WO2018025872A1

WO2018025872A1 - Liquid crystal display element equipped with liquid crystal panel having curved surface and liquid crystal aligning agent for same

Info

Publication number: WO2018025872A1
Application number: PCT/JP2017/027924
Authority: WO
Inventors: 政太郎大田; 亮一芦澤; 暁子杉山; 徳俊三木
Original assignee: 日産化学工業株式会社
Priority date: 2016-08-03
Filing date: 2017-08-01
Publication date: 2018-02-08
Also published as: KR102438830B1; JPWO2018025872A1; CN109791332B; CN109791332A; KR20190031570A; TW201821483A; TWI826353B

Abstract

Provided is a liquid crystal display device equipped with a liquid crystal panel which has a curved surface and is still free from a bright dot even if a physical friction such as rubbing by a spacer has occurred. A curved liquid crystal display element which is provided with a liquid crystal alignment film that contains a polymer having a structure represented by formula (1). (In the formula, Y¹ represents a single bond, -(CH₂)_a- (wherein a represents an integer of 1-15), -O-, -CH₂O-, -COO- or OCO-; Y² represents a single bond or (CH₂)_b- (wherein b represents an integer of 1-15); Y³ represents a single bond, -(CH₂)_c- (wherein c represents an integer of 1-15), -O-, -CH₂O-, -COO- or OCO-; Y⁴ represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (an arbitrary hydrogen atom on these cyclic groups may be substituted by an alkyl group having 1-3 carbon atoms, an alkoxyl group having 1-3 carbon atoms, a fluorine-containing alkyl group having 1-3 carbon atoms, a fluorine-containing alkoxyl group having 1-3 carbon atoms, or a fluorine atom), or a divalent organic group selected from among organic groups having a steroid skeleton and 12-25 carbon atoms; Y⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (an arbitrary hydrogen atom on these cyclic groups may be substituted by an alkyl group having 1-3 carbon atoms, an alkoxyl group having 1-3 carbon atoms, a fluorine-containing alkyl group having 1-3 carbon atoms, a fluorine-containing alkoxyl group having 1-3 carbon atoms, or a fluorine atom); n represents an integer of 2-4 in cases where Y⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or represents an integer of 0-4 in cases where Y⁴ is a divalent organic group selected from among organic groups having a steroid skeleton and 12-25 carbon atoms, and in cases where n is 2 or more, each of the plurality of Y⁵ moieties independently represents one of the groups defined above; and Y⁶ represents an alkyl group having 1-18 carbon atoms, a fluorine-containing alkyl group having 1-18 carbon atoms, an alkoxyl group having 1-18 carbon atoms or a fluorine-containing alkoxyl group having 1-18 carbon atoms.)

Description

LIQUID CRYSTAL DISPLAY ELEMENT WITH LIQUID CRYSTAL PANEL AND LIQUID CRYSTAL ALIGNANT

The present invention relates to a liquid crystal display element including a liquid crystal panel having a curved shape and a liquid crystal aligning agent therefor.

In recent years, liquid crystal display devices have been used in various electronic devices such as smartphones, mobile phones, televisions, navigation devices, electronic notebooks, electronic books, etc., along with reductions in thickness and power consumption. The liquid crystal display device includes a liquid crystal panel and a drive circuit, and is configured by attaching auxiliary equipment such as a backlight, a light guide plate, and a casing as necessary. When a normal liquid crystal display device is used in an electronic device, the display surface of the liquid crystal display device is configured to be arranged in a planar shape substantially parallel to the housing of the electronic device.

On the other hand, as liquid crystal display devices have been used in various fields in recent years, the display area of electronic devices has increased in display area, wideness, immersiveness, and design. A liquid crystal display device including a liquid crystal panel having a curved shape along the outer surface of a housing of a device has been proposed and used (see Patent Document 1).

Japanese Unexamined Patent Publication No. 10-268245 Japanese Unexamined Patent Publication No. 10-104633 Japanese Unexamined Patent Publication No. 8-76128

When manufacturing a display device having a curved liquid crystal panel, the liquid crystal panel is bent along the outer surface of the housing. Thereby, the spacer which exists in the inside of a liquid crystal panel moves within a liquid crystal panel, and rubs a liquid crystal aligning film. The liquid crystal alignment film stressed by the spacer cannot regulate the alignment of the liquid crystal, and although the liquid crystal panel is displayed black, for example, light escapes from the periphery of the spacer and is displayed as a bright spot. It has become a problem.

An object of the present invention has been made in view of the above circumstances, and a liquid crystal display device comprising a liquid crystal panel having a curved surface that can minimize bright spots even when physical friction such as rubbing by a spacer occurs. And providing a liquid crystal aligning agent therefor.

As a result of intensive studies, the present inventors have completed the present invention. That is, the present invention has the following gist.
(1) A liquid crystal display device comprising a curved liquid crystal panel having a liquid crystal alignment film obtained from a liquid crystal alignment agent containing a polymer having a structure represented by the following formula [1].

Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—, and Y ² is a single bond A bond or (CH ₂ ) _b — (b is an integer of 1 to 15), Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O —, —CH ₂ O—, —COO— or OCO—. Y ⁴ represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms) An alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom which may be substituted), or an organic group having 12 to 25 carbon atoms having a steroid skeleton Y ⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring (any hydrogen atom on these cyclic groups is a carbon atom). (It may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.) And n , Y ⁴ is a benzene ring, when a cyclic group selected from the group consisting of hexane ring and the heterocyclic cycloheteroalkyl is an integer of 2 ~ 4, Y ⁴ is an organic group having a carbon number of 12 to 25 having a steroid skeleton In the case of a divalent organic group selected, it is an integer of 0 to 4. Further, when n is plural, the plural Y ⁵ have the above definition independently. Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
(2) A liquid crystal aligning agent for a liquid crystal display device including a liquid crystal panel having a curved shape, and containing a polymer having a structure represented by the above formula [1].

According to the present invention, it is possible to provide a liquid crystal display device including a liquid crystal panel having a curved surface shape that can minimize the bright spot even when physical friction such as rubbing by a spacer occurs, and a liquid crystal aligning agent therefor. Can do.

It is the photograph which observed the liquid crystal cell produced using the board | substrate with a polyimide coating film which gave the scratch test (it explains in full detail in an Example) with the polarizing microscope. In this photograph, almost no bright spot is seen at the place where the scratch test was conducted. It is the photograph which observed the liquid crystal cell produced using the board | substrate with a polyimide coating film which gave the scratch test mentioned above with the polarizing microscope. In this photograph, it can be seen that light is transmitted from the place where the scratch test was performed, and is a bright spot.

A curved liquid crystal display element comprising a liquid crystal panel having a curved shape according to the present invention is a liquid crystal alignment obtained from a liquid crystal aligning agent containing a polymer containing a structure represented by the following formula [1] (also referred to as a specific structure). A membrane is provided.
<Specific structure>

In the formula [1], Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—. . Among these, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or COO— is preferable because a side chain structure is easily synthesized. More preferably, they are a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or COO—.
Y ² is a single bond or (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.
Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—. Among these, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO— is preferable because they are easily synthesized. More preferably, they are a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO— or OCO—.

Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁴ is a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton. Y ⁴ is preferably a C 12-25 organic group having a benzene ring, a cyclohexyl ring or a steroid skeleton.
Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.

n is, Y ⁴ is a benzene ring, when a cyclic group selected from the group consisting of hexane ring and the heterocyclic cycloheteroalkyl is an integer of 2 to 4, organic Y ⁴ carbon number of 12 to 25 having a steroid skeleton In the case of a divalent organic group selected from a group, it is an integer of 0 to 4. Further, when n is plural, the plural Y ⁵ have the above definition independently.
Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Of these, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

<Polymer having specific structure>
Although it does not specifically limit as a polymer which has the specific structure used for this invention, The group which consists of an acrylic polymer, a methacryl polymer, a novolak resin, a polyhydroxystyrene, a polyimide precursor, a polyimide, polyamide, polyester, cellulose, and polysiloxane The polymer is preferably selected from the group consisting of Among these, a polyimide precursor, polyimide or polysiloxane is preferable, and a polyimide precursor or polyimide is more preferable.
When the polymer used in the present invention is a polyimide precursor or polyimide, they are obtained by reaction of diamine and tetracarboxylic dianhydride, but have a specific structure from the viewpoint of ease of production. Is preferably a diamine.

<Diamine having a specific structure>
The above-described diamine having a specific structure (also referred to as a specific diamine) is represented by the following formula [2].

Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , and n in the formula [2] are the same as the above definition in the formula [1] including each preferable one. Note that m is an integer of 1 to 4, preferably 1.

Specific examples include, but are not limited to, the following formulas [2-1] to [2-23].

R ⁷ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.

R ⁸ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.

A ⁴ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ³ is a 1,4-cyclohexylene group or a 1,4-phenylene group, and A ² is An oxygen atom or COO- * (where a bond with “*” is bonded to A ³ ), and A ¹ is an oxygen atom or COO— * (where a bond with “*” is ( CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is 1.

<Other diamine compounds>
In this invention, other diamine compounds other than specific diamine can be used together as a diamine component. Specific examples are given below.
p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy -4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-diph Fluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, 2,3′-diaminodiphenylmethane, 4, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3 '-Sulphonyldianiline, bis (4-aminophenyl) silane, bis (3-amino Nophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 4,4′-diaminodiphenylamine, 3, 3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3 3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8- Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3 -Aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4aminophenyl) butane, 1,4-bis ( 3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) ben 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-amino) Benzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1,4-phenylenebis (methylene)] dianiline, 4,4 ′-[1,3-phenylenebis (methylene) ] Dianiline, 3,4 '-[1,4-phenylenebis (methylene)] dianiline, 3,4'-[1,3-phenylenebis (methylene)] dianiline, 3,3 '-[1,4-phenylene Bis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3 -Ami Phenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis ( 3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenzamide), N, N '-(1,3-phenylene) bis (4-aminobenzamide), N, N'-(1,4-phenylene) bi (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) terephthalamide, N, N′-bis (3 -Aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2 '-Bis (3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-amino) Phenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4 -Aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) Nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, 4- (aminomethyl) aniline, 3- (aminomethyl) aniline, 4- (2-aminoethyl) aniline, Aromatic diamine compounds such as 3- (2-aminoethylaniline); bis (4-aminocyclohexyl) methane, bis (4-amino-3-methyl) Cyclohexane) alicyclic diamine compounds such as methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -Aliphatic diamine compounds such as diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane.

As other diamines, diamines having an alkyl group or a fluorine-containing alkyl group in the diamine side chain can be used in combination. Specifically, diamines of the following formulas [DA1] to [DA12] can be exemplified.

A ⁵ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.

A ⁶ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or NH—, and A ⁷ represents an alkyl group having 1 to 22 carbon atoms. Or a fluorine-containing alkyl group is shown.

p is an integer of 1 to 10.

Also, diamines of the following formulas [DA13] to [DA20] can be used in combination.

m is an integer of 0 to 3, and n is an integer of 1 to 5.

Furthermore, a diamine having a carboxyl group in the molecule represented by the following formulas [DA21] to [DA25] can be used in combination.

m ₁ is an integer of 1 to 4, and A ⁸ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — or N (CH ₃ ) CO—, each of m ₂ and m ₃ is an integer of 0 to 4, and m ₂ + m ₃ is an integer of 1 to 4. m ₄ and m ₅ are each an integer of 1 to 5, A ⁹ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m ₆ is an integer of 1 to 5. A ¹⁰ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) —, —O—, —CO—, — NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — or N (CH ₃ ) CO— and m ₇ is an integer from 1 to 4.
The said other diamine compound can also be used 1 type or in mixture of 2 or more types according to characteristics, such as a liquid crystal aligning property at the time of setting it as a liquid crystal aligning film, a voltage holding rate, and an accumulation charge.

<Tetracarboxylic dianhydride component>
In order to obtain the specific polymer in the present invention, a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [3] is used.

In formula [3], Z ¹ is a tetravalent organic group, and the structure thereof is not particularly limited, but is a tetravalent organic group having 4 to 13 carbon atoms and a non-aromatic cyclic group having 4 to 10 carbon atoms. It preferably contains a hydrocarbon group.

Specifically, it is a group represented by the following formulas [3a] to [3j].

Z ² to Z ⁵ are each independently a group selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring. In the formula [3g], Z ⁶ and Z ⁷ are each independently a hydrogen atom or a methyl group. Particularly preferred examples of Z ¹ are the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f], and the formula [3g] because of polymerization reactivity and ease of synthesis.

<Other tetracarboxylic dianhydrides>
In the present invention, other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride (other tetracarboxylic dianhydrides can be used. Other tetracarboxylic dianhydrides are shown below. The tetracarboxylic dianhydride of tetracarboxylic acid is mentioned.

Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis ( 3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2 , 2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bi (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxy) Phenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic Examples include acids.
The other tetracarboxylic dianhydrides may be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding ratio, accumulated charge and the like when the liquid crystal alignment film is formed.

<Method for producing specific polymer>
The method for synthesizing the specific polymer in the present invention is not particularly limited. Usually, it is obtained by polycondensation reaction of a diamine component and a tetracarboxylic dianhydride component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid. In order to obtain the polyamic acid alkyl ester, a method of converting the carboxyl group of the polyamic acid into an ester is used.

Furthermore, in order to obtain a polyimide, the method of imidating the said polyamic acid or polyamic-acid alkylester to make a polyimide is used.
The liquid crystal alignment film obtained by using the specific polymer of the present invention increases the content ratio of the specific diamine in the diamine component, in addition to the initial characteristics, even after being exposed to the backlight for a long time, Charges accumulated by the voltage holding ratio and DC voltage are quickly relaxed. Moreover, the pretilt angle of a liquid crystal can be enlarged, so that the content rate of specific diamine in a diamine component increases. At that time, for the purpose of enhancing the above-mentioned characteristics, the content of the specific diamine compound in the diamine component is preferably 0.01 to 99 mol, more preferably 0.1 to 50 mol, relative to 1 mol of the specific diamine. Moles, more preferably 0.5 to 20 moles, and most preferably 0.5 to 10 moles.

Moreover, in order to obtain the specific polymer of this invention, it is preferable to use specific tetracarboxylic dianhydride for the tetracarboxylic dianhydride component. In that case, it is preferable that 1 mol% or more of a tetracarboxylic dianhydride component is a specific tetracarboxylic dianhydride, More preferably, it is 5 mol% or more, More preferably, it is 10 mol% or more. Further, 100 mol% of the tetracarboxylic dianhydride component may be a specific tetracarboxylic dianhydride.
Reaction of a diamine component and a tetracarboxylic dianhydride component is normally performed in an organic solvent. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, isopropyl alcohol, Methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene Glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether , Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether , 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n -Pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, Methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionate 3-methoxy propionic acid propyl, and the like 3-methoxypropionate butyl, diglyme or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction, and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred and the tetracarboxylic dianhydride component is used as it is or in an organic solvent. A method of adding by dispersing or dissolving in a solvent, a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component These may be used alternately, and any of these methods may be used. Moreover, when making it react using multiple types of diamine component or tetracarboxylic dianhydride component, respectively, you may make it react in the state mixed previously, you may make it react separately one by one, and it was made to react individually further Low molecular weight substances may be mixed and reacted to form a specific polymer. In this case, the polymerization temperature can be selected from -20 to 150 ° C., preferably in the range of −5 to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a specific polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. It becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization reaction for obtaining the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic dianhydride component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.
In the polyimide of the present invention, the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalyst imidization in which a catalyst is added to the polyimide precursor solution.

The temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
The catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. Examples of the solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.

The molecular weight of the specific polymer of the present invention was measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the polymer film obtained therefrom, workability when forming the polymer film, and uniformity of the polymer film. The weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal aligning agent>
The polymer in the liquid crystal aligning agent used in the present invention may all be the above specific polymer, or other polymers may be mixed. In that case, the content of the other polymer with respect to the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.
Examples of other polymers include a polyimide precursor obtained from a diamine component not containing a specific diamine and a tetracarboxylic dianhydride component, or a polyimide obtained from the polyimide precursor. Furthermore, a polyimide precursor and a polymer other than polyimide, specifically, an acrylic polymer, a methacrylic polymer, polystyrene, or polyamide are also included.

The organic solvent in the liquid crystal aligning agent used in the present invention preferably has an organic solvent content of 70 to 99% by mass from the viewpoint of forming a uniform polymer film by coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film. The organic solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer described above. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, Dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, Examples thereof include ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

<Additives>
The liquid crystal aligning agent used in the present invention includes a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group or an alkoxyl group It is preferable to contain a crosslinkable compound having a polymerizable unsaturated bond (hereinafter also referred to as a crosslinking agent).

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3 -Epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

Specifically, it is a crosslinkable compound represented by the following formulas [4a] to [4k].

Examples of the crosslinkable compound having a cyclocarbonate group include a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

Specifically, it is a crosslinkable compound represented by the following formulas [5-1] to [5-37].

In the formula [5-24], n is an integer of 1 to 5, in the formula [5-25], n is an integer of 1 to 5, and in the formula [5-36], n is 1 to 100. In the formula [5-37], n is an integer of 1 to 10.
Furthermore, polysiloxanes having at least one structure represented by the following formulas [5-38] to [5-40] can also be mentioned.

In the formulas [5-38] to [5-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, It is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, and at least one is a structure represented by the formula [5].
Specific examples include compounds of the following formula [5-41] or formula [5-42].

In the formula [5-42], n is an integer of 1 to 10.

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group or an alkoxyl group include, for example, amino resins having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used. Melamine derivatives or benzoguanamine derivatives can also exist as dimers or trimers. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring. Eight-substituted MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, methoxy such as Cymel 1123 Methylated ethoxyme Benzomethylamine, methoxymethyl butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 ) And the like. Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, methoxymethylolated glycoluril such as Powderlink 1174, and the like.

Benzene having a hydroxyl group or an alkoxyl group, or a phenolic compound can also be exemplified as a crosslinkable compound. For example, 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p -Tert-butylphenol and the like.

More specifically, it is a crosslinkable compound represented by the following formulas [6-1] to [6-48].

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol. Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( ) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di ( (Meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalate neopentyl glycol Crosslinkable compounds having two polymerizable unsaturated groups in the molecule such as di (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Pyr (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl Crosslinkable compounds having one polymerizable unsaturated group in the molecule such as (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester or N-methylol (meth) acrylamide It is done.

In addition, the compound represented by the following formula [7] can also be exemplified as the crosslinkable compound.

E ¹ is a monovalent group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring, and E ² is the following formula [7a ] Or a monovalent group consisting of the formula [7b], and n is an integer of 1 to 4.

The said compound is an example of a crosslinkable compound, It is not limited to these. Moreover, the crosslinkable compound contained in the liquid crystal aligning agent of this invention may be one type, and may be combined two or more types.

In the liquid crystal aligning agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer component, the crosslinking reaction proceeds, and the desired effect is exhibited. In order not to lower the orientation, the amount is more preferably 0.1 to 100 parts by mass, and particularly 1 to 50 parts by mass.
A nitrogen-containing heterocyclic amine compound represented by the following formulas [M1] to [M156] is added as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge loss of a liquid crystal cell using the liquid crystal alignment film. It is preferable to do. The amine compound may be added directly to the solution of the specific polymer, but it is preferable to add the amine compound after making a solution with a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent. . The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer described above.

The liquid crystal aligning agent of the present invention is an organic solvent (also referred to as a poor solvent) that improves the uniformity and surface smoothness of the polymer film when the liquid crystal aligning agent is applied, as long as the effects of the present invention are not impaired. Compounds can be included. Furthermore, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can also be contained. Specific examples of poor solvents that improve film thickness uniformity and surface smoothness include the following.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, 1-butoxy-2-propanol, 2-butoxy-1-propanol, dipropylene glycol monomethyl ether, Diethylene glycol, diethylene glycol mono Cetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether , Dipropylene glycol dimethyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, Diisobutyl ketone, 2,6-dimethyl-4-hept Tanol, diacetone alcohol, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid Propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- Propyl methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol Monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester Organic solvents having low surface tension such as lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, and lactyl isoamyl ester.
These poor solvents may be used alone or in combination. When the above poor solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the whole organic solvent contained in the liquid crystal aligning agent.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
Specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. .

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like.

When a compound that improves the adhesion to the substrate is used, the amount is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polymer component contained in the liquid crystal aligning agent. It is. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
In the liquid crystal aligning agent of the present invention, in addition to the crosslinkable compound, the poor solvent, and the compound that improves adhesion, the dielectric constant and conductivity of the liquid crystal aligning film are within the range in which the effects of the present invention are not impaired. For example, a dielectric material or a conductive material for changing electrical characteristics may be added.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal aligning agent of this invention can be used as a liquid crystal aligning film by apply | coating and baking on a board | substrate and performing alignment processing by a rubbing process, light irradiation, etc. In the case of vertical alignment, etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate used at this time is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.

As a method for applying the liquid crystal aligning agent, industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
After applying the liquid crystal aligning agent on the substrate, the solvent can be evaporated at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate to form a polymer film. If the thickness of the polymer film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm. When the liquid crystal is horizontally or tilted, the polymer film after baking is treated with rubbing or irradiation with polarized ultraviolet rays.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent and then preparing a liquid crystal cell by a known method.
As a method for manufacturing a liquid crystal cell, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of sealing the substrate by bonding the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed.
A characteristic of the present invention is that the liquid crystal display panel in the liquid crystal display element has a curved surface shape. That is, the pair of substrates constituting the liquid crystal display panel has a curved surface, and there are various shapes and degrees of the curved surface, and these are arbitrarily selected. In particular, the present invention is effective for a liquid crystal display panel having a curved surface shape in a section along a uniaxial direction and a curvature radius (R) of the curved surface shape of 1000 mm to 3000 mm.

Furthermore, the liquid crystal aligning agent of this invention has a liquid crystal layer between a pair of board | substrates provided with the electrode, and contains the polymeric compound superposed | polymerized by at least one of an active energy ray and heat between a pair of board | substrates. It is also preferably used for a liquid crystal display element produced by a step of polymerizing a polymerizable compound by disposing a liquid crystal composition and applying a voltage between electrodes while at least one of irradiation with active energy rays and heating. Here, the active energy ray is preferably ultraviolet rays.
The liquid crystal display element controls a pretilt angle of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound. The pretilt angle of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. . The PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt angle by the rubbing process.

That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, a liquid crystal cell is prepared, and a polymerizable compound is applied by at least one of ultraviolet irradiation and heating. The orientation of liquid crystal molecules can be controlled by polymerization.
If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is attached and sealed.

In the liquid crystal, a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases and the liquid crystal display element. The seizure characteristics of the steel deteriorate.
After the liquid crystal cell is produced, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of liquid crystal molecules can be controlled.

In addition, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates. The liquid crystal display element manufactured through the process of arrange | positioning the liquid crystal aligning film containing this, and applying a voltage between electrodes is used preferably. Here, the active energy ray is preferably ultraviolet rays.
In order to obtain a liquid crystal alignment film containing a polymerizable group that is polymerized from at least one of active energy rays and heat, a method of adding a compound containing the polymerizable group to a liquid crystal aligning agent, or a polymer containing a polymerizable group Examples include methods using components. Examples of the polymerizable group include polymerizable unsaturated groups such as an acryl group, a methacryl group, a vinyl group, and a maleimide group.

Since the liquid crystal aligning agent of the present invention contains a specific amine compound having a double bond site that reacts by heat or ultraviolet irradiation, the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. it can.
If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is attached and sealed.

After the liquid crystal cell is manufactured, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
As described above, the liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.

The present invention will be described more specifically with reference to the following examples, but is not limited thereto. In the following, the abbreviations used are as follows.
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

(Diamine)
3-AMPDA: 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide p-PDA: p-phenylenediamine PBCH5DAB: 1,3-diamino-4- {4- [trans-4- (trans-4 -N-pentylcyclohexyl) cyclohexyl] phenoxy} benzene PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

(Additive)

(Siloxane)
TEOS: Tetraethoxysilane UPS: 3-Ureidopropyltriethoxysilane MPMS: 3-Methacryloxypropyltrimethoxysilane HTMS: Hexadecyltrimethoxysilane (organic solvent)
NMP: N-methyl-2-pyrrolidone, NEP: N-ethyl-2-pyrrolidone BCS: butyl cellosolve, PB: propylene glycol monobutyl ether DME: 1,2-dimethoxyethane, DPM: dipropylene glycol monomethyl ether, DMI: 1, 3-Dimethyl-2-imidazolidinone, HG: hexylene glycol

<Measurement of molecular weight of polyimide>
The molecular weight of the polyimide in the synthesis example was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Science Co., Ltd. and a column (KD-803, KD-805) manufactured by Shodex.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran ( THF) is 10 ml / L), flow rate: 1.0 ml / min,
Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 9,000,150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, manufactured by Polymer Laboratories) 4,000, 1,000).

<Measurement of imidization ratio>
The imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku Co., Ltd.), add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidization rate (%) = (1−α · x / y) × 100

<Molecular weight measurement>
The molecular weights of polyimide and polysiloxane were measured as follows using a column manufactured by Shodex (sample side KF-803, reference side KF-800RH).
Column temperature: 40 ° C
Eluent: Tetrahydrofuran, flow rate: 1 ml / min, standard sample for preparing calibration curve: polystyrene manufactured by Shodex (molecular weight: about 52,400, 19,900, 7,200, 2,970, 580).

<Synthesis Example 1>
BODA (23.64 g, 94.5 mmol), p-PDA (5.11 g, 47.3 mmol), 3-AMPDA (16.0 g, 66.15 mmol), and DA-1 (32.86 g, 75.6 mmol) Were mixed in NMP (216.0 g) and reacted at 80 ° C. for 5 hours, then CBDA (18.53 g, 94.5 mmol) and NMP (94.6) g were added and reacted at 40 ° C. for 6 hours. A polyamic acid solution was obtained.
After adding NMP (62.3g) to this polyamic acid solution (30.0g) and diluting to 6 mass%, acetic anhydride (6.02g) and pyridine (1.87g) were added as an imidation catalyst, and it was 80 degreeC. The reaction was performed for 3 hours. This reaction solution was put into methanol (601.0 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (A). The imidation ratio of this polyimide was 75%, Mn (number average molecular weight) was 13,200, and Mw (weight average molecular weight) was 40,600.

<Synthesis Example 2>
BODA (23.64 g, 94.5 mmol), p-PDA (5.11 g, 47.3 mmol), 3-AMPDA (16.0 g, 66.15 mmol), DA-1 (16.43 g, 37.8 mmol), And DA-8 (14.39 g, 37.8 mmol) in NMP (207.8 g) and reacted at 80 ° C. for 5 hours, then CBDA (18.53 g, 94.5 mmol) and NMP (94. 6) g was added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.
After adding NMP (62.3g) to this polyamic acid solution (30.0g) and diluting to 6 mass%, acetic anhydride (6.15g) and pyridine (1.90g) were added as an imidation catalyst, and it was 80 degreeC. The reaction was performed for 3 hours. This reaction solution was put into methanol (602.1 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (B). The imidation ratio of this polyimide was 75%, Mn was 12,900, and Mw was 40,400.

<Synthesis Example 3>
BODA (23.14 g, 88.8 mmol), m-PDA (12.00 g, 111 mmol), DA-2 (16.60 g, 37 mmol), and DA-8 (16.08 g, 37 mmol) were mixed with NMP (170.7 g). ), And reacted at 80 ° C. for 5 hours. Then, CBDA (17.76 g, 90.7 mmol) and NMP (92.6) g were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. .
After adding NMP (87.1g) to this polyamic acid solution (30.0g) and diluting to 6 mass%, acetic anhydride (6.95g) and pyridine (2.15g) were added as an imidation catalyst, and it was 80 degreeC. The reaction was performed for 3 hours. This reaction solution was put into methanol (462.6 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (C). The imidation ratio of this polyimide was 75%, Mn was 11,800, and Mw was 39,600.

<Synthesis Example 4>
BODA (23.14 g, 88.8 mmol), m-PDA (12.00 g, 111 mmol), DA-3 (17.1 g, 37 mmol), and DA-8 (14.08 g, 37 mmol) were mixed with NMP (170.7 g). ), And reacted at 80 ° C. for 5 hours. Then, CBDA (17.78 g, 90.7 mmol) and NMP (92.6) g were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. .
After adding NMP (87.1g) to this polyamic acid solution (30.0g) and diluting to 6 mass%, acetic anhydride (6.95g) and pyridine (2.15g) were added as an imidation catalyst, and it was 80 degreeC. The reaction was performed for 3 hours. This reaction solution was put into methanol (462.6 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (D). The imidation ratio of this polyimide was 75%, Mn was 11,900, and Mw was 40,100.

<Synthesis Example 5>
BODA (23.14 g, 88.8 mmol), m-PDA (12.00 g, 111 mmol), and DA-4 (34.1 g, 74 mmol) were mixed in NMP (170.7 g) and at 80 ° C. for 5 hours. After the reaction, CBDA (17.78 g, 90.7 mmol) and NMP (92.6) g were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.
After adding NMP (87.1g) to this polyamic acid solution (30.0g) and diluting to 6 mass%, acetic anhydride (6.95g) and pyridine (2.15g) were added as an imidation catalyst, and it was 80 degreeC. The reaction was performed for 3 hours. This reaction solution was put into methanol (462.6 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (E). The imidation ratio of this polyimide was 75%, Mn was 14,100, and Mw was 41,000.

<Synthesis Example 6>
BODA (23.14 g, 88.8 mmol), m-PDA (12.00 g, 111 mmol), and DA-5 (28.6 g, 74 mmol) were mixed in NMP (255 g) and reacted at 80 ° C. for 5 hours. After that, CBDA (17.78 g, 90.7 mmol) and NMP (92.6) g were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.
After adding NMP (87.1g) to this polyamic acid solution (30.0g) and diluting to 6 mass%, acetic anhydride (6.95g) and pyridine (2.15g) were added as an imidation catalyst, and it was 80 degreeC. The reaction was performed for 3 hours. This reaction solution was put into methanol (462.6 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (F). The imidation ratio of this polyimide was 75%, Mn was 11,900, and Mw was 40,000.

<Synthesis Example 7>
BODA (23.14 g, 88.8 mmol), m-PDA (12.00 g, 111 mmol), and DA-6 (33.0 g, 74 mmol) were mixed in NMP (272.8 g) and at 80 ° C. for 5 hours. After the reaction, CBDA (17.78 g, 90.7 mmol) and NMP (71.1) g were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.
After adding NMP (87.1g) to this polyamic acid solution (30.0g) and diluting to 6 mass%, acetic anhydride (6.95g) and pyridine (2.15g) were added as an imidation catalyst, and it was 80 degreeC. The reaction was performed for 3 hours. This reaction solution was put into methanol (462.6 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (G). The imidation ratio of this polyimide was 75%, Mn was 11,400, and Mw was 39,000.

<Synthesis Example 8>
BODA (23.14 g, 88.8 mmol), m-PDA (12.00 g, 111 mmol), and DA-7 (33.0 g, 74 mmol) were mixed in NMP (272.8 g) and at 80 ° C. for 5 hours. After the reaction, CBDA (17.78 g, 90.7 mmol) and NMP (71.1) g were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.
After adding NMP (87.1g) to this polyamic acid solution (30.0g) and diluting to 6 mass%, acetic anhydride (6.95g) and pyridine (2.15g) were added as an imidation catalyst, and it was 80 degreeC. The reaction was performed for 3 hours. This reaction solution was put into methanol (462.6 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (H). The imidation ratio of this polyimide was 75%, Mn was 15,700, and Mw was 41,200.

<Synthesis Example 9>
A solution of alkoxysilane monomer was prepared by mixing 24.9 g of HG, 24.9 g of BCS, 52.5 g of TEOS, and 11.2 g of HTMS in a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube. A solution prepared by mixing 8.5 g of HG, 8.5 g of BCS, 16.2 g of water and 0.8 g of oxalic acid as a catalyst was added dropwise to the solution over 30 minutes at room temperature, and the mixture was further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.86 g of a methanol solution having a UPS content of 92% by mass, 0.86 g of HG and 0.86 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (I) having a SiO ₂ equivalent concentration of 12% by weight. This polysiloxane had Mn of 5,100 and Mw of 9,100.

<Synthesis Example 10>
An alkoxysilane monomer solution was prepared by mixing 28.4 g of HG, 21.3 g of BCS, 52.5 g of TEOS, and 18.4 g of Compound 3 in a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube. A solution prepared by mixing 8.5 g of HG, 8.5 g of BCS, 16.2 g of water and 0.8 g of oxalic acid as a catalyst was added dropwise to the solution over 30 minutes at room temperature, and the mixture was further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.86 g of a methanol solution having a UPS content of 92% by mass, 0.86 g of HG and 0.86 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (J) having a SiO ₂ equivalent concentration of 12% by weight. This polysiloxane had Mn of 2,400 and Mw of 4,800.

<Comparative Synthesis Example 1>
BODA (23.64 g, 94.5 mmol), p-PDA (5.11 g, 47.3 mmol), 3-AMPDA (16.0 g, 66.15 mmol), and DA-8 (28.77 g, 75.6 mmol) Were mixed in NMP (199.6 g) and reacted at 80 ° C. for 5 hours, then CBDA (18.53 g, 94.5 mmol) and NMP (94.6) g were added and reacted at 40 ° C. for 6 hours. A polyamic acid solution was obtained.
After adding NMP (62.3 g) to this polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (6.29 g) and pyridine (1.95 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was put into methanol (603.2 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (D). The imidation ratio of this polyimide was 75%, Mn was 13,200, and Mw was 39,300.

<Example 1>
NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution, and the liquid crystal aligning agent [1] was obtained by stirring for 5 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.
<Example 2>
NEP (54.0 g) was added to the polyimide powder (B) (6.0 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution, and the liquid crystal aligning agent [2] was obtained by stirring for 5 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 3>
NEP (54.0 g) was added to the polyimide powder (C) (6.0 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [3]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 4>
NEP (54.0 g) was added to the polyimide powder (D) (6.0 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [4]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 5>
NEP (54.0 g) was added to the polyimide powder (E) (6.0 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [5]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 6>
NEP (54.0 g) was added to the polyimide powder (F) (6.0 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [7]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 7>
NEP (54.0 g) was added to the polyimide powder (G) (6.0 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [7]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 8>
NEP (54.0 g) was added to the polyimide powder (H) (6.0 g) obtained in Synthesis Example 8, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [8]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 9>
NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. PB (40.0 g) was added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [9]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 10>
NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. DME (40.0 g) was added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [10]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 11>
NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. BCS (30.0 g) and DME (10.0 g) were added to this solution, and stirred for 5 hours to obtain a liquid crystal aligning agent [11]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 12>
NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. BCS (30.0 g) and DPM (10.0 g) were added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [12]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 13>
NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours, and then Compound 1 powder (0.6 g) was added and stirred for 24 hours to obtain a liquid crystal aligning agent [13]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 14>
NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours, and then Compound 2 powder (0.6 g) was added and stirred for 24 hours to obtain a liquid crystal aligning agent [14]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Example 15>
NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours, and then Compound 1 powder (0.3 g) and Compound 2 powder (0.3 g) were added and stirred for 24 hours, whereby a liquid crystal aligning agent [15 ] Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.
<Example 16>
A liquid crystal aligning agent [10] was obtained by mixing 10.0 g of the polysiloxane solution (I) obtained in Synthesis Example 9 and 15.0 g of HG and 15.0 g of BCS. It was confirmed that no abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent.

<Example 17>
A liquid crystal aligning agent [17] was obtained by mixing 10.0 g of the polysiloxane solution (J) obtained in Synthesis Example 10 and 15.0 g of HG and 15.0 g of BCS. It was confirmed that no abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent.

<Comparative Example 1>
NEP (54.0 g) was added to the polyimide powder (K) (6.0 g) obtained in Comparative Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. BCS (40.0g) was added to this solution, and it stirred at 50 degreeC for 15 hours, and obtained liquid crystal aligning agent [18]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

<Preparation of substrate with polyimide coating>
Each liquid crystal aligning agent obtained in Examples 1 to 17 and Comparative Example 1 was spin-coated on the ITO surface of a glass substrate with 3 cm × 4 cm ITO and baked on a hot plate at 70 ° C. for 1 minute and 30 seconds. The substrate was baked for 30 minutes in an infrared heating furnace at 0 ° C. to prepare a substrate with a polyimide coating film having a thickness of 100 nm.
In addition, in the case of the liquid crystal aligning agent obtained in Example 16, baking on a hot plate was performed at 80 ° C. for 3 minutes instead of 70 ° C. for 1 minute and 30 seconds.

<Evaluation of bright spots>
The polyimide coated substrate obtained in Example 1 and Comparative Example 1 was attached to UMT-2 (sensor is FVL, 1.6 mm sapphire sphere attached to the tip of the device) manufactured by Bruker AXS, and the horizontal axis A scratch test was performed from 0.5 mm (5 mm / second), 2 mm in the moving direction, from 1 mN to 20 mN over 100 seconds, and then MLC-3022 (manufactured by Merck Japan) was dropped. Then, a 4 μm spacer was sprayed onto the other polyimide-coated substrate obtained above and sandwiched toward the dropped MLC-3022 side. The place where the scratch test was done in the state which made the polarizing substrate (ECLIPSE E600WPOL) (made by Nikon Corp.) into 90 degrees of polarizing plates was observed, and light was permeate | transmitted.
As shown in FIG. 1, a state where almost no bright spot was seen was evaluated as “◯”, a state where a bright spot as shown in FIG. 2 was slightly seen was evaluated as “Δ”, and scratched as shown in FIG. The state where the spot became a bright spot was evaluated as “x”, and the results are shown in Table 1.

It should be noted that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2016-153149 filed on August 3, 2016 are cited herein as disclosure of the specification of the present invention. Incorporate.

Claims

A liquid crystal display element provided with the curved liquid crystal panel which has a liquid crystal aligning film obtained from the liquid crystal aligning agent containing the polymer which has a structure represented by following formula [1].

(Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—, and Y 2 is A single bond or (CH 2 ) b — (b is an integer of 1 to 15), Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), — O—, —CH 2 O—, —COO— or OCO— Y 4 represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (any hydrogen on these cyclic groups). The atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Or a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. A group, Y 5 is a benzene ring, any hydrogen atom on the divalent cyclic group (these cyclic group selected from the group consisting of hexane ring and the heterocyclic cycloheteroalkyl an alkyl group having 1-3 carbon atoms And optionally substituted with a C 1-3 alkoxyl group, a C 1-3 fluorine-containing alkyl group, a C 1-3 fluorine-containing alkoxyl group, or a fluorine atom. When 4 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, it is an integer of 2 to 4, and Y 4 is selected from an organic group having 12 to 25 carbon atoms having a steroid skeleton. When it is a divalent organic group, it is an integer of 0 to 4. When n is plural, a plurality of Y 5 each independently has the above definition, and Y 6 has 1 to 18 carbon atoms. Alkyl group, fluorine-containing amine having 1 to 18 carbon atoms Kill group, a fluorine-containing alkoxyl group 1-18 alkoxyl group or a carbon number of 1 to 18 carbon atoms.)
The liquid crystal display element according to claim 1, wherein the polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide.
The polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide which are a reaction product of a diamine containing a diamine represented by the following formula and a tetracarboxylic dianhydride component. The liquid crystal display element according to claim 1.

Y 1, Y 2, Y 3 in the formula [2], Y 4, Y 5, Y 6, n is, Y 1, Y 2, Y 3 in the formula [1], Y 4, Y 5, Y 6, n Is the same as each definition. m is an integer of 1 to 4.
The liquid crystal display element of Claim 3 in which the said tetracarboxylic dianhydride component contains the tetracarboxylic dianhydride represented by following formula [3].

In the formula [3], Z 1 is a tetravalent organic group, a tetravalent organic group having 4 to 13 carbon atoms, and a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms. preferable.
The liquid crystal display element according to claim 4, wherein Z 1 of the tetracarboxylic dianhydride represented by the formula [3] is at least one selected from the following structural formulas.

(Z 2 to Z 5 are each independently a group selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and Z 6 and Z 7 are each independently a hydrogen atom or a methyl group. is there.)
A liquid crystal aligning agent, which is a liquid crystal aligning agent for a liquid crystal display device including a liquid crystal panel having a curved shape, and contains a polymer having a structure represented by the following formula [1].

(Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—, and Y 2 is A single bond or (CH 2 ) b — (b is an integer of 1 to 15), Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), — O—, —CH 2 O—, —COO— or OCO— Y 4 represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (any hydrogen on these cyclic groups). The atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Or a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. A group, Y 5 is a benzene ring, any hydrogen atom on the divalent cyclic group (these cyclic group selected from the group consisting of hexane ring and the heterocyclic cycloheteroalkyl represents an alkyl group having 1 to 3 carbon atoms And optionally substituted with a C 1-3 alkoxyl group, a C 1-3 fluorine-containing alkyl group, a C 1-3 fluorine-containing alkoxyl group, or a fluorine atom. When 4 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, it is an integer of 2 to 4, and Y 4 is selected from an organic group having 12 to 25 carbon atoms having a steroid skeleton. When it is a divalent organic group, it is an integer of 0 to 4. When n is plural, a plurality of Y 5 each independently has the above definition, and Y 6 has 1 to 18 carbon atoms. Alkyl group, fluorine-containing amine having 1 to 18 carbon atoms Kill group, a fluorine-containing alkoxyl group 1-18 alkoxyl group or a carbon number of 1 to 18 carbon atoms.)
The liquid crystal aligning agent according to claim 6, wherein the polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide.
The polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide which are a reaction product of a diamine containing a diamine represented by the following formula and a tetracarboxylic dianhydride component. The liquid crystal aligning agent of Claim 6.
The polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide which are a reaction product of a diamine containing a diamine represented by the following formula and a tetracarboxylic dianhydride component. The liquid crystal aligning agent of Claim 6.

(Y 1 in the formula [2], Y 2, Y 3, Y 4, Y 5, Y 6, n is, Y 1, Y 2, Y 3 in the formula [1], Y 4, Y 5, Y 6, (It is the same as each definition of n. m is an integer of 1 to 4.)
The liquid crystal aligning agent of Claim 8 or 9 in which the said tetracarboxylic dianhydride component contains the tetracarboxylic dianhydride represented by following formula [3].

(Z 1 is a tetravalent organic group having 4 to 13 carbon atoms.)
Z 1 in the formula [3] is at least one selected from the following structural formulas, the liquid crystal aligning agent of claim 10.

(Z 2 to Z 5 are each independently a group selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and Z 6 and Z 7 are each independently a hydrogen atom or a methyl group. .)