KR20190031570A - A liquid crystal display element having a liquid crystal panel having a curved shape and a liquid crystal alignment agent therefor - Google Patents

Abstract

Provided is a liquid crystal display device provided with a liquid crystal panel having a curved surface shape without a bright spot even when physical friction such as rubbing of spacer occurs.
A curved liquid crystal display element comprising a liquid crystal alignment film containing a polymer containing the structure of the following formula [1]. (Wherein Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- and Y ² represents a single bond (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 atom on these cyclic groups is 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 an organic group having 12 to 25 carbon atoms and having a steroid skeleton and the divalent organic group is selected, Y ⁵ is a benzene ring, a cyclohexane ring, and any hydrogen atom in the divalent cyclic group selected from the group consisting of a heterocyclic (cyclic group thereof Carbon atoms are optionally 1-3 alkyl group, and substituted fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms, an alkoxyl group, having 1 to 3 fluorine-containing alkyl group, having 1 to 3 carbon atoms in the.), N is, Y ⁴ Is an integer of 2 to 4 when it is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and Y ⁴ is a divalent organic group selected from an organic group having 12 to 25 carbon atoms and having a steroid skeleton is an integer from 0 to 4. in addition, when n is plural, a plurality of Y ⁵ has the definition of each independently. Y ⁶ is a fluorine-containing alkyl group having 1 to 18 alkyl group, having 1 to 18, An alkoxyl group having 1 to 18 carbon atoms or a fluorinated alkoxyl group having 1 to 18 carbon atoms.)

Description

A liquid crystal display element having a liquid crystal panel having a curved shape and a liquid crystal alignment agent therefor

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

2. Description of the Related Art In recent years, a liquid crystal display device has been used in various electronic devices such as a smart phone, a mobile phone, a television, a navigation device, an electronic notebook, an electronic book, and the like, with reduction in thickness and low power consumption. The liquid crystal display device is provided with a liquid crystal panel and a driving circuit and, if necessary, is equipped with an auxiliary device such as a backlight, a light guide plate, and a casing. When a typical liquid crystal display device is used in an electronic device, the display surface of the liquid crystal display device is configured to be arranged substantially in parallel with the case of the electronic device and in a planar shape.

On the other hand, recently, as the liquid crystal display device has been used in various fields, a curved surface shape along the outer surface of the case of the electronic device has been developed in view of an increase in display area, a sense of wideness, immersion, A liquid crystal display device having a liquid crystal panel having a liquid crystal layer (not shown) is proposed and used (see Patent Document 1).

Japanese Patent Application Laid-Open No. 10-268245 Japanese Patent Application Laid-Open No. 10-104633 Japanese Patent Application Laid-Open 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 case. As a result, the spacer existing inside the liquid crystal panel moves in the liquid crystal panel to rub the liquid crystal alignment film. The liquid crystal alignment film stressed by the spacer can not regulate the orientation of the liquid crystal and the liquid crystal panel is displayed as a luminescent spot because the light escapes from the periphery of the spacer in spite of black display.

SUMMARY OF THE INVENTION The object of the present invention is to provide a liquid crystal display device having a liquid crystal panel having a curved surface shape which can minimize a luminescent spot even when physical friction such as rubbing by a spacer occurs, And to provide a liquid crystal aligning agent.

As a result of intensive studies, the present inventors have completed the present invention. That is, the present invention has the following points.

(1) A liquid crystal display element comprising a curved liquid crystal panel having a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polymer having a structure represented by the following formula [1].

[Chemical 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-, 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 atom on the cyclic group is preferably an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, 3 fluorine-containing alkyl group, or it may be substituted with a fluorine-containing alkoxy group or a fluorine atom having 1 to 3), or a divalent organic group selected from organic groups having a carbon number of 12 to 25 having a steroid skeleton, Y ⁵ is A benzene ring, a cyclohexane ring and a heterocyclic ring (any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms fluorine-containing alkyl group, or it may be substituted with a fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms), n is, Y ⁴ is a benzene ring, a cyclohexane ring, and the complex If the cyclic group is selected from the group consisting of Lee is an integer of 2 ~ ^4, Y 4 is a divalent organic group selected from organic groups having a carbon number of 12 to 25 having a steroid skeleton, if there is an integer of 0-4. When n is plural, a plurality of Y < ⁵ > s each independently have the above definition. 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 fluorinated alkoxyl group having 1 to 18 carbon atoms.

(2) A liquid crystal aligning agent for a liquid crystal display element comprising a liquid crystal panel having a curved shape, wherein the liquid crystal aligning agent contains a polymer having the structure represented by the formula (1).

According to the present invention, it is possible to provide a liquid crystal display device provided with a liquid crystal panel having a curved shape, and a liquid crystal aligning agent therefor, which can minimize a luminescent spot even when physical friction such as rubbing by a spacer occurs.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of a liquid crystal cell produced by using a polyimide coating film-attached substrate subjected to a scratch test (which will be described in detail in Examples) with a polarizing microscope. In this photograph, the bright spot is hardly visible at the spot where the scratch test was carried out.
Fig. 2 is a photograph of a liquid crystal cell produced by using the polyimide coating film-attached substrate subjected to the above-described scratch test with a polarizing microscope. In this photograph, it can be seen that the light is transmitted from the point where the scratch test is carried out and is made to be a luminescent spot.

The curved liquid crystal display element comprising the liquid crystal panel having the curved shape of the present invention comprises a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polymer containing a structure (also referred to as a specific structure) represented by the following formula [1] .

<Specific structure>

(2)

In 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 them, a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or COO- is preferable because the side chain structure is easy to synthesize. More preferably, it is 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 them, 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 them, a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- is preferable since it is easy to synthesize. More preferably, it is 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 bivalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups 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. Y ⁴ is a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton. Y ⁴ is preferably an organic group having 12 to 25 carbon atoms and having a benzene ring, a cyclohexyl ring or a steroid skeleton.

Y ⁵ is a bivalent 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 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.

n is an integer of 2 to 4 when Y ⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and Y ⁴ is selected from organic groups having 12 to 25 carbon atoms and having a steroid skeleton And is an integer of 0 to 4 when it is a divalent organic group. When n is plural, a plurality of Y &lt; ⁵ &gt; s each independently have the above definition.

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 fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, 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 fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

&Lt; Polymer having specific structure &gt;

The polymer having a specific structure to be used in the present invention is not particularly limited, but examples thereof include acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrene, polyimide precursors, polyimides, polyamides, It is preferable that the polymer is selected from the group consisting of polysiloxane. Among them, a polyimide precursor, a polyimide or a polysiloxane is preferable, and a polyimide precursor or a polyimide is more preferable.

When the polymer used in the present invention is a polyimide precursor or polyimide, they are obtained by the reaction of a diamine and a tetracarboxylic acid dianhydride. From the viewpoint of ease of production, it is preferable that the polymer has a specific structure is a diamine.

&Lt; Diamines having a specific structure &gt;

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

(3)

Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2] are the same as those in the formula [1], including preferred ones. M is an integer of 1 to 4, and preferably 1.

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

[Chemical Formula 4]

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

[Chemical Formula 5]

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

[Chemical Formula 6]

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, A ² is an oxygen atom or COO- * ( provided that the combined hand provided with an "*" in combination with a ^3), and, a ¹ is (are combined to give the hands, however, '*' (CH ₂₎ oxygen atom, or COO- * engages with a ₂₎₎ to be. A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is 1.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

&Lt; Other diamine compounds &gt;

In the present invention, other diamine compounds other than the specific diamine can be used in combination as the diamine component. Specific examples thereof are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamino Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- bis (3-aminophenyl) silane, Aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,3-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, (2,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 ' - diaminobenzophenone, 2,3'-diaminobenzophenone, Diaminonaphthalene, 1,6-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,6-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) ) Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1, (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, Phenylene bis (methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ , 4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-amino)] phenanthrene [(4-aminophenyl) methanone] Phenylenemethanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [ Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate) Bis (3-aminophenyl) isophthalate, bis (4-aminophenyl) isophthalate, N, N ' Bis (4-aminobenzamide), N, N '- (1,4-phenylene) bis (3-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- Bis (3-aminophenyl) terephthalamide, N, N'-bis (4- (4-aminophenoxy) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis [ Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane, (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4- Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) pentane, Aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- Phenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis -Bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- , 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- , Aromatic diamine compounds such as 3- (aminomethyl) aniline, 4- (2-aminoethyl) aniline, and 3- (2-aminoethylaniline); Alicyclic diamine compounds such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane; 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, Aliphatic diamine compounds such as 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 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.

[Chemical Formula 12]

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

[Chemical Formula 13]

A ⁶ is, -COO-, -OCO-, -CONH-, -NHCO- , -CH 2 - represents, -O-, -CO- or NH-, A ⁷ is an alkyl group or a fluorine having 1 to 22 Containing alkyl group.

[Chemical Formula 14]

p is an integer of 1 to 10;

The diamines of the following formulas [DA13] to [DA20] may also be used in combination.

[Chemical Formula 15]

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

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

[Chemical Formula 16]

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-, CON (CH ₃ ) - or N (CH ₃ ) CO-, m ₂ and m ₃ are each 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 represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C (CH ₃ ) ₂ -, -CF ₂ -, -C (CF ₃ ) -, -O-, _{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 of 1 to 4.

The other diamine compounds may be used alone or in combination of two or more thereof, depending on the properties such as liquid crystal alignment property, voltage holding ratio, and accumulated charge when the liquid crystal alignment film is used.

&Lt; Tetracarboxylic acid dianhydride component &gt;

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

[Chemical Formula 17]

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

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

[Chemical Formula 18]

Z ² to Z ⁵ each independently represent 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. A particularly preferable example of Z ¹ is a formula [3a], a formula [3c], a formula [3d], a formula [3e], a formula [3f] or a formula [3g] from the viewpoint of polymerization reactivity and ease of synthesis.

&Lt; Other tetracarboxylic acid dianhydrides &gt;

In the present invention, other tetracarboxylic acid dianhydrides other than the specific tetracarboxylic acid dianhydrides may be used. Examples of other tetracarboxylic acid dianhydrides include tetracarboxylic acid dianhydrides of the following tetracarboxylic acids.

Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, Anthracene tetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic 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) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2 , 6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid .

The other tetracarboxylic acid dianhydrides may be used alone or in combination of two or more thereof, depending on the properties such as liquid crystal alignability, voltage retention rate, and accumulated charge when the liquid crystal alignment film is used.

&Lt; Process for producing specific polymer &

The method for synthesizing the specific polymer in the present invention is not particularly limited. Is usually obtained by subjecting a diamine component and a tetracarboxylic acid dianhydride component to a polycondensation reaction. Generally, a polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic acid and a derivative thereof and a diamine component composed of one or more kinds of diamine compounds. In order to obtain a polyamide acid alkyl ester, a method of converting a carboxyl group of a polyamic acid into an ester is used.

Further, in order to obtain the polyimide, a method of imidizing the polyamic acid or polyamide acid alkyl ester described above into polyimide is used.

The liquid crystal alignment film obtained by using the specific polymer of the present invention is characterized in that the proportion of the specific diamine in the diamine component increases and the initial retention ratio The relaxation of the charge is fast. Further, as the content ratio of the specific diamine in the diamine component increases, the pretilt angle of the liquid crystal can be increased. At that time, for the purpose of enhancing the above 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, more preferably 0.1 to 50 mol, per mol of the specific diamine Preferably 0.5 to 20 moles, and most preferably 0.5 to 10 moles.

In order to obtain the specific polymer of the present invention, it is preferable to use a specific tetracarboxylic acid dianhydride for the tetracarboxylic acid dianhydride component. At this time, it is preferable that 1 mol% or more of the tetracarboxylic acid dianhydride component is a specific tetracarboxylic acid dianhydride, more preferably 5 mol% or more, and still more preferably 10 mol% or more. In addition, 100 mol% of the tetracarboxylic acid dianhydride component may be a specific tetracarboxylic acid dianhydride.

The reaction of the diamine component and the tetracarboxylic acid dianhydride component is usually carried out in an organic solvent. The organic solvent to be used at this time is not particularly limited as long as it dissolves the resulting polyimide precursor. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve, ethyl cellosolve, methyl cellosolve, But are not limited to, sorbose, methylcellosolve acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, 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 Recol 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, Ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, N-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, lactic acid, methylene chloride, propylene carbonate, propylene carbonate, Methyl, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, Butyl methoxypropionate, diglyme or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Further, even if the solvent does not dissolve the polyimide precursor, the solvent may be mixed with the polyimide precursor to the extent that the resulting polyimide precursor does not precipitate. In addition, since moisture in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, it is preferable to use an organic solvent which is dehydrated and dried.

When the diamine component and the tetracarboxylic acid dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid dianhydride component is dispersed in the organic solvent, A method in which a diamine component is added to a solution in which a tetracarboxylic acid dianhydride is dispersed or dissolved in an organic solvent, a method in which a tetracarboxylic acid dianhydride component and a diamine component are alternately added, And any of these methods may be used. When a plurality of diamine components or tetracarboxylic acid dianhydride components are used to carry out the reaction, they may be reacted in a preliminarily mixed state, or they may be reacted individually or sequentially, and the individually reacted low- And a specific polymer may be used. The polymerization temperature at that time may be any temperature within the range of -20 to 150 ° C, preferably -5 to 100 ° C. The reaction can be carried out at an arbitrary concentration. However, if the concentration is too low, it becomes difficult to obtain a specific polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, 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 the moles of the tetracarboxylic acid dianhydride component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by dehydrocondylating 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 / removal rate (imidization rate) of the amide acid group is not necessarily 100%, and can be arbitrarily adjusted depending on the purpose and purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization for directly heating the solution of the polyimide precursor or catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

When the polyimide precursor is thermally imidized in a solution, the temperature is preferably 100 to 400 DEG C, and more preferably 120 to 250 DEG C. It is preferable to carry out the removal while removing water generated by the imidization reaction from the system.

The catalyst 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 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has a basicity suitable for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferred because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by controlling the amount of catalyst, the reaction temperature, and the reaction time.

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

The molecular weight of the specific polymer of the present invention is preferably 5,000 to 5,000 in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography), considering the strength of the polymer film obtained therefrom, the workability in forming the polymer film, And more preferably 10,000 to 150,000.

<Liquid Crystal Aligner>

In the liquid crystal aligning agent used in the present invention, all of the polymers may be the specific polymers mentioned above, or may be mixed with other polymers. At that time, the content of other polymer relative to the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.

Examples of the other polymer include a polyimide precursor obtained from a diamine component containing no specific diamine and a tetracarboxylic acid dianhydride component, or a polyimide obtained from the polyimide precursor. Further, polyimide precursors and polymers other than polyimide, specifically, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, and the like can be mentioned.

The organic solvent in the liquid crystal aligning agent used in the present invention preferably has an organic solvent content of 70 to 99 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 intended liquid crystal alignment film. The organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving the above-mentioned specific polymer. More specifically, there may be mentioned N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, Examples of the aminosulfuron compounds include N-vinylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide,? -Butyrolactone, Nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

<Additives>

Examples of the liquid crystal aligning agent used in the present invention include 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 and an alkoxyl group, A crosslinkable compound having a polymerizable unsaturated bond (hereinafter also referred to as a crosslinking agent), and the like.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl amino diphenylene Tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate Diglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylpentanoyloxyphenyl) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl methadienyldiamine, 2- (4- (1, 4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane, 1,3- Oxy) phenyl) -1- (4- (1- (4- ( 2,3-epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

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

[Chemical Formula 19]

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

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

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].

(23)

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

&Lt; EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

In the formula [5-24], n is an integer of 1 to 5, and in the formula [5-25], n is an integer of 1 to 5, and in the formula [5-36], n is an integer of 1 to 100 , And in the formula [5-37], n is an integer of 1 to 10.

Also, a polysiloxane having at least one structure represented by the following formulas [5-38] to [5-40] may be used.

(32)

In the formulas [5-38] to [5-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a hydroxyl group, An alkyl group, an alkoxyl group, an aliphatic ring or an aromatic ring, and at least one of them is a structure represented by the formula [5].

Specifically, the compound represented by the following formula [5-41] or the formula [5-42] can be given.

(33)

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 and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group such as a melamine resin, Guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea-formaldehyde resin and the like. Specifically, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group, or a benzoguanamine derivative or glycoluril can be used. The melamine derivative or the benzoguanamine derivative may be present as a dimer or trimer. They preferably have 3 to 6 methylol groups or alkoxymethyl groups per one triazine ring on average.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750 in which a methoxymethyl group is substituted in an average of 3.7 methoxymethyl groups per one triazine ring of a commercial product, MW having an average of 5.8 methoxymethyl groups per triazine ring -30 (manufactured by Sanwa Chemical Co.), methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212, 253 , Methoxymethylated butoxymethylated melamine such as 254, butoxymethylated melamine such as Cymel 506 and 508, and methoxymethylated isobutoxymethylated melamine containing carboxyl group such as Cymel 1141, methoxymethylated ethoxymethylated Methoxymethylated butoxymethylated benzoguanamines such as benzoguanamine and Cymel 1123-10, butoxymethylated benzoguanamines such as Cymel 1128, and carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80. Nammin (over, Mitsu Between mid Ana Co., Ltd.) and the like. Examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluril such as Cymel 1172, and methoxymethylolglycoluril 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 crosslinking compound. For example, 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec-butoxymethyl) Dihydroxymethyl-p-tert-butylphenol and the like.

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

(34)

(35)

(36)

(37)

(38)

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri ) Crosslinkable compounds having three polymerizable unsaturated groups such as acryloyloxyethoxy trimethylol propane or glycerin polyglycidyl ether poly (meth) acrylate; Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di Acrylates such as di (meth) acrylate, butylene glycol di (meth) 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, hydroxypivalic acid di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalic acid neopentyl glycol di The crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as a tree; Hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- Ester or N-methylol (meth) acrylamide may be mentioned as the crosslinkable compound having one polymerizable unsaturated group in the molecule.

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

[Chemical Formula 39]

E ¹ is a cyclohexane ring, a non-cyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a 1, made of a naphthalene ring, fluorene ring, anthracene ring or phenanthrene ring divalent group, E ² is, to the Is a monovalent group of the formula [7a] or [7b], and n is an integer of 1 to 4.

(40)

The compound is an example of a crosslinking compound, but is not limited thereto. The crosslinking compound contained in the liquid crystal aligning agent of the present invention may be one kind or two or more kinds.

The content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably from 0.1 to 150 parts by mass per 100 parts by mass of the polymer component, and the crosslinking reaction proceeds to exhibit the intended effect, More preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, in order not to deteriorate the heat resistance.

It is preferable to add a nitrogen-containing heterocyclic amine compound represented by the following formulas [M1] to [M156] as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge-off of the liquid crystal cell using the liquid crystal alignment film. The amine compound may be directly added to a solution of a specific polymer, but it is preferable to add the amine compound in an appropriate solvent at a concentration of 0.1 to 10 mass%, preferably 1 to 7 mass%. This solvent is not particularly limited as long as it is an organic solvent for dissolving the above-mentioned specific polymer.

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

The liquid crystal aligning agent of the present invention may contain an organic solvent (also referred to as a poor solvent) or a compound which improves the film thickness uniformity or surface smoothness of the polymer film when the liquid crystal aligning agent is applied, &Lt; / RTI &gt; Further, a compound for improving the adhesion between the liquid crystal alignment film and the substrate may be contained. Specific examples of the poor solvent for improving the uniformity of the film thickness and the surface smoothness include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl Propyleneglycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, 1-butanediol, 2-ethylhexyl monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, 2-butoxy-1-propanol, 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 moiety Propyleneglycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3- Diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butylate, butyl ether, diisobutyl ketone, 2,6-dimethyl-4-heptanol, diacetone alcohol, methylcyclo Propylene glycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monobutyl ether, isobutyleneglycol monomethyl ether, isobutyleneglycol monomethyl ether, isobutyleneglycol monomethyl ether, isobutyleneglycol monomethyl ether, Methyl, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- 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, Ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid diisobutyl ester, and the like.

These poor solvents may be used alone or in combination. When such a poor solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the organic solvent contained in the liquid crystal aligning agent.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

Specifically, for example, EF Top EF301, EF303 and EF352 (manufactured by Tohchem Products), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC430 and FC431 (manufactured by Sumitomo 3M Limited) , Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The proportion of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

Specific examples of the compound improving the adhesion between the liquid crystal alignment layer 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 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl 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-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When a compound for improving adhesion with a substrate is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid crystal aligning agent of the present invention may contain, in addition to the crosslinkable compound, the poor solvent and the compound for improving the adhesiveness, the liquid crystal aligning agent of the present invention for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film, A dielectric material or a conductive material may be added.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate, and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Further, in the case of vertical alignment application, etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate to be used at this time is not particularly limited as long as it is a substrate having high transparency. In addition to the 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 or the like for liquid crystal driving is formed. In a reflection type liquid crystal display element, an opaque substrate such as a silicon wafer can be used only for a substrate on one side, and a material for reflecting light such as aluminum can be used as the electrode in this case.

As a method of applying the liquid crystal aligning agent, it is industrially generally carried out by a method such as screen printing, offset printing, flexographic printing, ink jet printing or the like. As other coating methods, there are dip, roll coater, slit coater, spinner and the like, and they may be used depending on the purpose.

After the liquid crystal aligning agent is coated on the substrate, the polymer film can be formed by evaporating the solvent at 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate. When the thickness of the polymer film after firing is too large, the power consumption of the liquid crystal display element is deteriorated. When the thickness of the polymer film is too thin, the reliability of the liquid crystal display element is deteriorated. Therefore, the thickness is preferably 5 to 300 nm, Is 10 to 100 nm. When the liquid crystal is horizontally aligned or tilted, the polymer film after firing is subjected to rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate having a liquid crystal alignment film is obtained from the above liquid crystal aligning agent, and then a liquid crystal cell is manufactured by a known method to obtain a liquid crystal display element.

As a manufacturing method of a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on the liquid crystal alignment film of the substrate of the single chamber, and the substrates of the other unilateral chamber are bonded A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed, and then a substrate is bonded and sealed.

A feature of the present invention resides in that the liquid crystal display panel in the liquid crystal display element has a curved shape. That is, although a pair of substrates constituting the liquid crystal display panel has a curved surface, the shape and degree of the curved surface are various and arbitrarily selected. Particularly, the present invention is effective for a liquid crystal display panel having a curved surface in a cross section along the uniaxial direction and a radius of curvature R of a curved surface shape of 1000 mm to 3000 mm.

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent comprising a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound polymerized by at least one of active energy rays and heat between a pair of substrates The present invention is preferably used for a liquid crystal display device produced by a process of arranging a liquid crystal composition and polymerizing a polymerizable compound by at least one of irradiation of an active energy ray and heating while applying a voltage between electrodes. Here, the active energy ray is preferably ultraviolet ray.

The above liquid crystal display element controls the pretilt angle of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed into a liquid crystal material, and a liquid crystal cell is assembled. Then, a predetermined voltage is applied to the liquid crystal layer, And controls the pretilt angle of the liquid crystal molecules by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed on the liquid crystal layer. In the PSA system, since the rubbing treatment is not required, it is suitable for forming a vertical alignment type liquid crystal layer which is difficult to control the pretilt angle by the rubbing treatment.

That is, the liquid crystal display element of the present invention can be obtained by preparing a liquid crystal alignment film-attached substrate from the liquid crystal aligning agent of the present invention by the above-mentioned technique, preparing a liquid crystal cell, and then polymerizing the polymerizable compound by at least one of irradiation with ultraviolet rays and heating The orientation of the liquid crystal molecules can be controlled by polymerization.

One example of manufacturing a liquid crystal cell is to prepare a pair of substrates having a liquid crystal alignment film formed thereon and spraying a spacer on the liquid crystal alignment film of the substrate of the single chamber so that the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed, and then a substrate is bonded and sealed.

The liquid crystal is mixed with a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays. Examples of the polymerizable compound include a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. At that time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. If the amount of the polymerizable compound is less than 0.01 part by mass, the alignment of the liquid crystal can not be controlled because the polymerizable compound is not polymerized. If more than 10 parts by mass, the unreacted polymerizable compound increases, .

After the liquid crystal cell is manufactured, the polymerizable compound is polymerized by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell. Thereby, the orientation of the liquid crystal molecules can be controlled.

Furthermore, the liquid crystal aligning agent of the present invention comprises a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group which polymerizes by at least one of active energy rays and heat between the pair of substrates It is preferably used for a liquid crystal display element manufactured by arranging a liquid crystal alignment film and applying a voltage between electrodes. Here, the active energy ray is preferably ultraviolet ray.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerizing 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 method of using a polymer component containing a polymerizable group . 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 moiety that reacts by irradiation with heat or ultraviolet rays, the orientation of the liquid crystal molecules can be controlled by at least one of irradiation with ultraviolet rays and heating have.

One example of manufacturing a liquid crystal cell is to prepare a pair of substrates having a liquid crystal alignment film formed thereon and spraying a spacer on the liquid crystal alignment film of the substrate of the single chamber so that the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed, and then a substrate is bonded and sealed.

After the liquid crystal cell is fabricated, the alignment of the liquid crystal molecules can be controlled by applying heat or ultraviolet rays while applying alternating current or direct current 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 preferably used for a liquid crystal television of a large screen and high precision.

Example

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto. In the following, the abbreviations used are as follows.

(Tetracarboxylic acid dianhydride)

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

(47)

(Diamine)

3-AMPDA: 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide

p-PDA: p-phenylenediamine

PBCH5DAB: 1,3-Diamino-4- {trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

(48)

(additive)

(49)

(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

&Lt; Measurement of molecular weight of polyimide &

The molecular weight of the polyimide in Synthesis Example was measured using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd., a column (KD-803, KD-805) Respectively.

Column temperature: 50 ° C

30 mmol / l of lithium bromide-hydrate (LiBr 占 O 2O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid), 30 ml of tetrahydrofuran (THF) as an additive, 10 ml / l), flow rate: 1.0 ml / min,

Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 9,000,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

&Lt; Measurement of imidization rate &

The imidization rate of the polyimide was measured as follows. 20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard 5 manufactured by Kusano Scientific Co., Ltd.), 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added, . This solution was subjected to proton NMR measurement at 500 MHz using an NMR meter (JNW-ECA500) manufactured by Nippon DATUM Co., A proton originating from a structure that does not change before and after imidization is defined as a reference proton and the proton peak integrated value derived from the NH group of amic acid appearing at about 9.5 to 10.0 ppm near the proton is used And was obtained by the following formula.

Imidization ratio (%) = (1 -? X / y) x 100

<Measurement of molecular weight>

The molecular weights of the polyimide and polysiloxane were measured as follows using a column (sample side KF-803, reference side KF-800RH) manufactured by Shodex.

Column temperature: 40 DEG C,

Eluent: tetrahydrofuran, flow rate: 1 ml / min, standard sample for calibration curve: polystyrene (molecular weight: about 52,400, 19,900, 7,200, 2,970, 580, manufactured by Shodex).

&Lt; Synthesis Example 1 &

A mixture of 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) After reacting at 80 ° C for 5 hours, CBDA (18.53 g, 94.5 mmol) and NMP (94.6 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.

NMP (62.3 g) was added to the polyamic acid solution (30.0 g) and diluted to 6 mass%, acetic anhydride (6.02 g) and pyridine (1.87 g) were added as an imidation catalyst, Lt; / RTI &gt; This reaction solution was poured into methanol (601.0 g), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A). The imidization ratio of the polyimide was 75%, Mn (number average molecular weight) was 13,200, and Mw (weight average molecular weight) was 40,600.

&Lt; Synthesis Example 2 &

(16.33 g, 37.8 mmol), DA-8 (14.39 g, 37.8 mmol), 3-aminopyridine (16.0 g, 66.15 mmol), B- (18.53 g, 94.5 mmol) and NMP (94.6 g) were added to the reaction mixture and reacted at 40 ° C for 6 hours to obtain polyamic acid Solution.

NMP (62.3 g) was added to the polyamic acid solution (30.0 g) and diluted to 6 mass%, acetic anhydride (6.15 g) and pyridine (1.90 g) were added as an imidation catalyst, Lt; / RTI &gt; This reaction solution was poured into methanol (602.1 g), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (B). The imidization ratio of the polyimide was 75%, Mn was 12,900, and Mw was 40,400.

&Lt; Synthesis Example 3 &

A mixture of 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) After reacting at 80 ° C for 5 hours, 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.

NMP (87.1 g) was added to the polyamic acid solution (30.0 g) and diluted to 6 mass%. Acetic anhydride (6.95 g) and pyridine (2.15 g) were added as an imidation catalyst, Lt; / RTI &gt; The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (C). The imidization rate of this polyimide was 75%, Mn was 11,800, and Mw was 39,600.

&Lt; Synthesis Example 4 &

A mixture of 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) After reacting at 80 ° C for 5 hours, 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.

NMP (87.1 g) was added to the polyamic acid solution (30.0 g) and diluted to 6 mass%. Acetic anhydride (6.95 g) and pyridine (2.15 g) were added as an imidation catalyst, Lt; / RTI &gt; The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (D). The imidization ratio of this polyimide was 75%, Mn was 11,900, and Mw was 40,100.

&Lt; 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) 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.

NMP (87.1 g) was added to the polyamic acid solution (30.0 g) and diluted to 6 mass%. Acetic anhydride (6.95 g) and pyridine (2.15 g) were added as an imidation catalyst, Lt; / RTI &gt; The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (E). The imidization rate of this polyimide was 75%, Mn was 14,100, and Mw was 41,000.

&Lt; 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) 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.

NMP (87.1 g) was added to the polyamic acid solution (30.0 g) and diluted to 6 mass%. Acetic anhydride (6.95 g) and pyridine (2.15 g) were added as an imidation catalyst, Lt; / RTI &gt; The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (F). The imidization rate of this polyimide was 75%, Mn was 11,900, and Mw was 40,000.

&Lt; Synthesis Example 7 &

(33.0 g, 74 mmol) was mixed in NMP (272.8 g), and the mixture was reacted at 80 ° C for 5 hours. Then, 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.

NMP (87.1 g) was added to the polyamic acid solution (30.0 g) and diluted to 6 mass%. Acetic anhydride (6.95 g) and pyridine (2.15 g) were added as an imidation catalyst, Lt; / RTI &gt; The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (G). The imidization rate of the polyimide was 75%, the Mn was 11,400, and the Mw was 39,000.

&Lt; Synthesis Example 8 &

7 (33.0 g, 74 mmol) was mixed in NMP (272.8 g), and the mixture was reacted at 80 ° C for 5 hours. Then, 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.

NMP (87.1 g) was added to the polyamic acid solution (30.0 g) and diluted to 6 mass%. Acetic anhydride (6.95 g) and pyridine (2.15 g) were added as an imidation catalyst, Lt; / RTI &gt; The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (H). The imidization rate of the polyimide was 75%, Mn was 15,700, and Mw was 41,200.

&Lt; Synthesis Example 9 &

A solution of the 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-neck reaction flask equipped with a thermometer and reflux tube. A solution prepared by previously 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 this solution over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, a mixed solution of 0.86 g of a methanol solution having a UPS content of 92 mass%, 0.86 g of HG and 0.86 g of BCS was added. Bangraeng then added and refluxed for another 30 minutes to obtain a polysiloxane solution (I) in terms of SiO ₂ concentration of 12% by weight. The polysiloxane had Mn of 5,100 and Mw of 9,100.

&Lt; Synthesis Example 10 &

A solution of alkoxysilane monomer was prepared by mixing 21.3 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-neck reaction flask equipped with a thermometer and reflux tube. A solution prepared by previously 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 this solution over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, a mixed solution of 0.86 g of a methanol solution having a UPS content of 92 mass%, 0.86 g of HG and 0.86 g of BCS was added. Bangraeng then added and refluxed for another 30 minutes to obtain a polysiloxane solution (J) in terms of SiO ₂ concentration of 12% by weight. The polysiloxane had 2,400 Mn and 4,800 Mw.

<Comparative Synthesis Example 1>

A mixture of 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) After reacting at 80 ° C for 5 hours, CBDA (18.53 g, 94.5 mmol) and NMP (94.6 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.

NMP (62.3 g) was added to the polyamic acid solution (30.0 g) and diluted to 6 mass%, acetic anhydride (6.29 g) and pyridine (1.95 g) were added as an imidation catalyst, Lt; / RTI &gt; This reaction solution was poured into methanol (603.2 g), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (K). The imidization ratio of the polyimide was 75%, Mn was 13,200, and Mw was 39,300.

&Lt; Example 1 &gt;

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 占 폚 for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain liquid crystal aligning agent [1]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 2 &gt;

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 占 폚 for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain liquid crystal aligning agent [2]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 3 &gt;

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 占 폚 for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain liquid crystal aligning agent [3]. No abnormality such as turbidity or precipitation was 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 占 폚 for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain liquid crystal aligning agent [4]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 5 &gt;

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 占 폚 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]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 6 &gt;

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 占 폚 for 40 hours. BCS (40.0 g) was added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent [6]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 7 &gt;

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 占 폚 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]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 8 &gt;

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 占 폚 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]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 9 &gt;

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 占 폚 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]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 10 &gt;

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 占 폚 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]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 11 &gt;

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 占 폚 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]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 12 &gt;

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 占 폚 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]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 13 &gt;

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 占 폚 for 40 hours. To this solution was added BCS (40.0 g), and the mixture was stirred for 5 hours. Compound 1 powder (0.6 g) was added and stirred for 24 hours to obtain a liquid crystal aligning agent [13]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 14 &gt;

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 占 폚 for 40 hours. BCS (40.0 g) was added to this solution, and the mixture was stirred for 5 hours. Compound 2 powder (0.6 g) was added and stirred for 24 hours to obtain liquid crystal aligning agent [14]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 15 &gt;

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 占 폚 for 40 hours. BCS (40.0 g) was added to this solution, and after stirring for 5 hours, Compound 1 powder (0.3 g) and Compound 2 powder (0.3 g) were added and stirred for 24 hours to obtain liquid crystal aligning agent [15]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Example 16 &gt;

10.0 g of the polysiloxane solution (I) obtained in Synthesis Example 9, 15.0 g of HG and 15.0 g of BCS were mixed to obtain a liquid crystal aligning agent [16]. It was confirmed that no abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent.

&Lt; Example 17 &gt;

10.0 g of the polysiloxane solution (J) obtained in Synthesis Example 10, 15.0 g of HG and 15.0 g of BCS were mixed to obtain a liquid crystal aligning agent [17]. It was confirmed that no abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent.

&Lt; 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 占 폚 for 40 hours. BCS (40.0 g) was added to this solution and stirred at 50 占 폚 for 15 hours to obtain a liquid crystal aligning agent [18]. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Preparation of polyimide coating film-attached substrate &gt;

Each liquid crystal aligning agent obtained in each of Examples 1 to 17 and Comparative Example 1 was spin-coated on the ITO surface of a 3 cm x 4 cm ITO-adhered glass substrate and fired at 70 ° C for 1 minute and 30 seconds on a hot plate, And fired in an infrared heating furnace at 230 캜 for 30 minutes to prepare a substrate having a polyimide coating film having a thickness of 100 nm.

In the case of the liquid crystal aligning agent obtained in Example 16, the firing in the hot plate was carried out at 80 캜 for 3 minutes instead of at 70 캜 for 1 minute and 30 seconds, but otherwise the same.

&Lt; Evaluation of bright spot &

The polyimide coating film-attached substrate obtained in Example 1 and Comparative Example 1 was mounted on UMT-2 (manufactured by Bruker AXES Co., Ltd.) (FVL sensor, 1.6 mm sapphire spheres mounted on the tip of the apparatus) A scratch test was conducted from 0.5 mils (5 mm / sec) in the horizontal axis to 2 mils in the moving direction and from 1 mN to 20 mN over 100 seconds, followed by the dropwise addition of MLC-3022 (Merck Japan). A spacer having a size of 4 mu m was spread thereon on another polyimide coating film-attached substrate obtained above, and sandwiched therebetween toward the side of the dropped MLC-3022. (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) with a polarizing plate of 90 deg., A scratch test was performed to observe whether or not light was transmitted.

As shown in Fig. 1, a state in which a bright spot is almost invisible is evaluated as &quot;? &Quot;, a state in which a bright spot is slightly visible as shown in Fig. 2 is evaluated as &quot;? &Quot;, and as shown in Fig. 3, The results are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

The entire contents of the specification, claims, drawings, and summary of Japanese Patent Application No. 2016-153149 filed on August 3, 2016 are incorporated herein by reference and incorporated herein by reference.

Claims (11)

A liquid crystal display element comprising a curved liquid crystal panel having a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polymer having a structure represented by the following formula [1].
[Chemical Formula 1]

(Wherein Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- and Y ² represents a single bond (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 atom on these cyclic groups is 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 an organic group having 12 to 25 carbon atoms and having a steroid skeleton and the divalent organic group is selected, Y ⁵ is a benzene ring, a cyclohexane ring, and any hydrogen atom in the divalent cyclic group selected from the group consisting of a heterocyclic (cyclic group thereof Carbon atoms are optionally 1-3 alkyl group, and substituted fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms, an alkoxyl group, having 1 to 3 fluorine-containing alkyl group, having 1 to 3 carbon atoms in the.), N is, Y ⁴ Is an integer of 2 to 4 when it is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and Y ⁴ is a divalent organic group selected from an organic group having 12 to 25 carbon atoms and having a steroid skeleton is an integer from 0 to 4. in addition, when n is plural, a plurality of Y ⁵ has the definition of each independently. Y ⁶ is a fluorine-containing alkyl group having 1 to 18 alkyl group, having 1 to 18, An alkoxyl group having 1 to 18 carbon atoms or a fluorinated alkoxyl group having 1 to 18 carbon atoms.) The method 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 method according to claim 1,
Wherein the polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide as a reaction product of a diamine containing diamine represented by the following formula and a tetracarboxylic acid dianhydride component.
(2)

Equation ^{[2] Y 1, Y 2} , Y 3, Y 4, Y 5, Y 6, n is the formula ^{[1] Y 1, Y 2} , Y 3, Y 4, Y in in ^5, Y ⁶ , and n. m is an integer of 1 to 4; The method of claim 3,
Wherein the tetracarboxylic acid dianhydride component contains a tetracarboxylic acid dianhydride represented by the following formula [3].
(3)

In the formula [3], Z ¹ is a tetravalent organic group and is a tetravalent organic group having 4 to 13 carbon atoms and preferably contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms. 5. The method of claim 4,
Wherein Z ¹ of the tetracarboxylic acid dianhydride represented by the above formula [3] is at least one selected from the following structural formulas.
[Chemical Formula 4]

(Z ² to Z ⁵ each independently represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and Z ⁶ and Z ⁷ each independently represent a hydrogen atom or a methyl group.) A liquid crystal aligning agent for a liquid crystal display element comprising a liquid crystal panel having a curved shape and comprising a polymer having a structure represented by the following formula [1].
[Chemical Formula 5]

(Wherein Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- and Y ² represents a single bond (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 atom on these cyclic groups is 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 an organic group having 12 to 25 carbon atoms and having a steroid skeleton and the divalent organic group is selected, Y ⁵ is a benzene ring, a cyclohexane ring, and any hydrogen atom in the divalent cyclic group selected from the group consisting of a heterocyclic (cyclic group thereof Carbon atoms are optionally 1-3 alkyl group, and substituted fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms, an alkoxyl group, having 1 to 3 fluorine-containing alkyl group, having 1 to 3 carbon atoms in the.), N is, Y ⁴ Is an integer of 2 to 4 when it is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and Y ⁴ is a divalent organic group selected from an organic group having 12 to 25 carbon atoms and having a steroid skeleton is an integer from 0 to 4. in addition, when n is plural, a plurality of Y ⁵ has the definition of each independently. Y ⁶ is a fluorine-containing alkyl group having 1 to 18 alkyl group, having 1 to 18, An alkoxyl group having 1 to 18 carbon atoms or a fluorinated alkoxyl group having 1 to 18 carbon atoms.) The method 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 method according to claim 6,
Wherein the polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide which are reactants of a diamine containing a diamine represented by the following formula and a tetracarboxylic acid dianhydride component. The method according to claim 6,
Wherein the polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide which are reactants of a diamine containing a diamine represented by the following formula and a tetracarboxylic acid dianhydride component.
[Chemical Formula 6]

Y ^3, Y ^4, Y ^5, Y ^6, n is the formula ^{[1] Y 1, Y 2} , Y 3, Y 4, Y 5 in (formula ^[2] Y ^1, Y 2 in, , Y ⁶ , and n, and m is an integer of 1 to 4.) 10. The method according to claim 8 or 9,
Wherein the tetracarboxylic acid dianhydride component contains a tetracarboxylic acid dianhydride represented by the following formula [3].
(7)

(Z ¹ is a tetravalent organic group having 4 to 13 carbon atoms) 11. The method of claim 10,
Wherein Z ¹ in the formula [3] is at least one selected from the following structural formulas.
[Chemical Formula 8]

(Z ² to Z ⁵ are each independently 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.)

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