In Formula (2), R <^2> is a hydrogen atom or a methyl group, Y <^1> and Y <^2> are an oxygen atom or a sulfur atom each independently; "*" represents a bond. The method according to claim 1 or 2,
The said compound [E] is a liquid crystal aligning agent which is a reaction product of the compound which has two or more epoxy groups, and the carboxylic acid which has the said polymerizable unsaturated bond. The method according to claim 1 or 2,
The compound [E] is a liquid crystal aligning agent which is a reaction product of at least one selected from the group consisting of a compound having two or more of the above polymerizable unsaturated bonds, an amino compound having an epoxy group and a thiol compound having an epoxy group. The method according to claim 1 or 2,
Furthermore, the liquid crystal aligning agent containing at least 1 sort (s) of polymer [A] chosen from the group which consists of a polyamic acid, a polyamic acid ester, a polyimide, and a polyorganosiloxane. The method according to claim 1 or 2,
The said compound [D] is a group which has the said polymerizable unsaturated bond, The liquid crystal aligning agent which has 2 or more of groups represented by following formula (3):

(In formula (3), R <^3> is a hydrogen atom or a methyl group, Y <^3> and Y <^4> are respectively independently an oxygen atom or a sulfur atom; "*" represents a bond.). delete The method according to claim 1 or 2,
As said compound [D], the liquid crystal aligning agent containing the compound which has two or more of said polymerizable unsaturated bonds, and group represented by following formula (4):

(Formula (4) of, Ac ¹ and Ac ² are, each independently, a benzene ring or a cyclohexane ring, which may have a substituent; X is ^a, provided that a bond, a divalent hydrocarbon group having 1 to 4 carbon atoms, An oxygen atom, a sulfur atom or -COO-; "*" represents a bond.). The 1st process of apply | coating the liquid crystal aligning agent of Claim 1 or 2 on the said electrically conductive film of a pair of board | substrates which have a electrically conductive film, respectively, and then heating this to form a coating film,
A second step of constructing a liquid crystal cell by arranging a pair of substrates on which the coating film is formed so as to face each other so that the coating film faces through a layer of liquid crystal molecules;
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
Method for producing a liquid crystal display device comprising a. The liquid crystal aligning film formed using the liquid crystal aligning agent of Claim 1 or 2. The liquid crystal display element provided with the liquid crystal aligning film of Claim 11.

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