KR102038394B1 - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and manufacturing method for the liquid crystal display device - Google Patents

Abstract

(식 중, X는 수소 원자 또는 메틸기이고; L은, 단결합 또는 탄소수 1∼20의 알칸디일기이며, 당해 알칸디일기는, 산소 원자가 서로 이웃하지 않는 조건에서 산소 원자에 의해 1∼10회 중단되어 있어도 좋고; Y는, 단결합, -O-, -COO-, -OCO- 또는 -OCOO-이고; 환 A는 나프탈렌환임)(Problem) Provides the liquid crystal aligning agent which can provide the desired pretilt angle characteristic with respect to a coating film in 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 contains the polymer which has group represented by following formula (1).

(Wherein X is a hydrogen atom or a methyl group; L is a single bond or an alkanediyl group having 1 to 20 carbon atoms, and the alkanediyl group is 1 to 10 times by an oxygen atom under conditions where the oxygen atoms are not adjacent to each other) May be interrupted; Y is a single bond, -O-, -COO-, -OCO-, or -OCOO-; ring A is a naphthalene ring)

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

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 for manufacture of a liquid crystal display element of a vertical alignment type.

Conventionally, as the liquid crystal display element, various driving methods having 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.

Moreover, in recent years, PSA (Polymer Sustained Alignment) technology is proposed as a new technique for controlling the orientation of liquid crystal molecules in a liquid crystal display element (for example, refer patent document 1). This PSA technique polymerizes a polymerizable component by mixing the polymerizable component which polymerizes by light irradiation in the liquid crystal layer of a liquid crystal cell, and irradiating light to the liquid crystal cell in the state which inclined liquid crystal molecule by voltage application, It is a technique of controlling the molecular orientation of liquid crystal molecules.

However, in the case of controlling the alignment of liquid crystal molecules by PSA technology, it is necessary to perform light irradiation at a relatively high irradiation dose, and thus adversely affect the liquid crystal molecules and the coating film, thereby degrading the display quality of the liquid crystal display element. There is concern. On the other hand, when the amount of light irradiation is reduced, problems such as delayed response speed of liquid crystal molecules with respect to voltage change may occur in the obtained liquid crystal display device. Therefore, a technique for obtaining a liquid crystal display element having a sufficiently low response speed of a liquid crystal molecule to a voltage change while providing a desired pretilt angle characteristic to a coating film with a relatively small light irradiation amount has been proposed (for example, , Patent Document 2). This patent document 2 forms a liquid crystal aligning 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, and a liquid crystal cell Forming and manufacturing a liquid crystal display element by light-irradiating a liquid crystal cell in the state which applied the voltage between board | substrates is disclosed.

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

Background Art In recent years, liquid crystal display elements are not only used in display terminals such as personal computers as in the past, but also used in various kinds of applications such as, for example, liquid crystal televisions, car navigation systems, mobile phones, smart phones, and information displays. With such versatility, the demand for high performance of the liquid crystal display element is increasing, and as a liquid crystal aligning agent, in the technique which provides pretilt angle characteristic to a coating film by light irradiation, even if the amount of light irradiation is small, liquid crystal molecules It is desired to be able to obtain a liquid crystal display element having a sufficiently high response speed.

This invention is made | formed in view of the said subject, The liquid crystal aligning agent which can obtain the liquid crystal display element with a quick response speed of a liquid crystal molecule even if a small amount of light irradiation is given to a pretilt angle characteristic to a coating film by light irradiation. The 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 including the polymer which has a specific structure 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.

This invention provides the liquid crystal aligning agent containing the polymer (P) which has group represented by following formula (1) in one aspect.

(In formula (1), X is a hydrogen atom or a methyl group; L is a single bond or a C1-C20 alkanediyl group, The said alkanediyl group may branch and the oxygen atom does not mutually adjoin.) May be interrupted 1 to 10 times by an oxygen atom at Y; Y is a single bond, -O-, * ¹ -COO-, * ¹ -OCO- or -OCOO-, provided that "* ¹ " Ring A is a naphthalene ring; "*" represents a bond.

According to the liquid crystal aligning agent of this invention, by including the polymer (P) which has group represented by said formula (1) as a polymer component, it performs light irradiation with respect to the coating film formed using the said liquid crystal aligning agent, and pretilt angle characteristic. In the case of expressing, the liquid crystal display element having a sufficiently high response speed of the liquid crystal molecules can be obtained even with a relatively small amount of light irradiation.

In another aspect of the present invention, the liquid crystal aligning agent of the present invention is applied onto the conductive film of a pair of substrates having a conductive film, and the first step is then heated to form a coating film, and the coating film. The second step of forming the liquid crystal cell by arranging the pair of substrates formed so as to face the coating film via the layer of liquid crystal molecules to form a liquid crystal cell, and applying a voltage to the liquid crystal cell in a state where a voltage is applied between the conductive film of the pair of substrates It provides the manufacturing method of the liquid crystal display element containing the 3rd process of light irradiation.

When manufacturing a liquid crystal display element using the liquid crystal aligning agent of this invention, by employ | adopting the said method, even if a comparatively small light irradiation amount can provide desired pretilt angle characteristic with respect to a coating film, A liquid crystal display element with sufficiently fast response speed can be manufactured.

This invention provides the liquid crystal display element provided with the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention, and this liquid crystal aligning film in one aspect. Moreover, in another aspect, this invention provides the polymer (P) which has group represented by said formula (1), for example, the polyorganosiloxane which has group represented by said formula (1).

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

(Form to carry out invention)

Below, each component contained in the liquid crystal aligning agent of this invention, and the other component arbitrarily mix | blended as needed are demonstrated.

<Polymer (P)>

The liquid crystal aligning agent of this invention contains a polymer component, and contains the polymer (P) which has at least the group represented by following formula (1) as the said polymer component.

(In formula (1), X is a hydrogen atom or a methyl group; L is a single bond or a C1-C20 alkanediyl group, The said alkanediyl group may branch and the oxygen atom does not mutually adjoin.) May be interrupted 1 to 10 times by an oxygen atom at Y; Y is a single bond, -O-, * ¹ -COO-, * ¹ -OCO- or -OCOO-, provided that "* ¹ " Ring A is a naphthalene ring; "*" represents a bond.

As L1 of said Formula (1), as a C1-C20 alkanediyl group, linear or branched form may be sufficient, for example, a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, butane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, Octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, dodecyl-1,12-diyl group, tetradecyl-1,14-diyl group, hexadecyl- And 1,16-diyl groups, octadecyl-1,18-diyl groups, and icosane-1,20-diyl groups. The alkanediyl group may be interrupted 1 to 10 times by an oxygen atom provided that oxygen atoms are not adjacent to each other, and specifically, for example, "-(CH ₂ ) _a -O- (CH ₂ ) _b". (Wherein a and b are integers of 1 or more satisfying a + b≤20) and "-(CH ₂ ) _c -O- (CH ₂ ) _d -O- (CH ₂ ) _e- " (where c , d and e are groups represented by one or more integers satisfying c + d + e ≦ 20).

As L, from a viewpoint which can speed up the response speed of a liquid crystal molecule among the above, Preferably it is C4-C20, More preferably, it is C6-C20, More preferably, it is C8-20 will be.

The bonding position of Y in the naphthalene ring (ring A) and other groups (wherein the group is represented by a bonding hand) is not particularly limited, and specifically, 1,3-position, 1,4-position, 1, 5-position, 1,6-position, 1,7 position, 2,6-position, 2,7-position, etc. are mentioned. Especially, it is preferable that it is a 2, 6-position.

As a specific example of group represented by said formula (1), the following are mentioned, for example.

(In formula, X represents a hydrogen atom or a methyl group, and "*" represents a bond.).

Although the main chain skeleton of a polymer (P) is not specifically limited, For example, a polyorganosiloxane skeleton, a polyester skeleton, a polyamic acid skeleton, a polyimide skeleton, etc. are mentioned. Among these, it is preferable that it is a polyorganosiloxane skeleton in the point which is easy to introduce the group represented by said formula (1) to a polymer main chain. That is, it is preferable that the liquid crystal aligning agent of this invention contains the polyorganosiloxane (henceforth a specific polyorganosiloxane hereafter) which has group represented by said formula (1) as a polymer component.

<Specific polyorganosiloxane>

The specific polyorganosiloxane in this invention can be manufactured by combining suitably the method of organic chemistry. For example, as one method, it is obtained by hydrolyzing and condensing a hydrolyzable silane compound (si-1) containing an epoxy group or a mixture of the silane compound (si-1) and other silane compounds. The method of making a polymer (epoxy group containing polyorganosiloxane) and carbonic acid (C-1) which has group represented by said formula (1) react.

[Silane compound (si-1)]

Although the structure is not specifically limited as long as it has an epoxy group, It is preferable to have a group represented by a following formula (ep-1) or a formula (ep-2).

 (In formula (ep-1), Z is a single bond or an oxygen atom, h is an integer of 1-3, i is an integer of 0-6; However, when i is 0, Z is a 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-1), 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-1), said thing can be used individually by 1 type or in combination of 2 or more types.

[Other silane compounds]

As a specific example of the other silane compound which can be used for the synthesis | combination of a specific polyorganosiloxane, For example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, Phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 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]

In the synthesis of the specific polyorganosiloxane, the hydrolysis condensation reaction of the silane compound is 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. Can be.

When synthesize | combining specific polyorganosiloxane by the said method (iii), the usage ratio of the silane compound (si-1) used for synthesis is 70 mol% or more with respect to the total amount of the silane compound used for reaction. It is preferable to make it, it is more preferable to set it as 80 mol% or more, and it is more preferable to set it as 90 mol% or more.

In the hydrolysis condensation reaction, the use ratio of water is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, based on 1 mol of the silane compound (total amount).

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 or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole: triethylamine, tri-n-propylamine, tri-n- Tertiary organic amines such as 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 an organic base is preferable among these in the point which can suppress side reactions, such as ring-opening of an epoxy group, the point which can speed up hydrolysis condensation rate, and the point which is excellent in storage stability, Especially Organic bases are preferred.

The amount of the organic base used varies depending on the type of organic base, reaction conditions such as temperature, and the like, and should be appropriately set. For example, the amount of the organic base is preferably 0.01 to 3 times molar, more preferably 0.05 to the total silane compound. It is -1 time molar.

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 above-mentioned silane compound in an organic solvent, mixing the solution with an organic base and water, and heating it with, for example, an oil bath or the like.

At the time of a hydrolysis condensation reaction, it is preferable to make heating temperature 130 degrees C or less, and it is more preferable to set it as 40-100 degreeC. The heating time is preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During 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, washing | cleaning using water containing a small amount of salts (for example, about 0.2 weight% of ammonium nitrate aqueous solution etc.) is preferable at the point which a washing operation becomes easy. The washing is performed until the aqueous layer after washing is neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve, if necessary, and then the solvent is removed to remove the target polyorganosiloxane. (In the case of method (iii), an epoxy group containing polyorganosiloxane) can be obtained.

[Carbonic acid (C-1)]

Carbonic acid (C-1) used for reaction with an epoxy group containing polyorganosiloxane is a carboxyl group-containing compound which has group represented by said formula (1), and is represented by following formula (c1) specifically ,.

(In formula (c1), X, L, Y, and A are synonymous with said Formula (1).).

Although the binding position of the carboxyl group and Y in a naphthalene ring (ring A) is not specifically limited, It is preferable that it is a 2, 6-position.

As a preferable specific example of carboxylic acid (C-1), the compound etc. which are represented by each of following formula (c1-1) (c1-4)-etc. are mentioned, for example.

(Wherein X is a hydrogen atom or a methyl group).

[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.

At the time of 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, a propionic acid, benzoic acid, methyl benzoic acid, the carbonic acid which has a perpendicular orientation group mentioned later, etc. are mentioned, for example.

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

The use ratio of the carbonic acid (total amount) is preferably 5 mol% or more, more preferably 10 to 90 mol%, and even more preferably 15 to the epoxy group of the epoxy group-containing polyorganosiloxane. It is -80 mol%. Moreover, the polyorganosiloxane which has group and epoxy group which are represented by said formula (1) can be obtained 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, for example as a so-called hardening accelerator which accelerates | stimulates reaction of an organic base and an epoxy compound.

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.

As the curing 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 type latent hardening accelerators, such as an amine addition type accelerator, such as a dicyandiamide, the addition product of an amine, and an epoxy resin; Microcapsule-type latent curing accelerators in which a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer; Amine salt type latent hardening accelerator; Latent hardening accelerators, such as high temperature dissociation type | mold thermocationic polymerization type latent hardening accelerators, such as a Lewis acid salt and a Bronsted salt salt, etc .; 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, in view of solubility of raw materials and products and ease of purification of products, ether compounds, ester compounds, ketone compounds are preferred, and as examples of particularly preferred solvents, 2-butanone, 2-hexanone, methyliso Butyl ketone, butyl acetate, etc. are mentioned.

It is preferable to use the organic 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 in the total weight of a solution) becomes 0.1 weight% or more, and the ratio which becomes 5 to 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.

As a method of manufacturing the specific polyorganosiloxane in this invention, in addition to the said method (iii), (ii) the hydrolyzable silane compound (si-2) which has at least 1 group represented by said Formula (1), or The method of hydrolytically condensing the mixture of the said silane compound (si-2) and another silane compound is mentioned. The silane compound (si-2) used at the time of the synthesis by the method (ii) is, for example, a silane compound (si-1) having an epoxy group and a carboxylic acid (C-) having a group represented by the formula (1). It can obtain by making 1) react. In addition, as another silane compound, the compound etc. which were illustrated as "other silane compound" in description of the said method (i) can be used.

The use ratio of the silane compound (si-2) in the hydrolysis condensation reaction is preferably 5 mol% or more, more preferably 10 to 70 mol%, based on the total amount of the silane compound used for the reaction. Preferably, it is more preferable to set it as 20-50 mol%. In addition, the description of the hydrolysis condensation reaction of the said method (v) can apply as it is to the use ratio of water in a hydrolysis condensation reaction, the kind and quantity of a catalyst and an organic solvent, and various reaction conditions.

[Vertical Orientation Group]

When using the liquid crystal aligning agent of this invention for manufacture of a liquid crystal display element of a vertical alignment type, specific polyorganosiloxane may have the 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; Examples of the group having a polycyclic structure include a 4,4'-biphenylene group, a 4,4'-bicyclohexylene group, and the following formula:

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

As a method of manufacturing the specific polyorganosiloxane which has a perpendicular orientation group, For example, (I) the method of making epoxy group containing polyorganosiloxane, carbonic acid (C-1), and a carbonic acid which has a vertical orientation group react; (II) A method of reacting a polyorganosiloxane having a group represented by the formula (1) and an epoxy group with a carbonic acid having a vertically oriented group; (III) a method of reacting a polyorganosiloxane having a polymerizable unsaturated bond with a nucleophilic compound (thiol compound or amine compound) having a vertically oriented group; Etc. can be mentioned.

In the case of the said method (I) and (II), as a specific example of the carboxylic acid which has a perpendicular orientation group, for example, caproic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid Long chain fatty acids such as 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, cholestenyloxycarbonylbenzoic 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, in the said method (III), as a specific example of the nucleophilic compound which has a perpendicular orientation group, it is an amine compound, for example, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine , Dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, 4- (4-pentylcyclohexyl) -phenylamine, 4-octyloxy Primary amines such as phenylamine; Dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didododecylamine, ditridecylamine, ditetradecylamine, dipentadecyl Secondary amines such as amine, 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.

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

The quantity of the specific polyorganosiloxane contained in the liquid crystal aligning agent of this invention WHEREIN: In the liquid crystal display element manufactured using the said liquid crystal aligning agent, it is a liquid crystal aligning agent from a viewpoint which can fully speed up the response speed of liquid crystal molecules. It is preferable that it is 1 weight% or more with respect to the total amount of the polymer component contained, and it is more preferable that it is 5 weight% or more.

<Polymer (Q)>

In the case where the polymer (P) is a specific polyorganosiloxane, the polymer (P) may contain at least one polymer (Q) selected from the group consisting of polyamic acid and polyimide together with the specific polyorganosiloxane. By containing a polymer (Q), it is preferable at the point which can improve various characteristics, such as liquid crystal aligning property, voltage preservation characteristic, heat resistance, and mechanical strength, of the coating film formed using the said liquid crystal aligning agent.

When containing a specific polyorganosiloxane and a polymer (Q) as a polymer component, it is preferable that content of a polymer (Q) is 1 to 99 weight% with respect to the total amount of the polymer component contained in a liquid crystal aligning agent, It is more preferable that it is 10 to 95 weight%. By making content of a polymer (Q) into 1 weight% or more, the improvement effect, such as liquid crystal aligning property, voltage preservation characteristic, heat resistance, and mechanical strength, can be acquired suitably, and by setting it as 99 weight% or less by specific polyorganosiloxane The improvement effect of the response speed of a liquid crystal molecule can be acquired suitably.

<Polyamic acid>

The polyamic acid contained in the liquid crystal aligning agent of this invention can be synthesize | combined, for example by making tetracarboxylic dianhydride and diamine react.

[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-carboxymethylnorbornan-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 acid dianhydride and the like;

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

In addition to these, tetracarboxylic dianhydride described in JP 2010-97188 A and the like 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 synthesizing polyamic acid, it is preferable to use alicyclic tetracarboxylic dianhydride alone or to use a mixture of alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride. Do. 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 an aliphatic diamine, For example, 1, 1- metha xylylenediamine, 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) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m- Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3 , 6-diaminocarbazole, N-phenyl -3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4- Bis- (4-aminophenyl) -piperazine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1- (4-amino Phenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholesteryl Oxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoic acid, 3,5 Diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3- (3,5-diaminobenzoyloxy) cholestane, 3 , 6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyl Oxy) cyclohexyl-3,5-dia Nobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclo Hexane, 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 of 0 to 2, c is an integer of 1 to 20, n is 0 or 1, provided that a and b do not become 0 at the same time.

Compounds represented by these;

As diamino organosiloxane, For example, 1, 3-bis (3-aminopropyl)-tetramethyl disiloxane, etc .; In addition to each of them, the diamines described in JP 2010-97188 A can be used. As a diamine, these can be used individually by 1 type or in combination of 2 or more types.

The expression in (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. Two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.

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 a 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 anhydride, 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. ; 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 be used, 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 the 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, an aprotic polar solvent, a phenol and its derivative (s), 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, hexamethylphosphortriamide and the like; As said phenol derivative, For example, 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, cyclohexanone, etc .;

As said ester, For example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, etc .;

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 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, isoamyl propionate, isoamyl isobutylate, diisopentyl ether, etc .; Each can be mentioned.

Among these organic solvents, one or more selected from the group consisting of aprotic polar solvents and phenols and derivatives thereof (first group of organic solvents), or one or more kinds selected from first group of organic solvents, and alcohols It is preferable to use a mixture with at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second group of organic solvents). 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 of organic solvent (a) 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 it 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.

<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.

The said polyimide may be a complete imide which dehydrated and closed all the dark acid structures which the polyamic acid which is its precursor had, and dehydrated and closed only 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 the dehydrating agent and the dehydrating ring-closure catalyst to 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 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 provide it to preparation of a liquid crystal aligning agent after isolating polyimide. After refine | purifying the isolated polyimide, you may provide for preparation of a liquid crystal aligning agent. These purification operations can be performed according to a well-known method.

<Other components>

The liquid crystal aligning agent of this invention may contain other components as needed. As such other components, other polymers other than those mentioned above, the compound which has at least 1 epoxy group in a molecule | numerator (henceforth "epoxy group containing compound"), a functional silane compound, etc. are mentioned, for example.

[Other polymers]

The said other polymer can be used for the improvement of a solution characteristic and an electrical property. Examples of such other polymers include, for example, other polyorganosiloxanes, polyamic acid esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, and poly (styrene-phenylmaleimides) other than the specific polyorganosiloxanes. ) Derivatives, poly (meth) acrylates, and the like.

When adding another polymer to a liquid crystal aligning agent, 50 weight% or less is preferable with respect to the total amount of polymers in the said composition, 0.1-40 weight% is more preferable, and 0.1-30 weight% More preferred.

Epoxy-containing Compounds

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 epoxy group containing compound, the epoxy group containing polyorganosiloxane of international publication 2009/096598 can 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 0.02-0.2 weight part is more preferable.

As other components, in addition to the above, the compound, antioxidant, etc. which have at least one oxetanyl group in a molecule | numerator can be used.

<Solvent>

The liquid crystal aligning agent of this invention is a polymer component, and the other component mix | blended arbitrarily as needed, Preferably melt | dissolves in the organic solvent, and is 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 Tate, dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutylate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Although solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies in 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 Is in the range of 1 to 10% by 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 small and it is difficult to obtain a favorable liquid crystal aligning film. On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and it is difficult to obtain a favorable liquid crystal aligning film, and also the viscosity of a liquid crystal aligning agent increases and it is inferior to coating characteristic.

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, when using the spinner method, it is especially preferable to make solid content concentration into the range of 1.5 to 4.5 weight%. 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. Below, the manufacturing method of the liquid crystal aligning film and liquid crystal display element of this invention is demonstrated. In addition, below, the manufacturing method of the liquid crystal display element of a vertical alignment type is mentioned as an example and demonstrated.

[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 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 photoetching, a method of using a mask having a desired pattern when forming a transparent conductive film, or the like Can be. At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, etc. The pretreatment to be 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 to 10 minutes, More preferably, it is 0.5 to 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 or the imidation polymer which has an imide ring structure and a dark acid structure, it heats further after coating film formation, and it advances dehydration ring-closure reaction, and further imidizes. It is good also as a finished coating film.

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 arranged 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 using a sealing agent, and the substrate surface and the sealing agent are partitioned. 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 to the predetermined place on one board | substrate among two board | substrates which provided the liquid crystal aligning film, and further dropping a liquid crystal in predetermined several places on a liquid crystal aligning film surface, a liquid crystal A liquid crystal cell is manufactured by bonding another board | substrate so that an oriented film may oppose, 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 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. desirable.

As a sealing agent, the epoxy resin etc. which contain the aluminum oxide sphere as a hardening | curing agent and a spacer can be used, for example.

Examples of the liquid crystals 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, cuban-based liquid crystals, and the like. Moreover, for these liquid crystals, For example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agents as sold under the brand names "C-15" and "CB-15" (manufactured by Merck); Ferroelectric liquid crystals, such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, may be added and used.

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 more and less than 100,000 J / m <2>, More preferably, it is 1,000-50,000 J / m <2>. For example, in manufacture of the liquid crystal display element of the conventionally known PSA mode, it was necessary to irradiate about 100,000 J / m <2> light, but in the manufacturing method of the liquid crystal display element of this invention, the amount of light irradiation is 50,000 J / m <2>. Hereinafter, 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 contributes to 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 | membrane" which absorbed iodine while extending | stretching orientation of polyvinyl alcohol, the polarizing plate which sandwiched the cellulose acetate protective film with the cellulose acetate protective film, or the H film itself is mentioned. have.

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

[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 Corp., TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf / ㎠

[Epoxy equivalent]

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

[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. H-NMR spectrum obtained from ^1, to the imidization ratio was calculated (%) according to the equation represented by the 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).

<Synthesis of Polyorganosiloxane>

Synthesis Example 1

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 98.6 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone, and 10 g of triethylamine were added. It put and mixed at room temperature. Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and reaction was performed 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. Then, the solvent and water were distilled off under reduced pressure, and the polyorganosiloxane containing an epoxy group was obtained as a viscous transparent liquid. As a result of performing ¹ H-NMR analysis on the epoxy group-containing polyorganosiloxane, the peak based on the epoxy group was obtained according to the theoretical strength near the chemical shift (δ) = 3.2 ppm, and no side reaction of the epoxy group occurred during the reaction. Confirmed.

Subsequently, in a 200 mL three-necked flask, 54.9 g of an epoxy group-containing polyorganosiloxane obtained above, 30.0 g of methyl isobutyl ketone as a solvent, and 4- (4-n-pentyl-cyclohexyl) benzoic acid (PCHBA) as carbonic acid 178 g of compound (1) in which X is a methyl group (equivalent to 20 mol% of the epoxy group of the epoxy group-containing polyorganosiloxane) and the compound represented by Formula (c1-1) (the epoxy group-containing polyorganosiloxane is It corresponds to 50 mol% with respect to the epoxy group to have), and 0.10 g of brand name "UCAT 18X" (made by San Afro Co., Ltd.) was put as a catalyst, and it reacted at 100 degreeC for 48 hours, stirring. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed with water three times, dried using magnesium sulfate, and then the solvent was distilled off to obtain polyorganosiloxane (PS-1). About this polyorganosiloxane (PS-1), the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography (GPC) was 8,400.

Synthesis Examples 2 to 6

Polyorganosiloxane (PS-2) by the same method as the said Synthesis Example 1 except having changed compound (1) into each of Table 1 among the carbon acids used for reaction with an epoxy-group containing polyorganosiloxane. ) To (PS-6), respectively. Mw of these polyorganosiloxanes is combined with Table 1 below. In addition, each of polyorganosiloxane (PS-1)-(PS-4) is corresponded to specific polyorganosiloxane.

In Table 1, the quantity of carbonic acid is a compounding quantity (mol%) with respect to the epoxy group which an epoxy group containing polyorganosiloxane has. The abbreviation of each compound is the following meanings, respectively.

Compound (2): X is a hydrogen atom in the compound represented by said formula (c1-2).

Compound (3): X is a methyl group in the compound represented by said formula (c1-3).

Compound (4): In the compound represented by the formula (c1-4), X is a hydrogen atom

Compound (5): Compound represented by the following formula (d-1)

Compound (6): a compound represented by the following formula (d-2)

<Synthesis of Polyimide>

Synthesis Example 7

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride (TCA) as tetracarboxylic dianhydride, 46 g (0.425 mol) of p-phenylenediamine (PDA) as a diamine and 3- (3,5 -39 g (0.075 mol) of diaminobenzoyloxy) cholestan (HCDA) was dissolved in 830 g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at 60 ° C for 6 hours. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight 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 closure reaction, the solvent in the system was replaced with fresh NMP (the pyridine and acetic anhydride used in the dehydration ring closure reaction in this operation were removed to the outside of the system) to thereby remove the polyimide (PI-1) having an imidization rate of about 50%. The solution containing 15 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.

Example 1

<Preparation of liquid crystal aligning agent>

To the solution containing polyimide (PI-1) as a polymer, NMP and butyl cellosolve (BC) were added as an organic solvent, and polyorganosiloxane (PS-1) was further added, and the polymer composition was polyimide (PI). -1): The polyorganosiloxane (PS-1) = 90:10 (weight ratio) was added, and the solvent composition was NMP: BC = 50: 50 (weight ratio), and it was set as the solution of 6.0 weight% of solid content concentration. 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>

Using the liquid crystal aligning agent prepared above, the presence or absence of the pattern of a transparent electrode and the amount of ultraviolet irradiation (3 levels) were changed, and four liquid crystal display elements in total were manufactured. In addition, various characteristics were evaluated about the manufactured liquid crystal display element.

[Production of Liquid Crystal Display Element with Transparent Electrode without Pattern]

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-Insatsu Co., Ltd.), and on a hotplate of 80 degreeC 1 After heating (prebaking) for 1 minute and removing a solvent, it heated (postbaking) for 10 minutes on the 150 degreeC hotplate, and formed the coating film of 600 kPa of average film thicknesses.

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 oxide containing epoxy resin adhesive of diameter 5.5micrometer to each outer diameter which has the liquid crystal aligning film of the said pair of board | substrates, it overlapped and crimped | bonded so that a liquid crystal aligning film surface could face and hardened the adhesive agent. 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.

Subsequently, an irradiation amount of 10,000 J / m 2 was applied to the liquid crystal cell obtained above using an ultraviolet irradiation device using a metal halide lamp as a light source while applying alternating current 10 V at a frequency of 60 Hz between the electrodes. Irradiated with ultraviolet rays. In addition, this irradiation amount is the value measured using the photometer measured with the wavelength 365nm reference.

[Evaluation of Voltage Integrity]

The voltage holding ratio (VHR) of 167 milliseconds after application | release cancellation was measured after applying the voltage of 5V at 23 degreeC with the application time of 60 microseconds and the span of 167 milliseconds using the liquid crystal display element manufactured above. The measurement results are 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]

The liquid crystal aligning agent of Example 1 prepared above was patterned in the slit shape as shown in FIG. 1, and the liquid crystal on each electrode surface of the board | substrate A and the board | substrate B made of glass which respectively have ITO electrodes partitioned into several area | regions After coating using an alignment film printing machine (manufactured by Nippon Shashin Insatsu Co., Ltd.) and heating for 1 minute on a hot plate at 80 ° C. (prebaking), the solvent is removed, and then heated on a hot plate at 150 ° C. for 10 minutes (postbaking). Thus, a coating film having an average film thickness of 600 kPa was formed. 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 the board | substrate which has a liquid crystal aligning film was obtained. 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 diameter which has the liquid crystal aligning film of the said pair of board | substrates, it overlapped and crimped | bonded so that a liquid crystal aligning film surface could face and hardened the adhesive agent. 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 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, the irradiation amount of 5,000 J / m 2 or 10,000 J / m 2 in the state in which voltage was applied between the conductive films by the same method as that in the case of manufacturing a liquid crystal display element having a transparent electrode without a pattern. After irradiating with each light, it provided for evaluation of the response speed of a liquid crystal molecule.

[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 is measured. The response of the liquid crystal molecule was evaluated.

The measurement result of each response speed of the liquid crystal display element of tailings irradiation, the liquid crystal display element of irradiation amount 5,000J / m <2>, and the liquid crystal display element of irradiation amount 10,000J / m <2> is shown in following Table 2.

[Examples 2 to 4 and Comparative Examples 1 and 2]

The liquid crystal aligning agent was prepared like Example 1 except having changed the quantity of the polyimide used for preparation of a liquid crystal aligning agent, the kind and quantity of polyorganosiloxane as shown in following Table 2, respectively. 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.

As shown in Table 2, in the liquid crystal display elements of Examples 1-4, the response speed of the liquid crystal molecule with respect to a voltage change is quick compared with Comparative Examples 1 and 2, especially in Examples 1, 3, and 4. did.

Claims (7)

Liquid crystal aligning agent for liquid crystal aligning film formation (The said liquid crystal aligning agent is not a structure contained in a liquid crystal composition) containing the polymer (P) which has group represented by following formula (1):

(In formula (1), X is a hydrogen atom or a methyl group; L is a single bond or a C1-C20 alkanediyl group, The said alkanediyl group may branch and the oxygen atom does not mutually adjoin.) May be interrupted 1 to 10 times by an oxygen atom at Y; Y is a single bond, -O-, * ¹ -COO-, * ¹ -OCO- or -OCOO-, provided that "* ¹ " Ring A is a naphthalene ring; "*" represents a bond. The method of claim 1,
L is a liquid crystal aligning agent for liquid crystal aligning film formation which is a C4-C20 alkanediyl group. The method of claim 1,
The said polymer (P) has a polyorganosiloxane skeleton, The liquid crystal aligning agent for liquid crystal aligning film formation. The method of claim 3,
The liquid crystal aligning agent for liquid crystal aligning film formation which further contains at least 1 sort (s) of polymer (Q) chosen from the group which consists of polyamic acid and polyimide. The 1st which apply | coats the liquid crystal aligning agent for liquid crystal aligning film formation of any one of Claims 1-4 on the said conductive film of a pair of board | substrates which have a conductive film, respectively, and then heats this and forms a liquid crystal aligning film. Fair,
A second step of arranging a pair of substrates on which the liquid crystal alignment film is formed so as to face the liquid crystal alignment film so as to face each other via a layer of liquid crystal molecules;
And 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. The liquid crystal aligning film formed using the liquid crystal aligning agent for liquid crystal aligning film formation as described in any one of Claims 1-4. The liquid crystal display element provided with the liquid crystal aligning film of Claim 6.

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