KR102420693B1 - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

The present invention relates to a polymer obtained from a diamine component containing at least one selected from diamines having a structure represented by the following formulas (1) to (3) and a diamine having a structure represented by the following formula (4) (wherein W and X are each independently an aromatic ring having 6 to 14 carbon atoms, Y is an oxygen atom or a sulfur atom, Z is a divalent organic group including an oxygen atom and alkylene, and R ₁ to R ₇ are each independently to a hydrogen atom or a monovalent organic group, and m, n, o, p and q are each independently an integer of 0 to 4.) and an organic solvent-containing liquid crystal aligning agent.
[Formula 1]

Description

Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element

This invention relates to the liquid crystal aligning agent for manufacturing the liquid crystal display element excellent in a baking characteristic, a liquid crystal aligning film, and a liquid crystal display element.

BACKGROUND ART A liquid crystal display element is known as a light-weight, thin, and low-power display device, and in recent years, it is used for a large-scale television use, and has achieved remarkable development. A liquid crystal display element clamps a liquid crystal layer with a pair of transparent board|substrates provided with an electrode, and is comprised, for example. And in a liquid crystal display element, the organic film which consists of an organic material is used as a liquid crystal aligning film so that a liquid crystal may become a desired orientation state between board|substrates.

That is, a liquid crystal aligning film is formed in the surface in contact with the liquid crystal of the board|substrate which clamps a liquid crystal as a structural member of a liquid crystal display element, and is playing the role of orientating a liquid crystal in a fixed direction between the board|substrates. And in addition to the role of orientating a liquid crystal in fixed directions, such as a direction parallel to a board|substrate, the role of controlling the pretilt angle of a liquid crystal may be calculated|required by a liquid crystal aligning film, for example. The ability to control the orientation of a liquid crystal in such a liquid crystal aligning film (henceforth orientation control ability) is provided by orientation-processing with respect to the organic film which comprises a liquid crystal aligning film.

Conventionally, the rubbing method is known as an orientation processing method of the liquid crystal aligning film for providing orientation control ability. The rubbing method refers to rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate with a cloth such as cotton, nylon, or polyester in a certain direction (rubbing direction), and rubbing direction (rubbing direction) A method of aligning liquid crystals. Since this rubbing method can implement|achieve the alignment state of a relatively stable liquid crystal easily, it has been used in the manufacturing process of the conventional liquid crystal display element. And as an organic film used for a liquid crystal aligning film, the polyimide-type organic film excellent in reliability, such as heat resistance, and an electrical property, has been mainly selected.

However, as for the rubbing method of rubbing the surface of the liquid crystal aligning film which consists of polyimide etc., generation|occurrence|production of dust generation and static electricity may become a problem. In addition, due to the recent high resolution of liquid crystal display elements or irregularities caused by the electrodes on the corresponding substrates or the switching active elements for driving liquid crystals, the surface of the liquid crystal aligning film cannot be uniformly rubbed with a cloth, resulting in uniform alignment of liquid crystals. There were cases where it could not be realized.

Then, as another orientation processing method of the liquid crystal aligning film which does not rub, the photo-alignment method is examined actively.

Although there are various methods for the photo-alignment method, anisotropy is formed in the organic film which comprises a liquid crystal aligning film by linearly polarized light or collimated light, and a liquid crystal is orientated according to the anisotropy.

As a main photo-alignment method, the decomposition-type photo-alignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet light, and anisotropic decomposition is generated using the polarization direction dependence of the ultraviolet absorption of the molecular structure. And it is made to orientate a liquid crystal with the polyimide which remained without decomposition|disassembly (for example, refer patent document 1).

Moreover, the photo-alignment method of a photocrosslinking type|mold and a photoisomerization type is also known. For example, using polyvinylcinnamate, polarized ultraviolet-ray is irradiated, and a dimerization reaction (crosslinking reaction) is generated in the double bond part of two side chains parallel to polarization|polarized-light. And a liquid crystal is orientated in the direction orthogonal to a polarization direction (for example, refer nonpatent literature 1). In addition, when a side chain polymer having azobenzene in the side chain is used, polarized ultraviolet light is irradiated, an isomerization reaction occurs in the azobenzene moiety of the side chain parallel to polarization, and the liquid crystal is oriented in a direction orthogonal to the polarization direction ( For example, refer to Non-Patent Document 2).

As in the above example, in the orientation processing method of the liquid crystal aligning film by the photo-alignment method, rubbing is made unnecessary, and there is no concern of generation|occurrence|production of dust and static electricity. And it can orientation-process also to the board|substrate of the liquid crystal display element with an unevenness|corrugation on the surface, and it becomes the method of the orientation treatment of the liquid crystal aligning film suitable for an industrial production process.

Japanese Patent No. 3893659

M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992). K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

As mentioned above, the photo-alignment method makes rubbing process itself unnecessary compared with the rubbing method conventionally used industrially as an orientation processing method of a liquid crystal display element, Therefore, it is equipped with a big advantage. And compared with the rubbing method in which orientation controllability becomes substantially constant by rubbing, by the photo-alignment method, the irradiation amount of the polarized light can be changed, and orientation control ability is controllable. However, in the photo-alignment method, when it is intended to realize the same degree of alignment control ability as in the case of the rubbing method, the irradiation amount of a large amount of polarized light is required, or stable alignment of the liquid crystal cannot be realized in some cases.

For example, in the decomposition type photo-alignment method described in Patent Document 1 described above, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp having an output of 500 W for 60 minutes, etc. will be needed Moreover, also in the case of the photo-alignment method of a dimerization type|mold or a photoisomerization type|mold, the ultraviolet irradiation of the large quantity of about several J (joule) - several tens of J may be required. In addition, in the case of the photo-alignment method of the photocrosslinking type or the photoisomerization type, since thermal stability and light stability of the alignment of the liquid crystal are inferior, when it is used as a liquid crystal display element, problems such as poor alignment and display baking occur. there was. In particular, in a liquid crystal display device of a transverse electric field drive type, since liquid crystal molecules are switched in-plane, the alignment shift of the liquid crystal after liquid crystal drive is easy to occur, and display baking resulting from AC drive becomes a big problem.

Therefore, in the photo-alignment method, high efficiency improvement of an orientation process and realization of the stable liquid-crystal orientation are calculated|required, and the liquid crystal aligning film and liquid crystal aligning agent which can provide high orientation control ability with respect to a liquid crystal aligning film with high efficiency are calculated|required.

An object of this invention is to provide the board|substrate which has a liquid crystal aligning film for transverse electric field drive type liquid crystal display elements which is provided with orientation control ability with high efficiency and is excellent in baking characteristics, and the transverse electric field drive type liquid crystal display element which has this board|substrate.

MEANS TO SOLVE THE PROBLEM The present inventors discovered the following invention, as a result of earnestly examining in order to achieve the said subject.

1. A polymer obtained from a diamine component comprising at least one selected from diamines having a structure represented by the following formulas (1) to (3) and a diamine having a structure represented by the following formula (4), and an organic solvent containing liquid crystal aligning agent (wherein W and X are each independently an aromatic ring having 6 to 14 carbon atoms, Y is an oxygen atom or a sulfur atom, Z is an oxygen atom and a divalent organic group containing alkylene, R ₁ to R ₇ are each independently a hydrogen atom or a monovalent organic group, and m, n, o, p and q are each independently an integer of 0 to 4).

[Formula 1]

ADVANTAGE OF THE INVENTION By this invention, orientation control ability is provided with high efficiency, and the board|substrate which has the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements excellent in a baking characteristic, and the transverse electric field drive type liquid crystal display element which has this board|substrate can be provided.

Since the lateral electric field drive type liquid crystal display element manufactured by the method of this invention is provided with orientation control ability with high efficiency, even if it drives continuously for a long time, a display characteristic is not impaired.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, this inventor came to complete this invention by obtaining the following knowledge.

The polymer composition used in the production method of the present invention has a photosensitive main chain polymer (hereinafter also simply referred to as a main chain polymer) capable of expressing liquid crystallinity, and the coating film obtained by using the polymer composition is , a film having a photosensitive main chain polymer capable of expressing liquid crystallinity. It orientation-processes by polarized light irradiation, without giving a rubbing process to this coating film. And it becomes the coating film (henceforth a liquid crystal aligning film) to which orientation control ability was provided through the process of heating the main chain polymer film after polarized light irradiation. At this time, the slight anisotropy expressed by polarized light irradiation becomes a driving force, and the main chain polymer itself efficiently reorients by self-organization. As a result, as a liquid crystal aligning film, highly efficient orientation processing is implement|achieved, and the liquid crystal aligning film to which high orientation control ability was provided can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

A polymer obtained from a diamine component comprising at least one selected from diamines having a structure represented by the following formulas (1) to (3) and a diamine having a structure represented by the following formula (4) (hereinafter also referred to as a main chain polymer) ) and a liquid crystal aligning agent containing an organic solvent (wherein W and X are each independently an aromatic ring having 6 to 14 carbon atoms, Y is an oxygen atom or a sulfur atom, and Z is an oxygen atom and alkylene It is a divalent organic group including; R ₁ to R ₇ are each independently a hydrogen atom or a monovalent organic group, and m, n, o, p and q are each independently an integer of 0 to 4).

Hereinafter, each condition will be described in detail.

[Formula 2]

<Diamine having a specific structure>

The liquid crystal aligning agent of this invention is a polymer obtained from the diamine component containing at least 1 sort(s) chosen from the diamine which has a structure shown by the said Formula (1)-(3), and the diamine which has a structure shown by the said Formula (4); , a liquid crystal aligning agent containing an organic solvent.

In said formula (1), W is a C6-C14 aromatic ring, and R< ₁ > is a monovalent organic group. Although a benzene ring, a naphthalene ring, biphenylene, etc. are mentioned as an aromatic ring here, From a viewpoint, such as solubility of the polymer obtained, a benzene ring is preferable.

Examples of the monovalent organic group include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Especially, as a monovalent organic group, a methyl group or a methoxy group is preferable.

As diamine which has the structure of the said Formula (1), the diamine which two amino groups couple|bonded with the said structure is preferable. Although the following can be illustrated as the specific example, it is not limited to these.

[Formula 3]

In said formula (2), X is a C6-C14 aromatic ring, and R< ₂ > is a monovalent organic group. Although a benzene ring, a naphthalene ring, biphenylene, etc. are mentioned as an aromatic ring here, From a viewpoint, such as solubility of the polymer obtained, a benzene ring is preferable. Examples of the monovalent organic group include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Especially, as a monovalent organic group, a methyl group or a methoxy group is preferable.

As diamine which has the structure of the said Formula (2), the diamine which two amino groups couple|bonded with the said structure is preferable. Although the following can be illustrated as the specific example, it is not limited to these.

[Formula 4]

In the formula (3), Y is an oxygen atom or a sulfur atom, and R ₃ to R ₅ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group herein include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. . Especially, as a monovalent organic group, a methyl group or a methoxy group is preferable.

As diamine which has the structure of the said Formula (3), the diamine which two amino groups couple|bonded with the said structure is preferable. Although the following can be illustrated as the specific example, it is not limited to these.

[Formula 5]

In the formula (4), Z is a divalent organic group containing an oxygen atom and alkylene, and the divalent organic group here is -O-(CH ₂ )rO- or -(OCH ₂ CH ₂ ) sO- is mentioned. R ₆ and R ₇ are each independently a monovalent organic group. Examples of the monovalent organic group herein include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. . Especially, as a monovalent organic group, a methyl group or a methoxy group is preferable.

As diamine which has the structure of the said Formula (4), the diamine which two amino groups couple|bonded with the said structure is preferable. Although the following can be illustrated as the specific example, it is not limited to these.

[Formula 6]

Here, when r is an even number, such as 2, 4, 6, and 8, the linearity of the obtained polymer increases as a result, WHEREIN: In the heating process after polarized light irradiation, by reorienting in a higher order, the liquid crystal aligning film to which high orientation control ability was provided. can be obtained

<Polymer>

The polymer of this invention is a polymer obtained using the said diamine. Although a polyamic acid, polyamic acid ester, a polyimide, a polyurea, polyamide etc. are mentioned as a specific example, From a viewpoint of use as a liquid crystal aligning agent, the structural unit represented by following formula (5), and following formula (6) It is more preferable that it is at least 1 sort(s) chosen from the polyimide precursor containing the structural unit represented by, and the polyimide which is its imidated product.

[Formula 7]

In the formula (5), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and Y ₁ is a divalent organic group derived from a diamine having a structure selected from Formulas (1) to (3). a device, and R ₁₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₁₁ is preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoint of easiness of imidation by heating.

<Tetracarboxylic dianhydride>

X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure thereof is not particularly limited. In addition, X ₁ in a polyimide precursor is the solubility to the solvent of a polymer, the applicability|paintability of a liquid crystal aligning agent, the orientation of the liquid crystal in the case of setting it as a liquid crystal aligning film, voltage retention, accumulation|storage charge, etc. to the grade of characteristics required. It is appropriately selected depending on the type of polymer and may be one type or two or more types may be mixed in the same polymer.

If the specific example of X< ₁ > is shown, the structure of Formula (X-1) - (X-46) etc. which are published on pages 13-14 of International Publication 2015/119168 will be mentioned.

Although the structure of preferable X< ₁ > is shown below, this invention is not limited to these.

[Formula 8]

[Formula 9]

In the above structures, (A-1) and (A-2) are particularly preferable from the viewpoint of further improvement in film hardness, and (A-4) is particularly preferable from the viewpoint of further improvement of the relaxation rate of the accumulated charge, (A-15) - (A-17) etc. are especially preferable from a viewpoint of the further improvement of the liquid-crystal orientation and the relaxation rate of an accumulated charge.

<Diamine>

In Formula (5), the structure which removed two amino groups from the diamine which has a structure chosen from said Formula (1)-(3) as a specific example of Y< ₁ > is mentioned.

In the formula (6), X ₂ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₂ is a divalent organic group derived from a diamine having a structure represented by the formula (4), and R ₁₂ is It is a hydrogen atom or a C1-C5 alkyl group. R ₁₂ is preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoint of easiness of imidation by heating.

[Formula 10]

As a specific example of X< ₂ >, the structure similar to what was illustrated by X< ₁ > of Formula (5) including a preferable example is mentioned. As a specific example of Y< ₂ >, the structure which removed two amino groups from the diamine which has a structure represented by said Formula (4) is mentioned.

<Polymer (other structural units)>

The polyimide precursor containing the structural unit represented by Formula (5) and the structural unit represented by Formula (6) is the range which does not impair the effect of this invention. WHEREIN: The structural unit represented by following formula (7), and its already You may contain at least 1 sort(s) chosen from the polyimide which is a dehydrated product.

[Formula 11]

In the formula (7), X ₃ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and Y ₃ is a diamine which does not contain any of the structures represented by the formulas (1) to (4) in the main chain direction. It is a divalent organic group derived from, R< ₁₃ > is the same as the definition of R< ₁₁ > of said Formula (5), and R< ₂₃ > represents a hydrogen atom or a C1-C4 alkyl group each independently. Moreover, it is preferable that at least one of two _R23 is a hydrogen atom.

As a specific example of X< ₃ >, the structure similar to what was illustrated by X< ₁ > of Formula (5) including a preferable example is mentioned. In addition, Y< ₃ > is a divalent organic group derived from the diamine which does not contain any of the structures shown by Formula (1)-(4) in a principal chain direction, The structure in particular is not limited. In addition, Y ₃ is suitably selected according to the degree of characteristics required, such as the solubility to the solvent of a polymer, the applicability|paintability of a liquid crystal aligning agent, the orientation of the liquid crystal in the case of setting it as a liquid crystal aligning film, voltage retention, accumulated electric charge, etc., One type may be sufficient in the same polymer, and two or more types may be mixed.

When specific examples of Y ₃ are shown, the structure of formula (2) published on page 4 of International Publication No. 2015/119168, and formulas (Y-1) to (Y-97), which are published on pages 8 to 12, structures of (Y-101) to (Y-118); A divalent organic group in which two amino groups were removed from Formula (2), which is published on page 6 of International Publication No. 2013/008906; A divalent organic group obtained by removing two amino groups from Formula (1) published on page 8 of International Publication No. 2015/122413; The structure of formula (3) published on page 8 of International Publication No. 2015/060360; a divalent organic group obtained by removing two amino groups from Formula (1) described on page 8 of JP 2012-173514 ; The divalent organic group etc. which removed two amino groups from Formula (A) - (F) published on the 9th page of international publication 2010-050523 are mentioned.

Although the structure of preferable Y3 is _shown below, this invention is not limited to these.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

Among the above structures, (B-28), (B-29), etc. are particularly preferable from the viewpoint of further improvement of film hardness, and (B-1) to (B-3), etc., further improve liquid-crystal orientation Particularly preferred from the viewpoint of It is especially preferable, and (B-26) etc. are preferable from a viewpoint of the further improvement of voltage retention.

At least one selected from a polyimide precursor comprising a structural unit represented by the formula (5) and a structural unit represented by the formula (6), and a polyimide that is an imidized product thereof, simultaneously containing a structural unit represented by the formula (7) In this case, the total of the structural unit represented by the formula (5) and the structural unit represented by the formula (6) is preferably 10 mol% or more with respect to the total of the formulas (5), (6) and (7), More preferably, it is 20 mol% or more, Especially preferably, it is 30 mol% or more.

As for the molecular weight of the polyimide precursor used for this invention, 2,000-500,000 are preferable at a weight average molecular weight, More preferably, it is 5,000-300,000, More preferably, it is 10,000-100,000.

As a polyimide containing the structural unit represented by Formula (5) and Formula (6), the polyimide obtained by ring-closing said polyimide precursor is mentioned. In this polyimide, the ring closure rate (it is also mentioned imidation rate) of an amic acid group does not necessarily need to be 100 %, It can adjust arbitrarily according to a use and objective.

As a method of imidating a polyimide precursor, the thermal imidation which heats the solution of a polyimide precursor as it is, or catalyst imidation which adds a catalyst to the solution of a polyimide precursor is mentioned.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is a polymer (specific polymer) obtained from the diamine component containing the diamine which has at least 1 sort(s) chosen from the diamine which has a structure shown by Formula (1)-(3), and Formula (4) ), but as long as the effect described in the present invention is exhibited, two or more types of specific polymers having different structures may be contained. Moreover, in addition to a specific polymer, you may contain the other polymer, ie, the polymer which does not have a divalent group represented by Formula (1) - Formula (4). Examples of other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or a derivative thereof, and poly(styrene-phenylmaleimide). ) derivatives, poly(meth)acrylates, and the like. When the liquid crystal aligning agent of this invention contains another polymer, it is preferable that the ratio of the specific polymer with respect to all polymer components is 5 mass % or more, and 5-95 mass % is mentioned as the example.

A liquid crystal aligning agent is used in order to produce a liquid crystal aligning film, and generally takes the form of a coating liquid from a viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is an above-described polymer component and it is preferable that it is a coating liquid containing the organic solvent in which this polymer component is dissolved. In that case, the density|concentration of the polymer in a liquid crystal aligning agent can be suitably changed with setting of the thickness of the coating film which you want to form. From the point of forming a uniform and defect-free coating film, it is preferable that it is 1 mass % or more, and it is preferable to set it as 10 mass % or less from the point of storage stability of a solution. A particularly preferable concentration of the polymer is 2 to 8% by mass.

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt|dissolves uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyro Lactone, 1, 3- dimethyl imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, etc. are mentioned. Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.

In addition, as for the organic solvent contained in a liquid crystal aligning agent, it is common to use the mixed solvent which used together the solvent which improves the applicability|paintability at the time of apply|coating a liquid crystal aligning agent, and the surface smoothness of a coating film in addition to the above solvent, Also in the liquid crystal aligning agent of this invention, such a mixed solvent is used preferably. Although the specific example of the organic solvent used together is given below, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-penta Non, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1- Methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol Monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol mono Methyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether Ethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3- Ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxybutyl propionate, methyl lactate ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester , lactic acid isoamyl ester, a solvent represented by the following formulas [D-1] to [D-3], and the like.

[Formula 16]

In formula [D- ¹ ], D1 represents a C1-C3 alkyl group, in formula [D- ² ], D2 represents a C1-C3 alkyl group, In formula [D- ³ ], D3 represents a C1-C4 alkyl group.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2- It is preferable to use pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether. The kind and content of such a solvent are suitably selected according to the coating apparatus of a liquid crystal aligning agent, application|coating conditions, application|coating environment, etc.

The liquid crystal aligning agent of this invention is the range which does not impair the effect of this invention. WHEREIN: It may contain components other than a polymer component and an organic solvent further. Such additional components include an adhesion aid for increasing the adhesion between the liquid crystal aligning film and the substrate or the adhesion between the liquid crystal aligning film and the sealing material, a crosslinking agent for increasing the strength of the liquid crystal aligning film, a dielectric or conductive material for adjusting the dielectric constant or electrical resistance of the liquid crystal aligning film and the like. Specific examples of these additional components are as variously disclosed in known documents related to liquid crystal aligning agents. The components disclosed in , etc. are mentioned.

<The manufacturing method of the board|substrate which has a liquid crystal aligning film> and <The manufacturing method of a liquid crystal display element>

The manufacturing method of the board|substrate which has a liquid crystal aligning film of this invention,

[I] A polymer obtained from a diamine component containing at least one selected from diamines having a structure represented by formulas (1) to (3) and a diamine having a structure represented by formula (4) and a polymer composition containing an organic solvent forming a coating film by coating the substrate on a substrate having a conductive film for lateral electric field driving;

[II] The process of irradiating the ultraviolet-ray which polarized to the coating film obtained by [I]; and

[III] Process of heating the coating film obtained in [II];

has

According to the said process, the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements to which orientation control ability was provided can be obtained, and the board|substrate which has this liquid crystal aligning film can be obtained.

Moreover, a transverse electric field drive type liquid crystal display element can be obtained by preparing a 2nd board|substrate other than the board|substrate (1st board|substrate) obtained above.

For the second substrate, the above steps [I] to [III] (the conductive film for the transverse electric field drive) is used in place of the substrate having the transverse electric field drive conductive film, except that a substrate not having the transverse electric field drive conductive film is used. In order to use the board|substrate which does not have, for convenience, in this application, by using process [I'] - [III']), the 2nd board|substrate which has a liquid crystal aligning film to which orientation control ability was provided can be obtained by using have.

A method for manufacturing a transverse electric field driving type liquid crystal display device,

[IV] The process of opposingly arrange|positioning the 1st and 2nd board|substrate obtained above so that the liquid crystal aligning film of a 1st and 2nd board|substrate may mutually face through a liquid crystal, and obtaining a liquid crystal display element;

has Thereby, a transverse electric field drive type liquid crystal display element can be obtained.

Hereinafter, each process of [I] - [III] and [IV] which the manufacturing method of this invention has is demonstrated.

<Process [I]>

In step [I], a polymer composition containing a photosensitive main chain polymer capable of expressing liquid crystallinity in a predetermined temperature range and an organic solvent is applied on a substrate having a conductive film for lateral electric field driving to form a coating film do.

<substrate>

Although limitation in particular is not carried out about a board|substrate, When the liquid crystal display element manufactured is a transmissive type, it is preferable that a board|substrate with high transparency is used. In that case, limitation in particular is not carried out, Plastic substrates, such as a glass substrate or an acryl substrate and a polycarbonate board|substrate, etc. can be used.

In addition, in consideration of application to a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can also be used.

<Conductive film for lateral electric field drive>

The substrate has a conductive film for driving a lateral electric field.

Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide: Indium Tin Oxide) and IZO (Indium Zinc Oxide: Indium Zinc Oxide) when the liquid crystal display element is a transmissive film.

Moreover, in the case of a reflection type liquid crystal display element, although the material etc. which reflect light, such as aluminum, are mentioned as a conductive film, it is not limited to these.

A conventionally well-known method can be used for the method of forming an electrically conductive film on a board|substrate.

The method of apply|coating the above-mentioned polymer composition on the board|substrate which has the electrically conductive film for lateral electric field drive is not specifically limited.

As for the coating method, industrially, the method of performing by screen printing, offset printing, flexographic printing, the inkjet method, etc. is common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method (rotary coating method), the spray method, etc., You may use these according to the objective.

After apply|coating the polymer composition on the board|substrate which has a conductive film for transverse electric field drive, 30-200 degreeC, preferably 50-150 by heating means, such as a hotplate, a heat circulation type oven, or an IR (infrared) type oven. A coating film can be obtained by evaporating the solvent at °C. It is preferable that the drying temperature at this time is lower than a process [III] from a viewpoint of liquid-crystal orientation stability.

When the thickness of the coating film is too thick, it becomes disadvantageous in terms of power consumption of the liquid crystal display element, and when it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm.

It is also possible to provide a step of cooling the substrate on which the coating film was formed to room temperature after the step [I] before the subsequent step [II].

<Process [II]>

In process [II], the polarized ultraviolet-ray is irradiated to the coating film obtained by process [I]. In the case of irradiating the polarized ultraviolet ray to the film surface of the coating film, the polarized ultraviolet ray is irradiated through the polarizing plate from a certain direction with respect to the substrate. As the ultraviolet ray to be used, an ultraviolet ray having a wavelength of 100 nm to 400 nm can be used. Preferably, an optimal wavelength is selected through a filter or the like according to the type of coating film to be used. And, for example, in order to selectively cause a photocrosslinking reaction, an ultraviolet ray having a wavelength of 290 nm to 400 nm may be selected and used. As the ultraviolet, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet-ray depends on the coating film to be used. The irradiation amount is 1 of the amount of polarized ultraviolet rays that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the perpendicular direction in the coating film It is preferable to set it as % - 70% of the range, and it is more preferable to set it as 1 % - 50% of the range.

<Process [III]>

In process [III], the coating film to which the ultraviolet-ray which polarized in process [II] was irradiated is heated. By heating, orientation control ability can be provided to a coating film.

Heating can use heating means, such as a hot plate, a heat circulation type oven, or an IR (infrared) type|mold oven. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film to be used is expressed.

It is preferable that heating temperature exists in the temperature range in which main-chain polymer|macromolecule expresses favorable liquid-crystal orientation stability. When the heating temperature is too low, the effect of amplifying the anisotropy by heat tends to be insufficient, and when the heating temperature is too high, the anisotropy imparted by irradiation of polarized ultraviolet rays tends to be lost, in this case, by self-organization It may become difficult to reorient in one direction.

The thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm from the same reason described in step [I].

By having the above process, in the manufacturing method of this invention, highly efficient and anisotropic introduction to a coating film can be implement|achieved. And the board|substrate in which the liquid crystal aligning film was formed can be manufactured with high efficiency.

<Process [IV]>

[IV] Process is the board|substrate (1st board|substrate) which has a liquid crystal aligning film on the electrically conductive film for transverse electric field drive obtained by [III], and the electrically conductive film obtained by said [I'] - [III'] similarly. A liquid crystal cell is fabricated by a known method by arranging a substrate (second substrate) having no liquid crystal aligning film formed thereon so that both liquid crystal aligning films face each other through a liquid crystal, and a transverse electric field driving type liquid crystal display element is produced is a process that In addition, in the steps [I'] to [III'], in the step [I], instead of the substrate having the conductive film for driving the lateral electric field, a substrate not having the conductive film for driving the lateral electric field was used, and the process [ It can carry out similarly to I]-[III]. Since the only difference between the steps [I] to [III] and the steps [I'] to [III'] is the presence or absence of the above-described conductive film, the description of the steps [I'] to [III'] is omitted.

If an example of preparation of a liquid crystal cell or a liquid crystal display element is given, the above-mentioned 1st and 2nd board|substrates are prepared, a spacer is disperse|distributed on the liquid crystal aligning film of one board|substrate, a liquid crystal aligning film surface is made inside, and the other side After bonding the board|substrates of a room, the method of pressure-reducing injection|pouring and sealing of a liquid crystal, or the liquid crystal aligning film surface which disperse|distributed the spacer, after dripping a liquid crystal, the method of bonding and sealing a board|substrate, etc. can be illustrated. In this case, it is preferable to use a substrate having an electrode having a structure similar to that of a comb for lateral electric field driving as the substrate on one side. The diameter of the spacer at this time is preferably 1 µm to 30 µm, and more preferably 2 µm to 10 µm. The spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the manufacturing method of the board|substrate with a coating film of this invention, after apply|coating a polymer composition on a board|substrate to form a coating film, it irradiates polarized ultraviolet-ray. Then, by heating, highly efficient anisotropic introduction|transduction with respect to a main chain type polymer film is implement|achieved, and the board|substrate with the liquid crystal aligning film provided with the orientation control ability of a liquid crystal is manufactured.

In the coating film used in the present invention, the principle of molecular reorientation caused by the photoreaction and self-organization ability of the main chain is utilized to realize highly efficient anisotropy introduction into the coating film. In the manufacturing method of this invention, after forming a coating film on a board|substrate using a main chain type polymer|macromolecule, polarized ultraviolet-ray is irradiated, Then, after heating, a liquid crystal display element is produced.

Therefore, the coating film used for the method of this invention can be set as the liquid crystal aligning film excellent in orientation control ability by introducing anisotropy with high efficiency by performing irradiation of the ultraviolet-ray which polarized with respect to a coating film, and heat processing sequentially.

And in the coating film used for the method of this invention, the irradiation amount of the ultraviolet-ray which polarized to a coating film, and the heating temperature in heat processing are optimized. Thereby, highly efficient and anisotropic introduction|transduction with respect to a coating film can be implement|achieved.

The optimal dose of polarized UV light for highly efficient anisotropy introduction into the coating film used in the present invention is that of polarized UV light that optimizes the amount of photosensitive group photocrosslinking reaction, photoisomerization reaction, or optical Fris dislocation reaction in the coating film. corresponding to the amount of irradiation. As a result of irradiating the polarized ultraviolet-ray with respect to the coating film used for this invention, when there are few photosensitive groups of the main chain which photocrosslinking reaction, a photoisomerization reaction, or an optical Fris rearrangement reaction, it will not become a sufficient photoreaction amount. In that case, even if it heats after that, sufficient self-organization does not advance. On the other hand, in the coating film used in the present invention, when polarized ultraviolet rays are irradiated with respect to a structure having a photocrosslinkable group, when the photosensitive groups of the main chain to be crosslinked are excessive, the crosslinking reaction between the main chains will proceed excessively. In that case, the obtained film|membrane becomes rigid, and it may interfere with advancing of the self-organization by subsequent heating. In addition, in the coating film used in the present invention, as a result of irradiating polarized UV light to a structure having an optical Fleece potential group, if there are many optical Fleece potential groups in the polymer film, the anisotropy obtained by the polarized UV light decreases, and then the magnetic field by heating A fall of liquid-crystal orientation stability may be caused by the obstruction of advancing of organization. In addition, when polarized ultraviolet rays are irradiated with respect to a structure having an optical Fris dislocation group, if the irradiation amount of ultraviolet rays is too large, the main chain polymer is photodecomposed and the progress of self-organization by subsequent heating is hindered, or obtained The quality of a liquid crystal display element may fall by the deterioration of the electrical characteristic of a liquid crystal aligning film.

Therefore, in the coating film used in the present invention, the optimal amount in which the photosensitive group of the main chain undergoes a photocrosslinking reaction, a photoisomerization reaction, or a photoFris relocation reaction by irradiation of polarized ultraviolet light is the amount of the photosensitive group of the main chain polymer film. It is preferable to set it as 0.1 mol% - 90 mol%, and it is more preferable to set it as 0.1 mol% - 80 mol%. By setting the amount of the photosensitive group of the photoreactive main chain in such a range, self-organization in the subsequent heat treatment proceeds efficiently, and highly efficient anisotropy formation in the film is attained.

In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, the amount of photocrosslinking reaction, photoisomerization reaction, or photoFris rearrangement reaction of the photosensitive group in the main chain of the main chain polymer film Optimize. And with subsequent heat processing, highly efficient and anisotropic introduction|transduction with respect to the coating film used for this invention is implement|achieved. In that case, about the quantity of a preferable polarization|polarized-light ultraviolet-ray, it can implement based on evaluation of the ultraviolet absorption of the coating film used for this invention.

That is, with respect to the coating film used for this invention, the ultraviolet absorption of the direction parallel to the polarization direction of the polarized ultraviolet-ray after polarized-ultraviolet irradiation, and the ultraviolet absorption of the perpendicular|vertical direction are measured, respectively. From the measurement result of ultraviolet absorption, (DELTA)A which is the difference of the ultraviolet absorbance of the direction parallel to the polarization direction of the ultraviolet-ray which polarized in the coating film, and the ultraviolet absorbance of the perpendicular|vertical direction is evaluated. And the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the amount of irradiation of polarized ultraviolet rays that realize it are calculated. In the manufacturing method of this invention, on the basis of the polarization|polarized-light ultraviolet irradiation amount which implement|achieves this (DELTA)Amax, the amount of the ultraviolet-ray which polarized in the preferable quantity irradiated in manufacture of a liquid crystal aligning film can be determined.

From the above, in the production method of the present invention, in order to realize highly efficient anisotropy introduction to the coating film, the main chain polymer provides the excellent liquid crystal orientation stability in the temperature range as a reference, and the preferable heating as described above. It is desirable to set the temperature. Therefore, it is preferable to set the temperature of the heating after polarization|polarized-light ultraviolet irradiation into 100 degreeC - 300 degreeC, and it is more preferable to set it as 150 degreeC - 250 degreeC. By doing in this way, larger anisotropy is provided in the coating film used for this invention.

By doing so, the liquid crystal display device provided by the present invention exhibits high reliability against external stress such as light or heat.

As mentioned above, the board|substrate for lateral electric field drive type liquid crystal display elements manufactured using the composition of this invention, or the lateral electric field drive type liquid crystal display element which has the board|substrate becomes a thing excellent in reliability, and a large-screen, high-definition liquid crystal television etc. can be used preferably. In addition, since the liquid crystal aligning film produced by the method of the present invention has excellent liquid crystal alignment stability and reliability, it can be used also for a variable phase machine using liquid crystal, and this variable phase machine can vary the resonance frequency, for example. It can be used suitably for an antenna etc.

Example

The abbreviation used in the Example is as follows.

NMP: N-methyl-2-pyrrolidone

BCS : Butyl Cellosolve

DA-1: the following structural formula (DA-1)

DA-2: the following structural formula (DA-2)

DA-3: the following structural formula (DA-3)

DA-4: the following structural formula (DA-4)

DA-5: the following structural formula (DA-5)

DA-6: the following structural formula (DA-6)

DA-7: the following structural formula (DA-7)

DA-8: the following structural formula (DA-8)

DA-9: the following structural formula (DA-9)

DA-10: the following structural formula (DA-10)

DA-11: the following structural formula (DA-11)

DA-12: the following structural formula (DA-12)

DA-13: the following structural formula (DA-13)

DA-14: the following structural formula (DA-14)

DA-15: the following structural formula (DA-15)

CA-1: the following structural formula (CA-1)

CA-2: the following structural formula (CA-2)

[Formula 17]

[Formula 18]

[Formula 19]

<Measurement of viscosity>

In the synthesis example, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Industries, Ltd.) at a sample amount of 1.1 ml, cone rotor TE-1 (1°34', R24), at a temperature of 25°C. measured.

(Synthesis Example 1)

1.88 g (7.0 mmol) of DA-1 and 1.61 g (7.0 mmol) of DA-7 are weighed to a 100 ml 4-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 30.6g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.61g (13.3 mmol), 13.1g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 263 mPa*s.

14.5 g of this polyamic acid solution is fractionated in a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.6 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-1) got

(Synthesis Example 2)

1.88 g (7.0 mmol) of DA-1 and 1.71 g (7.0 mmol) of DA-8 are weighed to a 100 ml 4-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 31.1 g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.57g (13.1 mmol), 13.3g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 326 mPa*s.

14.9 g of the solution of this polyamic acid is fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 13.0 g of NMP and 12.0 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-2) got

(Synthesis Example 3)

1.74 g (6.5 mmol) of DA-1 and 1.68 g (6.5 mmol) of DA-9 are weighed to a 100 ml four-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 29.6g of NMP was added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.36g (12.0mmol), 12.7g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 261 mPa*s.

14.5 g of the solution of this polyamic acid is fractionated in the 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.6 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-3) got

(Synthesis Example 4)

1.74 g (6.5 mmol) of DA-1 and 1.77 g (6.5 mmol) of DA-10 are weighed to a 100 ml four-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 30.1 g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.37g (12.1 mmol), 12.9g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and the solution of the polyamic acid was obtained. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 302 mPa*s.

14.6 g of the solution of this polyamic acid is fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 12.7 g of NMP and 11.7 g of BCS are added, it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-4) got

(Synthesis Example 5)

1.74 g (6.5 mmol) of DA-1 and 1.86 g (6.5 mmol) of DA-11 are weighed to a 100 ml four-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 30.5 g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.35g (12.0mmol), 13.1g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and the solution of the polyamic acid was obtained. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 294 mPa*s.

14.6 g of the solution of this polyamic acid is fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS are added, it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-5) got

(Synthesis Example 6)

1.74 g (6.5 mmol) of DA-1 and 1.95 g (6.5 mmol) of DA-12 are weighed to a 100 ml 4-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 31.0 g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.37g (12.1 mmol), 13.3g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 304 mPa*s.

14.6 g of the solution of this polyamic acid is fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS are added, it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-6) got

(Synthesis Example 7)

1.61 g (6.0 mmol) of DA-1 and 1.89 g (6.0 mmol) of DA-13 are weighed to a 100 ml 4-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 29.1 g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.18g (11.1 mmol), 12.5g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 305 mPa*s.

15.0 g of the solution of this polyamic acid is fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 13.0 g of NMP and 12.0 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-7) got

(Synthesis Example 8)

1.78 g (7.0 mmol) of DA-2 and 1.71 g (7.0 mmol) of DA-8 are weighed to a 100 ml four-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 31.0 g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, 2.55 g (13.0 mmol) of CA-1 was added, 13.3 g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 334 mPa*s.

14.9 g of the solution of this polyamic acid is fractionated in a 100 ml Erlenmeyer flask containing a stirrer, 13.0 g of NMP and 12.0 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-8) got

(Synthesis Example 9)

1.88 g (7.0 mmol) of DA-3 and 1.71 g (7.0 mmol) of DA-8 are weighed to a 100 ml 4-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 31.5 g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.55g (13.0 mmol), 13.5g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 315 mPa*s.

14.6 g of the solution of this polyamic acid is fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-9) got

(Synthesis Example 10)

1.74 g (6.5 mmol) of DA-1 and 1.59 g (6.5 mmol) of DA-8 are weighed to a 100 ml 4-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 29.6g of NMPs were added, and nitrogen It was dissolved by stirring while sending. 1.86 g (9.5 mmol) CA-1 was added, stirring this diamine solution under water cooling, and it stirred at 23 degreeC for 30 minute(s) in nitrogen atmosphere. After that, 0.57 g (2.6 mmol) of CA-2 was added, 12.7 g of NMP was further added, and it stirred at 50 degreeC in nitrogen atmosphere for 15 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 308 mPa*s.

14.6 g of the solution of this polyamic acid is fractionated in a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS are added, it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-10) got

(Synthesis Example 11)

0.80 g (3.5 mmol) of DA-4 and 2.57 g (10.5 mmol) of DA-8 are weighed in a 100 ml four necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 30.4g of NMP was added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, 2.55 g (13.0 mmol) of CA-1 was added, 13.0 g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 324 mPa*s.

14.9 g of the solution of this polyamic acid is fractionated in a 100 ml Erlenmeyer flask containing a stirrer, 13.0 g of NMP and 12.0 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-11) got

(Synthesis Example 12)

1.13 g (3.3 mmol) of DA-5 and 2.38 g (9.8 mmol) of DA-8 are weighed to a 100 ml four-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 30.2g of NMP was added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.37g (12.1 mmol), 12.9g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and the solution of the polyamic acid was obtained. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 298 mPa*s.

14.6 g of this polyamic acid solution is fractionated in a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS are added, stirred with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-12) got

(Synthesis Example 13)

0.74 g (3.5 mmol) of DA-6 and 2.57 g (10.5 mmol) of DA-8 are weighed to a 100 ml 4-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 30.1 g of NMPs were added, and nitrogen It was dissolved by stirring while sending. 2.55 g (13.0 mmol) of CA-1 was added, stirring this diamine solution under water cooling, 12.9 g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 337 mPa*s.

14.6 g of the solution of this polyamic acid is fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-13) got

(Comparative Synthesis Example 1)

3.49 g (13.0 mmol) of DA-1 was weighed in the 100 mL four necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 29.9 g of NMPs were added, and it stirred, sending nitrogen, and it was made to melt|dissolve. While stirring this diamine solution under water cooling, CA-1 was added 2.33g (11.9 mmol), 12.8g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 357 mPa*s.

14.9 g of the solution of this polyamic acid is fractionated in a 100 ml Erlenmeyer flask containing a stirrer, 13.0 g of NMP and 12.0 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (B-1) got

(Comparative Synthesis Example 2)

1.88 g (7.0 mmol) of DA-1 and 1.40 g (7.0 mmol) of DA-14 are weighed to a 100 ml 4-necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 30.1 g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, 2.58g (13.2 mmol) of CA-1 was added, 12.9g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 288 mPa*s.

14.6 g of this polyamic acid solution is fractionated in a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS are added, stirred with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (B-2) got

(Comparative Synthesis Example 3)

1.88 g (7.0 mmol) of DA-1 and 1.39 g (7.0 mmol) of DA-15 are weighed to a 100 ml four necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 30.0g of NMPs were added, and nitrogen It was dissolved by stirring while sending. While stirring this diamine solution under water cooling, CA-1 was added 2.59g (13.2 mmol), 12.9g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 279 mPa*s.

14.6 g of the solution of this polyamic acid is fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS are added, it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (B-3) got

(Comparative Synthesis Example 4)

3.20 g (14.0 mmol) of DA-4 was weighed in the 100 ml four necked flask in which the stirring apparatus and the nitrogen introduction tube were formed, 29.4g of NMP was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. While stirring this diamine solution under water cooling, CA-1 was added 2.53g (12.9 mmol), 12.6g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 364 mPa*s.

14.6 g of the solution of this polyamic acid is fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS are added, it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (B-4) got

<Preparation of the liquid crystal cell for liquid-crystal orientation evaluation>

Below, the preparation method of the liquid crystal cell for evaluating liquid-crystal orientation is shown.

The liquid crystal cell provided with the structure of the liquid crystal display element of the FFS system was produced. First, a substrate to which an electrode is attached was prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. On the board|substrate, the IZO electrode which comprises a counter electrode as a 1st layer was formed in the whole surface. On the counter electrode of the 1st layer, the SiN (silicon nitride) film|membrane formed into a film by the CVD method was formed as a 2nd layer. The film thickness of the SiN film of the second layer is 500 nm, and functions as an interlayer insulating film. On the SiN film of the 2nd layer, as a 3rd layer, the comb-tooth-shaped pixel electrode formed by patterning an IZO film was arrange|positioned, and two pixels of a 1st pixel and a 2nd pixel were formed. The size of each pixel is 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the 3rd layer has a comb-tooth-shaped shape comprised by arranging a plurality of "<"-shaped electrode elements in which the center part was bent similarly to the figure described in Unexamined-Japanese-Patent No. 2014-77845 (Unexamined-Japanese-Patent No. 7). The width in the width direction of each electrode element is 3 µm, and the interval between the electrode elements is 6 µm. Since the pixel electrode forming each pixel is constituted by arranging a plurality of "<"-shaped electrode elements in which the central part is bent, the shape of each pixel is not a rectangular shape, but is bent in the central part similarly to the electrode element, It has a shape similar to the letter ' in bold letters. And each pixel is divided|segmented up and down with the bent part in the center as a boundary, and has the 1st area|region above and the 2nd area|region below the bending|flexion part.

Comparing the 1st area|region and the 2nd area|region of each pixel, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, when the direction of the line segment projected on the substrate by the polarization plane of the polarized ultraviolet light to be described later is taken as a reference, in the first area of the pixel, the electrode element of the pixel electrode forms an angle of +10° (clockwise), In the second region of , the electrode element of the pixel electrode was formed to form an angle (clockwise) of -10°. That is, in the first region and the second region of each pixel, the direction of the rotational operation (in-plane switching) of the liquid crystal caused by the voltage application between the pixel electrode and the counter electrode in the substrate plane is opposite to each other. configured to be this.

Next, after filtering the liquid crystal aligning agent obtained by the synthesis example and the comparative synthesis example with a 1.0-micrometer filter, it apply|coated to the board|substrate with the said electrode prepared by spin coat application|coating. Then, it dried for 90 second on the hotplate set to 70 degreeC. Next, using the exposure apparatus manufactured by Ushio Electric Co., Ltd.: APL-L050121S1S-APW01, the linearly polarized light of the ultraviolet-ray was irradiated from the perpendicular direction with respect to the board|substrate through a wavelength selective filter and a polarizing plate. At this time, the polarization plane direction was set so that the direction of the line segment which projected the polarization plane of a polarized ultraviolet-ray on the board|substrate might become the direction inclined by 10 degrees with respect to the 3rd layer IZO comb electrode. Next, it baked for 30 minutes with IR (infrared) type|mold oven set to 230 degreeC, and obtained the board|substrate with a polyimide liquid crystal aligning film with a film thickness of 100 nm to which orientation processing was performed. Moreover, the board|substrate with the polyimide liquid crystal aligning film to which the orientation process was carried out similarly to the above also to the glass substrate which has a columnar spacer with a height of 4 micrometers by which the ITO electrode is formed in the back surface as a counter board|substrate was obtained. The liquid crystal aligning film surface of these two sheets is set as one set, and the sealing compound is printed in the form which left a liquid crystal injection hole on the board|substrate of one side, and liquid crystal aligning film surfaces face each other for the other board|substrate, and the polarization surface of polarized ultraviolet rays was joined and crimped so that the direction of the line segment projected onto the substrate was parallel. Then, the sealing compound was hardened and the cell gap produced the empty cell whose cell gap is 4 micrometers. Liquid crystal MLC-7026-100 (Negative liquid crystal by Merck Corporation) was inject|poured into this empty cell by the pressure reduction injection method, the injection port was sealed, and the liquid crystal cell of the FFS system was obtained. Then, after heating the obtained liquid crystal cell at 120 degreeC for 30 minutes and leaving it to stand at 23 degreeC overnight, it was used for evaluation of the liquid-crystal orientation.

<Evaluation of liquid crystal orientation>

Using this liquid crystal cell, the alternating voltage of 16VPP was applied by the frequency of 30 Hz in a 70 degreeC constant temperature environment for 168 hours. Then, it was set as the state which short-circuited between the pixel electrode of a liquid crystal cell, and a counter electrode, and it was left to stand at 23 degreeC overnight as it is.

After standing, the liquid crystal cell was installed between two polarizing plates arranged so that the polarization axes were orthogonal to each other, and the backlight was turned on in a state where no voltage was applied, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of the transmitted light was the smallest. And the rotation angle at the time of rotating the liquid crystal cell from the angle at which the 2nd area|region of a 1st pixel becomes the darkest to the angle at which the 1st area|region becomes the darkest was computed as angle (DELTA). Similarly, in the second pixel, the second region and the first region were compared to calculate the same angle Δ. And the average value of the angle (DELTA) value of a 1st pixel and a 2nd pixel was computed as angle (DELTA) of a liquid crystal cell. When the value of the angle (DELTA) of this liquid crystal cell was less than 1.5 degrees, when the value of "good|favorableness" and the angle (DELTA) was 1.5 degrees or more, it defined and evaluated it as "poor".

<Production of liquid crystal cell for voltage retention evaluation>

Using a glass substrate with an ITO electrode, before printing of the sealing compound, except that a 4 µm bead spacer was dispersed on the liquid crystal aligning film surface on one side of the substrate, in the same procedure as the preparation of the liquid crystal cell for evaluation of liquid crystal alignment, The liquid crystal cell for voltage retention measurement was produced.

<Evaluation of voltage retention>

Voltage retention was evaluated using this liquid crystal cell. Specifically, to the liquid crystal cell obtained by the above method, an alternating voltage of 2 VPP is applied for 60 μsec at a temperature of 70 ° C., the voltage 167 m second later is measured, and the voltage retention rate ( Also called VHR). In addition, the measurement was performed using the voltage retention measuring apparatus (VHR-1, the Toyo Technica company make), Voltage: +/-1V, Pulse Width: 60 microseconds, Flame Period: 167 milliseconds setting. When the value of the voltage retention of this liquid crystal cell was 80 % or more, when the value of "good|favorableness" and voltage retention was less than 80 %, it defined as "defect" and evaluated.

(Example 1)

Using the liquid crystal aligning agent (A-1) obtained by the synthesis example 1, two types of liquid crystal cells were produced as described above. Irradiation of polarized ultraviolet light was performed using a high-pressure mercury vapor lamp through a wavelength selective filter: 240 LCF and a 254 nm type polarizing plate. The amount of irradiation of polarized ultraviolet rays is measured using a illuminometer UVD-S254SB manufactured by Ushio Electric Co., Ltd., and the wavelength of 254 nm is changed in the range of 200 to 1500 mJ/cm 2 , three different polarized ultraviolet irradiation amounts The above liquid crystal cell was produced.

As a result of evaluating the liquid-crystal orientation about these liquid crystal cells, the polarization|polarized-light ultraviolet irradiation amount with which angle (DELTA) was the most favorable was 900 mJ/cm<2>, and angle (DELTA) was favorable at 1.06 degrees.

Moreover, when voltage retention was evaluated with respect to the liquid crystal cell produced with the same amount of polarization|polarized-light ultraviolet irradiation, voltage retention was favorable at 85.3 %.

(Examples 2 to 12)

Except having used the liquid crystal aligning agent obtained by the synthesis examples 2-12, the method similar to Example 1 evaluated the liquid-crystal orientation and voltage retention.

(Example 13)

What used the liquid crystal aligning agent (A-13) obtained in Synthesis Example 13, and irradiation of polarized ultraviolet rays using a metal halide lamp, wavelength selective filter: i-wide BPF, and 313-365 nm type polarizing plate interposed The liquid-crystal orientation and voltage retention were evaluated by the method similar to Example 1 except having carried out and carrying out, changing the irradiation amount of a polarized-light ultraviolet-ray in wavelength 365nm, respectively in the range of 1000-4000 mJ/cm<2>.

(Comparative Examples 1 to 4)

Except having used the liquid crystal aligning agent obtained by the comparative synthesis examples 1-4, the method similar to Example 1 evaluated the liquid-crystal orientation and voltage retention.

When the liquid crystal aligning agent obtained by the synthesis example and the comparative synthesis example is used for Table 1, the polarization ultraviolet irradiation wavelength when the angle (Delta) was the most favorable, the result of evaluation of the liquid-crystal orientation, and the evaluation of the voltage retention indicates

As shown in Table 1, in Examples 1 to 13, the angle Δ, which is the difference between the orientation and azimuth angles before and after the AC drive, was good at less than 1.5°, and the VHR was also 80% or more, showing good characteristics, all of which had good afterimage characteristics. Since it is, it is excellent in the display quality improvement of a liquid crystal display element. On the other hand, in Comparative Examples 1-4, the characteristic which made the angle (DELTA) and voltage retention compatible was not confirmed.

Thus, it was confirmed that the liquid crystal display element manufactured by the method of this invention shows the very excellent afterimage characteristic.

A substrate for a transverse electric field driving type liquid crystal display device manufactured by using the composition of the present invention or a transverse electric field driving type liquid crystal display device having the substrate has excellent reliability and can be preferably used for a large-screen, high-definition liquid crystal television, etc. have. In addition, since the liquid crystal aligning film produced by the method of the present invention has excellent liquid crystal alignment stability and reliability, it can be used also for a variable phase machine using liquid crystal, and this variable phase machine is, for example, an antenna capable of varying the resonance frequency. etc. can be used preferably.

Claims (11)

A polymer obtained from a diamine component containing at least one selected from diamines having a structure represented by the following formulas (1) to (3) and a diamine having a structure represented by the following formula (4) (wherein W and X are each independently an aromatic ring having 6 to 14 carbon atoms, Y is an oxygen atom or a sulfur atom, Z is an oxygen atom and a divalent organic group including alkylene, R ₁ to R ₇ are each independently a hydrogen atom or It is a monovalent organic group, and m, n, o, p and q are each independently an integer of 0-4.) Diamine which has a structure represented by Formula (4) as a liquid crystal aligning agent containing and an organic solvent The liquid crystal aligning agent which is a diamine represented by following formula (4)-1.

The method of claim 1,
The liquid crystal aligning agent whose said polymer is an at least 1 sort(s) of polymer chosen from the group which consists of the polyimide precursor which is the polymer of the said diamine component, and tetracarboxylic dianhydride, and the polyimide which is its imidation. 3. The method of claim 2,
The said polyimide precursor is a following formula (5) (in Formula (5), X< ₁ > is a tetravalent organic group derived from a tetracarboxylic-acid derivative, Y< ₁ > is selected from Formula (1)-(3) It is a divalent organic group derived from the diamine containing the structure, and R ₁₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) and the structural unit represented by the following formula (6) (in formula (6), X ₂ is It is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y2 is a _divalent organic group derived from the diamine containing the structure represented by Formula ( ₄ ), R12 is a hydrogen atom or a C1-C5 alkyl group The liquid crystal aligning agent which has a structural unit represented by .).

4. The method of claim 3,
The liquid crystal aligning agent whose structure of X< ₁ > and the structure of X< ₂ > are at least 1 sort(s) chosen from the group which consists of the following structures each independently in said Formula (5) and Formula (6).

4. The method of claim 3,
The liquid crystal aligning agent in which the polymer which has a structural unit represented by said Formula (5) and Formula (6) contains 10 mol% or more with respect to all the polymers contained in a liquid crystal aligning agent. 4. The method of claim 3,
The liquid crystal aligning agent containing at least 1 sort(s) chosen from the group which consists of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether in the said organic solvent. [I] Process of apply|coating the liquid crystal aligning agent in any one of Claims 1-6 on the board|substrate which has a conductive film for a transverse electric field drive, and forming a coating film;
[II] The process of irradiating the ultraviolet-ray which polarized to the coating film obtained by [I]; and
[III] Process of heating the coating film obtained in [II];
The manufacturing method of the board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for lateral electric field drive type liquid crystal display elements to which orientation control ability was provided by having. The board|substrate which has a liquid crystal aligning film for lateral electric field drive type liquid crystal display elements manufactured by the method of Claim 7. The transverse electric field drive type liquid crystal display element which has the board|substrate of Claim 8. [I] Process of apply|coating the liquid crystal aligning agent in any one of Claims 1-6 on the board|substrate which has a conductive film for a transverse electric field drive, and forming a coating film;
[II] The process of irradiating the ultraviolet-ray which polarized to the coating film obtained by [I]; and
[III] Process of heating the coating film obtained in [II];
The process of preparing the 1st board|substrate which has this liquid crystal aligning film which obtains the liquid crystal aligning film for lateral electric field drive type liquid crystal display elements to which orientation control ability was provided by having;
[I'] Process of apply|coating the liquid crystal aligning agent in any one of Claims 1-6 on a 2nd board|substrate, and forming a coating film;
[II'] The process of irradiating the polarized ultraviolet-ray to the coating film obtained by [I']; and
[III'] The process of heating the coating film obtained by [II'];
The process of obtaining the 2nd board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film to which orientation control ability was provided by having; and
[IV] a step of arranging the first and second substrates opposite to each other so that the liquid crystal aligning films of the first and second substrates face each other through a liquid crystal to obtain a liquid crystal display element;
The manufacturing method of the liquid crystal display element which obtains a transverse electric field drive type liquid crystal display element by having. A transverse electric field driving type liquid crystal display device manufactured by the method according to claim 10 .