KR20190054084A - Liquid crystal aligning agent, liquid crystal alignment 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 kind 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 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 containing an oxygen atom and alkylene, and R ₁ to R ₇ are each independently And m, n, o, p and q are each independently an integer of 0 to 4), and an organic solvent.
[Chemical Formula 1]

Description

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

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element for producing a liquid crystal display element having excellent baking properties.

BACKGROUND ART [0002] Liquid crystal display devices are known as lightweight, thin and low power consumption display devices, and recently, they have been used for a large-sized television application and have achieved remarkable development. The liquid crystal display element is constituted by sandwiching the liquid crystal layer by a pair of transparent substrates having electrodes, for example. In the liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.

That is, the liquid crystal alignment film is formed as a constituent member of the liquid crystal display element on the surface of the substrate which holds the liquid crystal in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. In addition to the role of aligning the liquid crystal in a certain direction, such as a direction parallel to the substrate, for example, the liquid crystal alignment film may be required to control the pretilt angle of the liquid crystal. The ability to control the orientation of the liquid crystal in such a liquid crystal alignment film (hereinafter referred to as orientation control ability) is imparted by subjecting the organic film constituting the liquid crystal alignment film to an orientation treatment.

Conventionally, a rubbing method is known as an alignment treatment method of a liquid crystal alignment film for imparting alignment control ability. The rubbing method is a method of 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 predetermined direction, To orient the liquid crystal. This rubbing method has been used in a manufacturing process of a conventional liquid crystal display element since a relatively stable liquid crystal alignment state can be realized easily. As an organic film used for a liquid crystal alignment film, a polyimide-based organic film having excellent reliability and electrical characteristics such as heat resistance has been mainly selected.

However, in the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, generation of oscillation or static electricity is a problem in some cases. Further, due to the recent finer definition of the liquid crystal display element and the unevenness due to the electrode on the substrate or the switching active element for driving the liquid crystal, the surface of the liquid crystal alignment film can not be uniformly rubbed with the cloth, There was a case that it could not be realized.

Therefore, as another method of aligning the liquid crystal alignment film without rubbing, a photo alignment method is actively studied.

There are various methods for the photo-alignment method. Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is oriented in accordance with the anisotropy.

As a main photoalignment method, a photoalignment method of a decomposition type is known. For example, polarized ultraviolet rays are irradiated to the polyimide film, and anisotropic decomposition is generated by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure. Then, the liquid crystal is oriented by the polyimide remaining ungraded (see, for example, Patent Document 1).

In addition, a photo-crosslinking method or a photo-isomerization type optical alignment method is also known. For example, polyvinyl cinnamate is used to irradiate polarized ultraviolet rays to generate a dimerization reaction (crosslinking reaction) at the double bond portions of two side chains parallel to the polarized light. Then, the liquid crystal is oriented in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). When a side chain type polymer having azobenzene as a side chain is used, polarized ultraviolet light is irradiated to generate an isomerization reaction in the azobenzene moiety of the side chain parallel to the polarized light to align the liquid crystal in a direction orthogonal to the polarization direction See, for example, Non-Patent Document 2).

As in the example described above, in the alignment treatment method of the liquid crystal alignment film by the photo alignment method, rubbing is unnecessary, and there is no fear of occurrence of oscillation or static electricity. In addition, it is possible to perform orientation treatment on a substrate of a liquid crystal display element having irregularities on its surface, which is a preferred method of alignment treatment of a liquid crystal alignment film in 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 described above, the photo-alignment method makes the rubbing process itself unnecessary as compared with the rubbing method which has conventionally been industrially used as an alignment processing method of a liquid crystal display element, and thus has a great advantage. In contrast, in the optical alignment method, the alignment control ability can be controlled by changing the irradiation amount of the polarized light, as compared with the rubbing method in which the alignment control ability is made substantially constant by rubbing. However, in the photo alignment method, when it is desired to achieve the same degree of alignment control ability as in the case of the rubbing method, a large amount of polarized light is required to be irradiated or a stable liquid crystal alignment can not be realized.

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 with an output power of 500 W for 60 minutes, and a long time and a large amount of ultraviolet irradiation . In addition, even in the case of the diminution type or optical isomerization type photo-alignment method, a large amount of ultraviolet light irradiation of several tens to several tens J may be required. Further, in the case of the photo-crosslinking or photo-isomerization type optical alignment method, since the thermal stability and optical stability of alignment of liquid crystals are inferior, problems such as occurrence of orientation defects and display baking there was. Particularly, in a liquid crystal display device of a transversely-field-driven type, liquid crystal molecules are switched in the plane, and alignment of liquid crystals after driving the liquid crystal is liable to occur, and display baking caused by AC driving becomes a big problem.

Therefore, in the photo alignment method, it is required to achieve high efficiency of alignment treatment and realization of stable liquid crystal alignment, and a liquid crystal alignment film and a liquid crystal alignment agent capable of highly imparting a high alignment control ability to the liquid crystal alignment film can be performed with high efficiency.

An object of the present invention is to provide a substrate having a liquid crystal alignment film for a liquid crystal display element of a transverse electric field drive type, which has high controllability of orientation with high efficiency and is excellent in baking property, and a liquid crystal display element of transverse electric field driving type having the substrate.

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found the following inventions.

1. A polymer comprising a polymer obtained from a diamine component containing at least one kind 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) A 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 a divalent organic group containing an oxygen atom and alkylene, M, n, o, p and q are each independently an integer of 0 to 4), and R < ₁ > to R < ₇ > each independently represent a hydrogen atom or a monovalent organic group.

[Chemical Formula 1]

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type, which has high controllability of alignment with high efficiency and excellent baking property, and a transverse electric field driven liquid crystal display element having the substrate.

Since the transverse electric-field-driven liquid crystal display device manufactured by the method of the present invention has the alignment control ability with high efficiency, the display characteristics are not impaired even after continuous driving for a long time.

As a result of intensive studies, the present inventors have obtained the following findings and have completed the present invention.

The polymer composition used in the production method of the present invention has a photosensitive main chain type polymer capable of exhibiting liquid crystallinity (hereinafter, simply referred to as a main chain type polymer), and a coating film obtained using the above polymer composition , And a film having a photosensitive main chain type polymer capable of exhibiting liquid crystallinity. This coating film is subjected to orientation treatment by polarized irradiation without rubbing treatment. After the polarized light irradiation, the main chain type polymer film is heated to obtain a coating film (hereinafter, also referred to as a liquid crystal alignment film) imparted with orientation control ability. At this time, a slight anisotropy expressed by polarized light becomes a driving force, and the main chain type polymer itself is efficiently rearranged by self-organization. As a result, a highly efficient alignment treatment can be realized as a liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.

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

A polymer obtained from a diamine component containing at least one kind 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 type polymer And W is an aromatic ring having 6 to 14 carbon atoms, Y is an oxygen atom or a sulfur atom, Z is an oxygen atom and an alkylene group, And m, n, o, p and q are each independently an integer of 0 to 4), wherein R ₁ to R ₇ are each independently a hydrogen atom or a monovalent organic group.

Hereinafter, each condition will be described in detail.

(2)

≪ Diamines having a specific structure >

The liquid crystal aligning agent of the present invention comprises a polymer obtained from a diamine component containing at least one kind selected from diamines having a structure represented by the above formulas (1) to (3) and a diamine having a structure represented by the above formula (4) , And a liquid crystal aligning agent containing an organic solvent.

In the formula (1), W is an aromatic ring having 6 to 14 carbon atoms, and R ₁ is a monovalent organic group. Examples of the aromatic ring include a benzene ring, a naphthalene ring and biphenylene. From the standpoint of solubility and the like of the obtained polymer, 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, and a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Among them, the monovalent organic group is preferably a methyl group or a methoxy group.

As the diamine having the structure of the above formula (1), a diamine in which two amino groups are bonded to the above structure is preferable. Specific examples thereof include, but are not limited to, the following.

(3)

In the formula (2), X is an aromatic ring having 6 to 14 carbon atoms, and R ₂ is a monovalent organic group. Examples of the aromatic ring include a benzene ring, a naphthalene ring and biphenylene. From the standpoint of solubility and the like of the obtained polymer, 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, and a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Among them, the monovalent organic group is preferably a methyl group or a methoxy group.

As the diamine having the structure of the formula (2), a diamine in which two amino groups are bonded to the above structure is preferable. Specific examples thereof include, but are not limited to, the following.

[Chemical 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 here include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, and a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms . Among them, the monovalent organic group is preferably a methyl group or a methoxy group.

As the diamine having the structure of the formula (3), a diamine in which two amino groups are bonded to the above structure is preferable. Specific examples thereof include, but are not limited to, the following.

[Chemical Formula 5]

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

As the diamine having the structure of the formula (4), a diamine in which two amino groups are bonded to the above structure is preferable. Specific examples thereof include, but are not limited to, the following.

[Chemical Formula 6]

In the case where r is an even number such as 2, 4, 6 and 8, the linearity of the resulting polymer is increased. As a result, in the heating step after the irradiation of polarized light, the liquid crystal alignment film having higher orientation control ability Can be obtained.

<Polymer>

The polymer of the present invention is a polymer obtained by using the above diamine. Specific examples thereof include polyamic acid, polyamic acid ester, polyimide, polyurea and polyamide. From the viewpoint of use as a liquid crystal aligning agent, the structural unit represented by the following formula (5) and the following formula (6) , A polyimide precursor containing a structural unit represented by the following general formula (1), and an imide thereof.

(7)

In the formula (5), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁ is a divalent group derived from a diamine containing a structure selected from the formulas (1) to (3) 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 imidization by heating.

&Lt; Tetracarboxylic acid dianhydride &gt;

X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure thereof is not particularly limited. Further, X ₁ in the polyimide precursor is preferably at least _{one selected} from the group consisting of the solubility of the polymer in the solvent, the coating property of the liquid crystal aligning agent, the orientation of the liquid crystal when the liquid crystal alignment film is used, the voltage holding ratio, And may be one type in the same polymer or two or more types may be mixed.

Specific examples of X _{1 include} the structures of the formulas (X-1) to (X-46) shown on pages 13 to 14 of International Publication No. 2015/119168.

Hereinafter, preferable X ₁ structure is shown, but the present invention is not limited thereto.

[Chemical Formula 8]

[Chemical Formula 9]

Of these structures, (A-1) and (A-2) are particularly preferable from the viewpoint of further improvement of the film hardness, and (A-4) is particularly preferable from the viewpoint of further improvement of the relaxation rate of the accumulated charges, (A-15) to (A-17) and the like are particularly preferable from the viewpoint of further improving the liquid crystal aligning property and the relaxation speed of the accumulated charges.

<Diamine>

In the formula (5), specific examples of Y ₁ include a structure in which two amino groups are excluded from a diamine having a structure selected from the formulas (1) to (3).

In the formula (6), X ₂ is a tetracarboxylic a tetravalent organic group derived from a carboxylic acid derivative thereof, Y ₂ is a divalent organic group derived from a diamine containing the structure represented by the formula (4), R ₁₂ is A hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₁₂ is preferably a hydrogen atom, a methyl group or an ethyl group in view of ease of imidization by heating.

[Chemical formula 10]

Specific examples of X ₂ include the same structures as exemplified in X ₁ of formula (5), including preferred examples. A specific example of Y ₂ is a structure in which two amino groups are removed from a diamine having a structure represented by the formula (4).

&Lt; Polymer (other structural units) &gt;

The polyimide precursor containing the structural unit represented by the formula (5) and the structural unit represented by the formula (6) may contain a structural unit represented by the following formula (7) And at least one selected from the group consisting of polyimide which is a polycondensed polyimide.

(11)

In the formula (7), X ₃ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and Y ₃ is a diamine in which none of the structures represented by the formulas (1) to (4) , R ₁₃ is the same as defined for R ₁₁ in the formula (5), and each R ₂₃ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferable that at least one of the two R ₂₃ groups is a hydrogen atom.

Specific examples of X &lt; ₃ &gt; include the same structures as exemplified in X &lt; ₁ &gt; in formula (5), including preferred examples. Y ₃ is a divalent organic group derived from a diamine not containing any of the structures represented by the formulas (1) to (4) in the main chain direction, and its structure is not particularly limited. Further, Y ₃ is suitably selected according to the degree of the required properties such as solubility of the polymer in the solvent, coating property of the liquid crystal aligning agent, orientation of the liquid crystal in the case of the liquid crystal alignment film, voltage holding ratio, In the same polymer, one type may be used, or two or more types may be mixed.

Y represents a _third embodiment of the formula (Y-1) ~ (Y -97) is placed on the structure, and, on page 8-12 of the formula (2) is placed on the page 4 of International Publication No. 2015/119168, (Y-101) to (Y-118); A bivalent organic group excluding two amino groups from the formula (2), which is listed on page 6 of International Publication No. 2013/008906; A bivalent organic group excluding two amino groups from the formula (1) shown on page 8 of International Publication No. 2015/122413; The structure of equation (3) published on page 8 of International Publication No. 2015/060360; A divalent organic group excluding two amino groups from the formula (1) described on page 8 of Japanese Laid-Open Patent Publication No. 2012-173514; Di-valent organic groups excluding two amino groups from the formulas (A) to (F) shown on page 9 of International Publication No. 2010-050523.

Hereinafter, the preferred structure of Y ₃ is shown, but the present invention is not limited thereto.

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

Among the above structures, (B-28) and (B-29) are particularly preferable from the viewpoint of further improvement of the film hardness, and (B-1) (B-2), (B-9), (B-14) to (B-18) and (B-27) are preferable from the viewpoint of further improvement of the relaxation rate of the accumulated charges (B-26) and the like are preferable from the viewpoint of further improvement of the voltage holding ratio.

At least one kind selected from a polyimide precursor including a structural unit represented by the formula (5) and a structural unit represented by the formula (6), and an imide thereof, and a polyimide including the structural unit represented by the formula (7) , The total of the structural unit represented by the formula (5) and the structural unit represented by the formula (6) is preferably at least 10 mol% based on the sum of the formula (5) and the formula (6) and the formula (7) More preferably 20 mol% or more, and particularly preferably 30 mol% or more.

The molecular weight of the polyimide precursor used in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000 in terms of weight average molecular weight.

Examples of the polyimide including the structural unit represented by the formula (5) and the formula (6) include a polyimide obtained by ring closure of the polyimide precursor. In this polyimide, the closed rate (also referred to as the imidization rate) of the amidic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the application and purpose.

Methods for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalyst imidation in which the catalyst is added to the solution of the polyimide precursor.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is a polymer obtained from a diamine component containing at least one kind selected from diamines having the structures represented by the formulas (1) to (3) and diamines having the structure represented by the formula (4) ). However, the polymer may contain two or more kinds of specific polymers having different structures to the extent that the effects described in the present invention are exerted. In addition to the specific polymer, other polymers, that is, polymers having no bivalent groups represented by the formulas (1) to (4), may be contained. Examples of the other polymer include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or a derivative thereof, poly (styrene-phenylmaleimide ) Derivatives, and poly (meth) acrylates. When the liquid crystal aligning agent of the present invention contains other polymer, the proportion of the specific polymer to the total polymer component is preferably 5% by mass or more, and may be 5% to 95% by mass, for example.

The liquid crystal aligning agent is used for producing a liquid crystal alignment film and generally takes the form of a coating liquid from the viewpoint of forming a uniform thin film. The liquid crystal aligning agent of the present invention is also preferably a coating liquid containing the above polymer component and an organic solvent for dissolving the polymer component. At that time, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed according to the setting of the thickness of the coating film to be formed. In view of forming a uniform and defect-free coating film, it is preferably 1% by mass or more, and from the viewpoint of the storage stability of the solution, 10% by mass or less is preferable. A particularly preferable concentration of the polymer is 2 to 8 mass%.

The organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- Lactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, and cyclopentanone. Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.

As the organic solvent contained in the liquid crystal aligning agent, a mixed solvent in which a solvent for improving the coating property and the surface smoothness of the coating film when the liquid crystal aligning agent is applied is generally used in addition to the above-mentioned solvent, Also in the liquid crystal aligning agent of the invention, such a mixed solvent is preferably used. Specific examples of the organic solvent used in combination include, but are not limited to, the following examples.

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, 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, Ethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, Ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, propylene carbonate, ethylene carbonate, propylene carbonate, (Methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene Propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene 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 mono Ethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl 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-ethoxypropionic acid, 3 Lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, dicarboxylic acid ester of the following formula [D- 1] to [D-3].

[Chemical Formula 16]

Of the formula ^[D-1], D 1 represents an alkyl group having a carbon number of 1 to 3, wherein ^[D-2], D 2 represents an alkyl group having a carbon number of 1 to 3, formula ^[D-3], D 3 Represents an alkyl group having 1 to 4 carbon atoms.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy- Pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used. The kind and content of the solvent are appropriately selected according to the application device of the liquid crystal aligning agent, application conditions, application environment, and the like.

The liquid crystal aligning agent of the present invention may further contain components other than the polymer component and the organic solvent within the range not hindering the effect of the present invention. Examples of such additional components include adhesion auxiliary agents for enhancing adhesion between the liquid crystal alignment film and the substrate, adhesion between the liquid crystal alignment film and the sealant, cross-linking agents for enhancing the strength of the liquid crystal alignment film, dielectric materials for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film, And the like. Specific examples of these additional components are variously disclosed in a known document relating to a liquid crystal aligning agent. For example, in the publication pamphlet of Publication No. 2015/060357, page 53, pages [0105] to [555] And the like.

&Lt; Manufacturing Method of Substrate Having Liquid Crystal Alignment Film &gt; &lt; Production Method of Liquid Crystal Display Element &

A method of manufacturing a substrate having a liquid crystal alignment film of the present invention includes:

[I] a polymer obtained from a diamine component containing at least one kind selected from diamines having the structures represented by the formulas (1) to (3) and diamines having the structure represented by the formula (4) On a substrate having a conductive film for driving a transverse electric field to form a coating film;

[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; And

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

Respectively.

By this process, it is possible to obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which alignment control ability is imparted, and a substrate having the liquid crystal alignment film can be obtained.

Further, by preparing a second substrate in addition to the substrate (first substrate) obtained above, a transverse electric field driven liquid crystal display element can be obtained.

The second substrate may be a substrate which does not have a conductive film for driving a transversal electric field in place of the substrate having a conductive film for driving a transversal electric field. In addition to the above-mentioned steps [I] to [III] , A second substrate having a liquid crystal alignment film imparted with orientation control ability can be obtained by using, for convenience, the steps [I '] to [III'] in the present invention have.

A method of manufacturing a transverse electric field driven liquid crystal display element,

[IV] a step of arranging the first and second substrates obtained above so as to oppose each other so that the liquid crystal alignment layers of the first and second substrates face each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element;

Respectively. As a result, a transverse electric field driven liquid crystal display element can be obtained.

Hereinafter, the respective steps of [I] to [III] and [IV] of the production method of the present invention will be described.

&Lt; Process [I] &gt;

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

<Substrate>

The substrate is not particularly limited, but when the liquid crystal display element to be manufactured is a transmissive type, it is preferable that a substrate having high transparency is used. In this case, there is no particular limitation, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.

Also, considering the application to a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used.

&Lt; Conductive film for driving a transverse electric field &

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

When the liquid crystal display element is a transmissive type, ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide) may be used as the conductive film, but the present invention is not limited thereto.

In the case of a reflective liquid crystal display element, a conductive film may be used as the material for reflecting light such as aluminum, but the present invention is not limited thereto.

As a method of forming a conductive film on a substrate, conventionally known techniques may be used.

The method of applying the above-described polymer composition onto a substrate having a conductive film for driving a transverse electric field is not particularly limited.

As a coating method, a method generally carried out by screen printing, offset printing, flexographic printing, inkjet printing or the like is generally used. Examples of other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (spin coating method), a spraying method, and the like, depending on the purpose.

After the polymer composition is applied onto a substrate having a conductive film for transversal electric field driving, the substrate is heated at 30 to 200 DEG C, preferably 50 to 150 DEG C, by heating means such as a hot plate, a heat circulation type oven or an IR The solvent can be evaporated at &lt; RTI ID = 0.0 &gt; 20 C &lt; / RTI &gt; The drying temperature at this time is preferably lower than the [III] process in view of the liquid crystal alignment stability.

The thickness of the coating film is disadvantageous from the viewpoint of the power consumption of the liquid crystal display element if it is excessively large and from 5 to 300 nm, Nm to 150 nm.

It is also possible to form a step of cooling the substrate on which the coated film has been formed to the room temperature after the [I] process and the subsequent [II] process.

&Lt; Process [II] &gt;

In the step [II], the coated film obtained in the step [I] is irradiated with polarized ultraviolet rays. When polarized ultraviolet rays are irradiated to the film surface of the coating film, polarized ultraviolet rays are irradiated to the substrate from a certain direction through the polarizer. As the ultraviolet ray to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of the coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm may be selected and used so as to selectively cause photo-crosslinking reaction. As ultraviolet rays, 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 amount of irradiation is determined by the amount of polarized ultraviolet light (1) that realizes the maximum value of? A (hereinafter also referred to as? Amma) which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction , More preferably in the range of 1% to 70%, and more preferably in the range of 1% to 50%.

&Lt; Process [III] &gt;

In the step [III], the coated film irradiated with polarized ultraviolet rays in the step [II] is heated. By heating, orientation control ability can be imparted to the coating film.

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

The heating temperature is preferably within a temperature range in which the main chain type polymer exhibits good liquid crystal alignment stability. When the heating temperature is too low, the amplifying effect of anisotropy due to heat tends to be insufficient. When the heating temperature is too high, anisotropy imparted by irradiation with polarized ultraviolet rays tends to disappear. In this case, It may be 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 the step [I].

By the above process, the production method of the present invention can realize introduction of anisotropy to the coating film with high efficiency. A substrate on which a liquid crystal alignment film is formed with high efficiency can be produced.

&Lt; Process [IV] &gt;

[Step IV] is a step of preparing a substrate (first substrate) having a liquid crystal alignment film on a conductive film for driving a transverse electric field obtained in [III] (Second substrate) on which a liquid crystal alignment film having no liquid crystal alignment film was formed was disposed opposite to the liquid crystal alignment films facing each other with liquid crystal interposed therebetween to manufacture a liquid crystal cell by a known method, . It is to be noted that the steps [I '] to [III'] are the same as the steps [I '] to [III'] except that a substrate having no conductive film for transversal field driving is used instead of the substrate having a conductive film for driving a transversal electric field, I] to [III]. Since the difference between the steps [I] to [III] and the steps [I '] to [III'] is only the existence of the conductive film described above, the description of the steps [I '] to [III'] is omitted.

For example, the above-described first and second substrates are prepared, the spacer is dispersed on the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is made inward, A method in which a substrate of a room is sealed and a liquid crystal is injected under reduced pressure or a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which spacers are dispersed and a substrate is then bonded and sealed. At this time, it is preferable to use a substrate having electrodes of a structure like a comb-like driving electrode for lateral electric field driving on one side of the substrate. The diameter of the spacer at this time is preferably 1 mu m to 30 mu m, more preferably 2 mu m to 10 mu m. This spacer diameter determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the method for producing a substrate on which a coating film is formed according to the present invention, a polarizing ultraviolet ray is irradiated after coating a polymer composition on a substrate to form a coating film. Subsequently, by heating, introduction of high efficiency anisotropy into the main chain type polymer film is realized, and a substrate on which a liquid crystal alignment film having a liquid crystal alignment control ability is formed is produced.

In the coating film used in the present invention, the introduction of high efficiency anisotropy into the coating film is realized by utilizing the principle of molecular reorientation induced by the light reaction and self-organizing ability of the main chain. In the manufacturing method of the present invention, a coating film is formed on a substrate by using a main chain type polymer, then polarized ultraviolet rays are irradiated, and then, a liquid crystal display device is manufactured after heating.

Therefore, the coating film used in the method of the present invention can be made into a liquid crystal alignment film having anisotropy introduced at high efficiency and excellent in orientation control capability, by sequentially irradiating the coating film with polarized ultraviolet light and heat treatment.

In the coating film used in the method of the present invention, the irradiation amount of the polarized ultraviolet ray to the coating film and the heating temperature in the heating treatment are optimized. Thus, introduction of anisotropy into the coating film with high efficiency can be realized.

The irradiation amount of the polarized ultraviolet ray which is most suitable for introducing the high efficiency anisotropy into the coating film used in the present invention is not particularly limited as long as the amount of the polarized ultraviolet ray which optimizes the amount of the photosensitive group to react with the light crosslinking reaction or the optical isomerization reaction, Corresponds to dose. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, a sufficient photoreaction amount can not be obtained when the number of photosensitive groups of the main chain which is subjected to photo-crosslinking reaction, photoisomerization reaction, or light- In that case, sufficient self-organization does not proceed even after heating. On the other hand, in the coating film used in the present invention, the structure having the photo-crosslinkable group is irradiated with polarized ultraviolet rays, and as a result, when the photosensitive group of the main chain to be crosslinked is excessive, the cross-linking reaction between the main chains is excessively advanced. In such a case, the obtained film becomes rigid, which may interfere with the progress of self-organization by subsequent heating. In the coating film used in the present invention, the structure having a light-free stress period is irradiated with polarized ultraviolet rays. As a result, if the light-free stress period in the polymer film is large, the anisotropy obtained by polarized ultraviolet light becomes small, There is a case where the stability of the liquid crystal alignment is lowered due to the interruption of the progress of the organization. In the case of irradiating a polarized ultraviolet ray to a structure having a light-free stress period, if the irradiation amount of ultraviolet light is excessively large, the main chain type polymer is photodegraded and the progress of self-organization by heating is interrupted, The quality of the liquid crystal display element may deteriorate due to deterioration of the electrical characteristics of the liquid crystal alignment film.

Therefore, in the coating film used in the present invention, the optimum amount of photo-crosslinking reaction, photoisomerization reaction, or light-free potential reaction of the photosensitive group of the main chain by irradiation with polarized ultraviolet light is preferably such that the photosensitive group of the main chain type polymer membrane Is preferably from 0.1 mol% to 90 mol%, and more preferably from 0.1 mol% to 80 mol%. By setting the amount of the photosensitive group of the photoreactive main chain in such a range, the self-organization in the subsequent heating treatment proceeds efficiently, and high anisotropy can be formed in the film.

In the coating film used in the method of the present invention, by optimizing the dose of polarized ultraviolet light, the amount of photo-crosslinking reaction, optical isomerization reaction, or optical free-electric potential reaction of the photosensitive group in the main chain of the main- Optimize. In addition to the subsequent heat treatment, introduction of anisotropy into the coating film used in the present invention with high efficiency is realized. In this case, the preferable amount of the polarized ultraviolet ray can be carried out based on the evaluation of the ultraviolet absorption of the coating film used in the present invention.

That is, for the coating film used in the present invention, ultraviolet ray absorption in a direction parallel to the polarization direction of polarized ultraviolet rays after irradiation with polarized ultraviolet rays and ultraviolet ray absorption in a perpendicular direction are respectively measured. From the measurement results of ultraviolet absorption, ΔA which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction in the coating film is evaluated. Then, the maximum value DELTA Amax realized in the coating film used in the present invention (DELTA Amax) and the irradiation amount of the polarized ultraviolet ray to realize it are obtained. In the production method of the present invention, the amount of polarized ultraviolet ray to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of irradiated polarized ultraviolet ray realizing the DELTA Amx.

As described above, in the production method of the present invention, in order to realize introduction of high efficiency anisotropy into the coating film, the above-mentioned preferable heating It is preferable to set the temperature. Therefore, it is preferable that the heating temperature after the polarized ultraviolet irradiation is 100 占 폚 to 300 占 폚, more preferably 150 占 폚 to 250 占 폚. By doing so, a greater anisotropy is imparted to the coating film used in the present invention.

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

As described above, the substrate for a transverse electric field driving type liquid crystal display element manufactured using the composition of the present invention or the transverse electric field driving type liquid crystal display element having the substrate is excellent in reliability, And the like. Further, the liquid crystal alignment film produced by the method of the present invention can be used in a variable phase shifter using liquid crystals in that it has excellent liquid crystal alignment stability and reliability, and this variable phase shifter can be used, for example, Antennas and the like.

Example

The abbreviations used in the examples are as follows.

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

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

DA-2: a compound represented by the following structural formula (DA-2)

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

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

DA-5: a compound represented by the following structural formula (DA-5)

DA-6: a compound represented by the following structural formula (DA-6)

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

DA-8: a compound represented by the following structural formula (DA-8)

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

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

DA-11: A compound represented by the following structural formula (DA-11)

DA-12: A compound represented by 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: a compound represented by the following structural formula (CA-2)

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

&Lt; Measurement of viscosity &

In the synthesis example, the viscosity of the polymer solution was measured by using an E-type viscometer TVE-22H (manufactured by TOKI INDUSTRIAL CO., LTD.) At a sample amount of 1.1 ml, cone rotor TE-1 (1 DEG 34 ' Respectively.

(Synthesis Example 1)

1.88 g (7.0 mmol) of DA-1 and 1.61 g (7.0 mmol) of DA-7 were weighed, and 30.6 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.61 g (13.3 mmol) of CA-1 was added, and further 13.1 g of NMP was added. The mixture was stirred at 23 占 폚 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 263 mPa s.

14.5 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing 12.6 g of NMP and 11.6 g of BCS and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-1) &Lt; / RTI &gt;

(Synthesis Example 2)

1.88 g (7.0 mmol) of DA-1 and 1.71 g (7.0 mmol) of DA-8 were weighed, and 31.1 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While this diamine solution was stirred under water-cooling, 2.57 g (13.1 mmol) of CA-1 was added, and further 13.3 g of NMP was added. The mixture was stirred at 23 캜 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 326 mPa..

14.9 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing a stirrer, 13.0 g of NMP and 12.0 g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-2) .

(Synthesis Example 3)

1.74 g (6.5 mmol) of DA-1 and 1.68 g (6.5 mmol) of DA-9 were weighed, and 29.6 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.36 g (12.0 mmol) of CA-1 was added, and further 12.7 g of NMP was added. The mixture was stirred at 23 캜 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 261 mPa s.

14.5 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing 12.6 g of NMP and 11.6 g of BCS and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-3) &Lt; / RTI &gt;

(Synthesis Example 4)

1.74 g (6.5 mmol) of DA-1 and 1.77 g (6.5 mmol) of DA-10 were weighed, and 30.1 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.37 g (12.1 mmol) of CA-1 was added, and further 12.9 g of NMP was added. The mixture was stirred at 23 占 폚 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the solution of the polyamic acid at 25 캜 was 302 mPa..

14.6 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing a stirrer, 12.7 g of NMP and 11.7 g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-4) .

(Synthesis Example 5)

1.74 g (6.5 mmol) of DA-1 and 1.86 g (6.5 mmol) of DA-11 were weighed, and 30.5 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.35 g (12.0 mmol) of CA-1 was added, and further 13.1 g of NMP was added. The mixture was stirred at 23 占 폚 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 294 mPa..

12.6 g of NMP and 11.7 g of BCS were added and the mixture was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (A-5). The liquid crystal aligning agent (A-5) .

(Synthesis Example 6)

1.75 g (6.5 mmol) of DA-1 and 1.95 g (6.5 mmol) of DA-12 were weighed, and 31.0 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While this diamine solution was stirred under water-cooling, 2.37 g (12.1 mmol) of CA-1 was added, and further 13.3 g of NMP was added. The mixture was stirred at 23 占 폚 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 304 mPa s.

14.6 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing 12.6 g of NMP and 11.7 g of BCS and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-6) &Lt; / RTI &gt;

(Synthesis Example 7)

1.61 g (6.0 mmol) of DA-1 and 1.89 g (6.0 mmol) of DA-13 were weighed, and 29.1 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.18 g (11.1 mmol) of CA-1 was added, and further 12.5 g of NMP was added. The mixture was stirred at 23 ° C for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 305 mPa s.

15.0 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing 13.0 g of NMP and 12.0 g of BCS and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-7) &Lt; / RTI &gt;

(Synthesis Example 8)

1.78 g (7.0 mmol) of DA-2 and 1.71 g (7.0 mmol) of DA-8 were weighed, and 31.0 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While this diamine solution was stirred under water-cooling, 2.55 g (13.0 mmol) of CA-1 was added, and further 13.3 g of NMP was added. The mixture was stirred at 23 캜 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the solution of the polyamic acid at 25 캜 was 334 mPa..

14.9 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing 13.0 g of NMP and 12.0 g of BCS and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-8) &Lt; / RTI &gt;

(Synthesis Example 9)

1.88 g (7.0 mmol) of DA-3 and 1.71 g (7.0 mmol) of DA-8 were weighed, and 31.5 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.55 g (13.0 mmol) of CA-1 was added, and further 13.5 g of NMP was added. The mixture was stirred at 23 캜 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the solution of the polyamic acid at 25 캜 was 315 mPa..

14.6 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing 12.6 g of NMP and 11.7 g of BCS and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-9) .

(Synthesis Example 10)

1.74 g (6.5 mmol) of DA-1 and 1.59 g (6.5 mmol) of DA-8 were weighed, and 29.6 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While this diamine solution was stirred under water-cooling, 1.86 g (9.5 mmol) of CA-1 was added, and the mixture was stirred at 23 캜 for 30 minutes under a nitrogen atmosphere. Thereafter, 0.57 g (2.6 mmol) of CA-2 was added, 12.7 g of NMP was further added, and the mixture was stirred at 50 캜 for 15 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 308 mPa..

14.6 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-10) &Lt; / RTI &gt;

(Synthesis Example 11)

0.30 g (3.5 mmol) of DA-4 and 2.57 g (10.5 mmol) of DA-8 were weighed, and 30.4 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.55 g (13.0 mmol) of CA-1 was added, and further 13.0 g of NMP was added. The mixture was stirred at 23 占 폚 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 324 mPa..

14.9 g of this polyamic acid solution was dispensed into a 100-ml Erlenmeyer flask, 13.0 g of NMP and 12.0 g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-11) &Lt; / RTI &gt;

(Synthesis Example 12)

1.13 g (3.3 mmol) of DA-5 and 2.38 g (9.8 mmol) of DA-8 were weighed and placed into a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 30.2 g of NMP was added, And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.37 g (12.1 mmol) of CA-1 was added, and further 12.9 g of NMP was added. The mixture was stirred at 23 占 폚 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the solution of the polyamic acid at 25 캜 was 298 mPa..

12.6 g of NMP and 11.7 g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-12). The liquid crystal aligning agent (A-12) .

(Synthesis Example 13)

0.74 g (3.5 mmol) of DA-6 and 2.57 g (10.5 mmol) of DA-8 were weighed, and 30.1 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While this diamine solution was stirred under water-cooling, 2.55 g (13.0 mmol) of CA-1 was added, and further 12.9 g of NMP was added and stirred at 23 占 폚 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the solution of the polyamic acid at 25 캜 was 337 mPa..

14.6 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing 12.6 g of NMP and 11.7 g of BCS and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-13) &Lt; / RTI &gt;

(Comparative Synthesis Example 1)

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, 3.49 g (13.0 mmol) of DA-1 was weighed, 29.9 g of NMP was added and dissolved with stirring while nitrogen was being supplied. While stirring the diamine solution under water-cooling, 2.33 g (11.9 mmol) of CA-1 was added, and further 12.8 g of NMP was added. The mixture was stirred at 23 캜 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 357 mPa..

14.9 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing 13.0 g of NMP and 12.0 g of BCS and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-1) &Lt; / RTI &gt;

(Comparative Synthesis Example 2)

1.88 g (7.0 mmol) of DA-1 and 1.40 g (7.0 mmol) of DA-14 were weighed, and 30.1 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.58 g (13.2 mmol) of CA-1 was added, and further 12.9 g of NMP was added. The mixture was stirred at 23 占 폚 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the solution of the polyamic acid at 25 캜 was 288 mPa..

12.6 g of NMP and 11.7 g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-2). The liquid crystal aligning agent (B-2) .

(Comparative Synthesis Example 3)

1.88 g (7.0 mmol) of DA-1 and 1.39 g (7.0 mmol) of DA-15 were weighed, and 30.0 g of NMP was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen- And the mixture was stirred and dissolved. While stirring the diamine solution under water-cooling, 2.59 g (13.2 mmol) of CA-1 was added, and further 12.9 g of NMP was added. The mixture was stirred at 23 캜 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the solution of the polyamic acid at 25 캜 was 279 mPa..

14.6 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-3) &Lt; / RTI &gt;

(Comparative Synthesis Example 4)

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, 3.20 g (14.0 mmol) of DA-4 was weighed, 29.4 g of NMP was added, and dissolved with stirring while nitrogen was being supplied. While this diamine solution was stirred under water-cooling, 2.53 g (12.9 mmol) of CA-1 was added, and further 12.6 g of NMP was added. The mixture was stirred at 23 캜 for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of this polyamic acid solution at 25 캜 was 364 mPa..

14.6 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.7 g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-4) .

&Lt; Production of Liquid Crystal Cell for Liquid Crystal Orientation Evaluation &

Hereinafter, a method of manufacturing a liquid crystal cell for evaluating liquid crystal alignability will be described.

A liquid crystal cell having a configuration of a liquid crystal display element of the FFS system was produced. First, a substrate with an electrode attached thereto was prepared. The substrate is a glass substrate having a size of 30 mm x 35 mm and a thickness of 0.7 mm. On the substrate, an IZO electrode constituting the counter electrode as the first layer was formed on the entire surface. On the first layer counter electrode, a SiN (silicon nitride) film formed by the CVD method was formed as the second layer. The thickness of the second-layer SiN film is 500 nm and functions as an interlayer insulating film. On the second-layer SiN film, a comb-like pixel electrode formed by patterning an IZO film as a third layer was disposed, and two pixels, a first pixel and a second pixel, were formed. The size of each pixel is 10 mm in length and 5 mm in width. At this time, the first-layer counter electrode and the third-layer pixel electrode are electrically insulated by the action of the second-layer SiN film.

The third-layer pixel electrode has a comb-like shape formed by arranging a plurality of elongated electrode elements bent at a central portion in the same manner as in the figure described in JP-A-2014-77845 (Japanese Unexamined Patent Application Publication). The width of each electrode element in the width direction is 3 mu m, and the interval between the electrode elements is 6 mu m. Since the pixel electrode forming each pixel is constituted by arranging a plurality of elongated electrode elements bent at the center portion, the shape of each pixel is not a rectangle shape, It has a bold, similar shape. Each pixel has a first region on the upper side of the bent portion and a second region on the lower side, which are vertically divided with the bent portion at the center as a boundary.

When the first region and the second region of each pixel are compared with each other, the electrode elements of the pixel electrodes constituting the first region and the second region are different from each other. That is, when the direction of the line segment projecting the polarizing plane of the polarized ultraviolet ray to be described later is referred to as a reference, the electrode element of the pixel electrode is formed so as to form an angle of +10 degrees (clockwise direction) in the first region of the pixel, The electrode elements of the pixel electrodes were formed so as to form an angle of -10 degrees (clockwise direction). That is, in the first region and the second region of each pixel, the direction of the rotation (inflation / switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode in the substrate surface is opposite Respectively.

Next, the liquid crystal aligning agent obtained in Synthesis Examples and Comparative Synthesis Examples was filtered with a filter of 1.0 占 퐉, and then applied to the substrate to which the electrode was attached by spin coat coating. Then, it was dried on a hot plate set at 70 DEG C for 90 seconds. Subsequently, linearly polarized ultraviolet light was irradiated to the substrate from the vertical direction through a wavelength selection filter and a polarizing plate using an exposure apparatus: APL-L050121S1S-APW01 manufactured by Ushio Inc. At this time, the polarization plane direction was set such that the direction of the line segment projecting the polarizing plane of the polarized ultraviolet ray on the substrate was a direction inclined by 10 占 with respect to the third-layer IZO interdigital electrode. Subsequently, the substrate was fired in an IR (infrared) type oven set at 230 DEG C for 30 minutes to obtain a substrate on which a polyimide liquid crystal alignment film having a thickness of 100 nm and subjected to alignment treatment was formed. A substrate on which a polyimide liquid crystal alignment film having been subjected to alignment treatment was formed on a glass substrate having a columnar spacer having a height of 4 占 퐉 and having ITO electrodes on its back surface as a counter substrate was obtained. A sealant was printed on the substrate having the two liquid crystal alignment films formed thereon in the form of leaving a liquid crystal injection hole on the substrate of the single crystal and the other liquid crystal alignment layer faces the liquid crystal alignment film faces and the polarization plane of the polarized ultraviolet ray So that the directions of the line segments projected on the substrate are parallel to each other, and are pressed. Thereafter, the sealant was cured to prepare an empty cell having a cell gap of 4 탆. A liquid crystal MLC-7026-100 (negative liquid crystal manufactured by Merck Ltd.) was injected into this empty cell by a low pressure injection method and the injection port was sealed to obtain an FFS type liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120 캜 for 30 minutes, left at 23 캜 for one night, and then used for evaluation of liquid crystal alignability.

<Evaluation of Liquid Crystal Alignment Property>

Using this liquid crystal cell, an AC voltage of 16 VPP was applied for 168 hours at a frequency of 30 Hz under a constant temperature environment of 70 占 폚. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left as they were at 23 占 폚 for one night.

After leaving the liquid crystal cell, the liquid crystal cell was placed between two polarizing plates arranged so that the polarization axis thereof was orthogonal to each other, and the backlight was turned on in a voltage unapplied state, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of the transmitted light was minimized. The rotation angle at which the liquid crystal cell was rotated from the angle at which the second area of the first pixel was darkest to the angle at which the first area became darkest was calculated as the angle?. Similarly, in the second pixel, the second region and the first region were compared to calculate the same angle?. Then, the average value of the angles? Of the first and second pixels was calculated as the angle? Of the liquid crystal cell. When the value of the angle DELTA of the liquid crystal cell was less than 1.5 DEG, it was defined as &quot; good &quot;, and when the value of the angle DELTA was 1.5 DEG or more, it was defined as &quot;

<Fabrication of liquid crystal cell for evaluation of voltage holding ratio>

In the same manner as in the production of the liquid crystal cell for evaluation of liquid crystal alignability, except that a glass substrate with an ITO electrode was used and before the printing of the sealing agent, a bead spacer of 4 mu m was dispersed on the liquid crystal alignment film surface on the substrate of the single- A liquid crystal cell for measuring the voltage holding ratio was prepared.

&Lt; Evaluation of voltage holding ratio &

The liquid crystal cell was used to evaluate the voltage holding ratio. Specifically, an AC voltage of 2 VPP was applied to the liquid crystal cell obtained by the above method at a temperature of 70 占 폚 for 60 占 퐏, a voltage after 167m seconds was measured, and a voltage holding ratio VHR). The measurement was carried out by using a voltage holding ratio measuring device (VHR-1, manufactured by Toyo Technica Co., Ltd.) with a voltage of ± 1 V, a pulse width of 60 μs and a flame period of 167 ms. &Quot; Good &quot; when the voltage holding ratio of the liquid crystal cell was 80% or more, and &quot; Bad &quot; when the voltage holding ratio was less than 80%.

(Example 1)

Using the liquid crystal aligning agent (A-1) obtained in Synthesis Example 1, two kinds of liquid crystal cells were prepared as described above. Polarized ultraviolet rays were irradiated using a high-pressure mercury lamp and a polarizing plate of a wavelength selection filter: 240 LCF and a 254 nm type. The irradiation amount of the polarized ultraviolet ray was measured by changing the light amount in the range of 200 to 1500 mJ / cm 2 at a wavelength of 254 nm by using a light guide UVD-S254SB manufactured by Ushio Co., Ltd. and changing the irradiation amount of three polarized ultraviolet rays Or more.

As a result of evaluating the liquid crystal alignability of these liquid crystal cells, the polarized ultraviolet radiation amount with the best angle? Was 900 mJ / cm 2, and the angle? Was good at 1.06 °.

Further, the voltage holding ratio was evaluated with respect to the liquid crystal cell manufactured with the same polarized ultraviolet radiation dose, and as a result, the voltage holding ratio was as good as 85.3%.

(Examples 2 to 12)

The liquid crystal alignability and the voltage holding ratio were evaluated in the same manner as in Example 1 except that the liquid crystal aligning agent obtained in Synthesis Examples 2 to 12 was used.

(Example 13)

Using a liquid crystal aligning agent (A-13) obtained in Synthesis Example 13 and irradiating with polarized ultraviolet rays, a metal halide lamp was used and a wavelength selection filter: i-wide BPF and a polarizing plate of 313 to 365 nm type were interposed The liquid crystal alignability and the voltage holding ratio were evaluated in the same manner as in Example 1 except that the irradiation amount of the polarized ultraviolet ray was changed in the range of 1000 to 4000 mJ / cm 2 at a wavelength of 365 nm.

(Comparative Examples 1 to 4)

The liquid crystal alignability and the voltage holding ratio were evaluated in the same manner as in Example 1 except that the liquid crystal aligning agent obtained in Comparative Synthesis Examples 1 to 4 was used.

Table 1 shows the results of the evaluation of the polarized ultraviolet irradiation wavelength, the polarized ultraviolet radiation dose with the best angle?, The result of the evaluation of the liquid crystal alignability and the evaluation of the voltage holding ratio when the liquid crystal aligning agent obtained in the synthesis examples and comparative synthesis examples were used .

As shown in Table 1, in Examples 1 to 13, the angle?, Which is the difference between the orientation azimuth angles before and after the AC drive, was satisfactory at less than 1.5 DEG, and VHR was 80% or more and good characteristics were exhibited. , The display quality of the liquid crystal display element is improved. On the other hand, in Comparative Examples 1 to 4, the characteristics in which the angle?

As described above, it was confirmed that the liquid crystal display device manufactured by the method of the present invention exhibits very excellent afterimage characteristics.

Industrial availability

The transverse electric field driving type liquid crystal display element manufactured using the composition of the present invention or the transverse electric field driven liquid crystal display element having the substrate has excellent reliability and can be preferably used for a liquid crystal television with a large screen have. Since the liquid crystal alignment film produced by the method of the present invention has excellent liquid crystal alignment stability and reliability, it can also be used in a variable phase shifter using liquid crystals. The variable phase shifter is, for example, an antenna capable of varying the resonant frequency And the like.

Claims (11)

A polymer obtained from a diamine component containing at least one kind 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) 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 containing an oxygen atom and alkylene, R ₁ to R ₇ are each independently a hydrogen atom or M, n, o, p and q are each independently an integer of 0 to 4), and an organic solvent.

The method according to claim 1,
Wherein the polymer is at least one polymer selected from the group consisting of a polyimide precursor which is a polymer of the diamine component and a tetracarboxylic acid dianhydride and a polyimide which is an imide thereof. 3. The method according to claim 1 or 2,
Wherein the polyimide precursor is, according to the following formula (5) (the formula (5), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁ is selected from the formulas (1) - (3) (Wherein R ₁₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and a structural unit represented by the following formula (6): wherein 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), R ₁₂ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms An alkyl group).

The method of claim 3,
Wherein the structure of X _{1 and} the structure of X ₂ in the formulas (5) and (6) are each independently at least one selected from the group consisting of the following structures.

The method according to claim 3 or 4,
Wherein the polymer having a structural unit represented by the formula (5) and the formula (6) is contained in an amount of 10 mol% or more based on the total polymer contained in the liquid crystal aligning agent. 6. The method according to any one of claims 3 to 5,
Wherein the liquid crystal aligning agent contains at least one member selected from the group consisting of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether in the organic solvent. [I] a step of coating the composition described in any one of claims 1 to 6 on a substrate having a conductive film for driving a transverse electric field to form a coated film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; And
[III] a step of heating the coating film obtained in [II];
To obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field drive type in which orientation control ability is imparted. A substrate having a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type manufactured by the method according to any one of claims 1 to 7. 9. A transverse electric field driving type liquid crystal display element having the substrate according to claim 8. Preparing a substrate (first substrate) according to claim 8;
[I '] a step of applying a composition according to any one of claims 1 to 6 on a second substrate to form a coating film;
A step of irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet light; And
Heating the coating film obtained in [III '] [II'];
A step of obtaining a liquid crystal alignment film having alignment control ability by being provided with a liquid crystal alignment film; And
[IV] A step of arranging the first and second substrates so that the liquid crystal alignment layers of the first and second substrates face each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element;
To obtain a transverse electric field driven liquid crystal display element. A transverse electric field driving type liquid crystal display element manufactured by the method according to claim 10.