WO2008053848A1

WO2008053848A1 - Agent for alignment treatment of liquid crystal and liquid crystal display element using the same

Info

Publication number: WO2008053848A1
Application number: PCT/JP2007/071045
Authority: WO
Inventors: Kazuyoshi Hosaka; Kohei Goto; Noritoshi Miki; Kenzo Yada
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-11-01
Filing date: 2007-10-29
Publication date: 2008-05-08
Also published as: JPWO2008053848A1; CN101600989A; TWI407214B; KR20090076944A; JP5218062B2; KR101455418B1; CN101600989B; TW200841093A

Abstract

Disclosed is an agent for the alignment treatment of a liquid crystal, which has a highly stabilized pretilt angle. Also disclosed is a liquid crystal display element which has less change in a pretilt angle and also has excellent display reliability. The agent for the alignment treatment of a liquid crystal comprises at least one polymer selected from the group consisting of polyamic acid and polyimide and a crosslinkable compound having at least two oxetane groups represented by the formula [I] in the molecule.

Description

Specification

Liquid crystal alignment treatment agent and liquid crystal display element using the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film, and a liquid crystal display element using the same.

Background art

In a liquid crystal display element, a liquid crystal alignment film plays a role of aligning liquid crystals in a certain direction. Currently, the main liquid crystal alignment film that is industrially used is produced by applying a polyimide-based liquid crystal alignment treatment agent composed of a polyimide precursor, a polyamic acid or a polyimide solution, onto a substrate, and forming a film. When the liquid crystal is aligned in parallel or inclined with respect to the substrate surface, a surface stretching process is further performed by rubbing after film formation. As an alternative to rubbing treatment, a method using an anisotropic photochemical reaction such as irradiation with polarized ultraviolet rays has been proposed. In recent years, studies for industrialization have been conducted.

[0003] The liquid crystal alignment film is used for controlling the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal, the performance of the liquid crystal display element becomes higher, and the range of use expands year by year. Among them, the stability of the pretilt angle which is not just a predetermined pretilt angle can be obtained.

[0004] From the viewpoint of the stability of the pretilt angle, a compound having two or more epoxy groups in the molecule is used for the purpose of obtaining a constant pretilt angle regardless of the rubbing conditions in the manufacturing process of the liquid crystal alignment film. It has been proposed to be included in a liquid crystal alignment treatment agent (for example, see Patent Document 1).

[0005] In addition, in the manufacturing process of a liquid crystal display element, in order to improve the alignment uniformity of the liquid crystal, the liquid crystal is sometimes isotropically treated by heat treatment after sealing the liquid crystal. If the pretilt angle stability is low, if the pretilt angle of the desired size cannot be obtained after this isotropic treatment, or if the pretilt angle has a variation force S! /, Problems arise. In particular, liquid crystal display elements that use a backlight that generates a large amount of heat to obtain high brightness, and liquid crystal display elements that are used in in-vehicle applications, such as car navigation systems. The one panel may be used or left in a high temperature environment for a long time. Under such severe conditions, if the pretilt angle changes gradually, problems such as failure to obtain initial display characteristics and uneven display may occur.

[0006] Patent Document 1: Japanese Patent Laid-Open No. 7-234410

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention has been made in view of the above circumstances, and its problem is to provide a liquid crystal aligning agent having excellent pretilt angle stability even under a high temperature environment for a long time, and pretilt. To provide a liquid crystal display element with little change in corners and excellent display reliability.

In addition, as the density of pixels in liquid crystal display elements has increased in recent years and the surface structure of the substrate has been increased to three-dimensional (surface irregularities are large), the variation in the rubbing strength in the liquid crystal display surface has become larger than before. In the portion where rubbing is weak, the alignment regulating force of the liquid crystal is weakened, causing a problem that a partial display defect occurs. Therefore, in addition to improving the stability of the pretilt angle, the present invention also provides a liquid crystal aligning agent that does not deteriorate the alignment of the liquid crystal even under weak rubbing conditions, that is, regardless of the rubbing conditions. Make it an issue

Yes

Means for solving the problem

That is, the present invention has the following gist.

(1) A liquid crystal aligning agent containing the following (i) component and (ii) component.

(I) At least one polymer selected from the group consisting of polyamic acid and polyimide (ii) A crosslinkable compound having at least two oxetane groups represented by the following formula [1] in the molecule.

[0009] [Chemical 1]

(2) The liquid crystal aligning agent according to the above (1), wherein the component (B) is a compound represented by the following formula [2].

[0010] [Chemical 2]

(In the formula [2], X represents N, NH, CO, 0, S, SO, Si, cinoresesquioxane, polysiloxa

1 2

Or an organic group having 1 to 20 carbon atoms, and the organic group may contain a heteroatom (N, 0, S, Si). X and X are each independently , Single bond, NH, CO, 0,

twenty three

S, SO, or an organic group having 1 to 20 carbon atoms, which includes a heteroatom (N

2

, 〇, S, Si) may be included Y and Y are each independently a carbon number;

1 2

And m and n each independently represents an integer of 0 to 20, and may contain heteroatoms (N, 0, S, Si). And m + n is an integer from 2 to 20)

(3) The liquid crystal aligning agent according to (1), wherein the component (B) is a compound represented by the following formula [3].

[0011] [Chemical 3]

(In the formula [3], X and X are each independently a single bond, NH, CO, 0, S, SO, or

2 3 2 represents an organic group having 2 to 2 carbon atoms;! -20, and the organic group may contain heteroatoms (N, 0, S, Si). Y and Y are independent of each other. Indicating an organic group with 20 to 20 carbon atoms

1 2

However, the organic group may contain hetero atoms (N, 0, S, Si). Z is a single bond, NH, N (CH), NHCO, CONH, NHCONH, CO, COO , 0, S, SO, CF,

3 2 2

C (CF), Si (CH), OSi (CH), Si (CH) 0, OSi (CH) 0, or carbon number; 10 represents an alkyl group, m and n each independently represent an integer of 0 to 10 and m + n represents an integer of 2 to 10;

(4) The liquid crystal aligning agent according to (1), wherein the component (B) is a compound represented by the following formula [4].

[0012] [Chemical 4]

(In the formula [4], X is NH, N (CH), NHCO, CONH, NHCONH, CO, COO, OC

13

0, 0, S, SO, CF, C (CF), Si (CH), OSi (CH), Si (CH) 0, or OSi (

2 2 3 2 3 2 3 2 3 2

CH) O, Y and Y each independently represent an alkyl group having carbon number;! -10

3 2 1 2

)

(5) The liquid crystal aligning agent according to the above (1), wherein the component (ii) is a compound represented by the following formula [5].

[0013] [Chemical 5]

(In the formula [5], X force S, N, an aliphatic ring having 1 to 20 carbon atoms, an aromatic ring having 1 to 20 carbon atoms, or an alkylene having 1 to 20 carbon atoms, and Y and Y are each carbon. Number ;! ~ 10 alkyl groups

1 2

M and n are integers from 0 to 20, and m + n is an integer from 2 to 20. )

(6) The liquid crystal alignment treatment according to any one of the above (1) to (5), wherein the content of the component (B) is 0.;! To 150 parts by mass with respect to 100 parts by mass of the component (A) Agent.

(7) The liquid crystal aligning agent according to any one of (1) to (6) above, further containing an organic solvent.

(8) The liquid crystal aligning agent according to the above (7), wherein the organic solvent contains 5 to 80% by mass of a solvent having a low surface tension in the total organic solvent.

(9) A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of (1) to (8). (10) A liquid crystal display device having the liquid crystal alignment film according to (9).

The invention's effect

By using the liquid crystal alignment treatment agent of the present invention, a liquid crystal alignment film having excellent pretilt angle stability can be obtained even under a high temperature environment for a long time, and a liquid crystal display element having this liquid crystal alignment film Is excellent in reliability. In addition, the liquid crystal alignment treatment agent of the present invention is particularly useful in applications that require rubbing treatment because the orientation of the liquid crystal does not decrease even under weak rubbing conditions in which the stretchability of the polymer by rubbing is difficult to be inhibited. is there.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] <Component (A): Polyamic acid and polyimide>

The liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of polyamic acid and polyimide. The specific structures of the polyamic acid and polyimide are not particularly limited, and may be, for example, polyamic acid or polyimide contained in a known liquid crystal aligning agent.

The polyamic acid can be easily obtained by reacting tetracarboxylic acid or a tetracarboxylic acid derivative with diamine.

[0016] The method for producing the polyamic acid and polyimide as the component (A) used in the present invention is not particularly limited. In general, a polycarboxylic acid is reacted with a tetracarboxylic acid component selected from tetracarboxylic acids and derivatives thereof and a diamine component consisting of one or more diamine compounds to form a polyamic acid. A method is used in which the polyamic acid is imidized to form a polyimide.

At that time, the polyamic acid obtained is obtained by using a force S to make a monopolymer (homopolymer) or a copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component as raw materials.

Here, tetracarboxylic acid and its derivatives are tetracarboxylic acid, tetracarboxylic acid dihalide, and tetracarboxylic dianhydride. Of these, tetracarboxylic dianhydride is preferred because it has a high reactivity with diamine compounds! /.

[0017] In particular white birch (Pyromellitic acid, 2, 3, 6, 7-Naphthalene tetra-force norebonic acid, 1, 2, 5, 6- 4'-biphenyltetracarboxylic acid, 2, 3, 3 ', 4'-biphenyltetracarboxylic acid, bis (

3,4-dicarboxyphenenole) ether, 3, 3 ', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenenole) sulfone, bis (3,4) —Dicarboxyphenenole) methane, 2,2 bis (3,4 dicarboxyphenenole) propane, 1,1,1,1,3,3,3—hexafluoro-2,2bis (3,4 dicarboxyphene) Ninole) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2, 3, 4, 5 pyridinetetracarboxylic acid, 2, 6 Bis (3,4 dicarboxyphenole) pyridine, 2,2bis [4— (3,4 dicarboxyphenoxy) phenole] propane, 3, 3,4,4, diphenenores norephone Power Norevonic acid, 3, 4, 9, 10-perylene carboxylic acid, 1,3-Didinitro 1, 2, 3, 4— Clobutanetetracarboxylic acid, oxydiphthalanolate norevonic acid, 1, 2, 3, 4-cyclopentane forcenolevonic acid, 1, 2, 3, 4-cyclopentanetetracarboxylic acid, 1, 2, 4 , 5-cyclohexanetetracarboxylic acid, 1, 2

, 3, 4-tetramethyl-1,2,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4, cyclobutanetetraforce norebonic acid, 1,3 dimethinole 1,2,3,4 Tantetrahydronorebonic acid, 1, 2, 3, 4-cycloheptanetetrahydronorebonic acid, 2, 3, 4, 5-tetrahydrofurantetracarboxylic acid, 3,4-dicarboxy 1-cyclohexylsuccinic acid, 2, 3 , 5 Tricanolepoxycyclopentinoleacetic acid, 3, 4 Dicanolepoxy 1, 2, 3, 4 Tetrahydro 1 Naphthalene succinic acid, Bicyclo [3, 3, 0] Octane 2, 4, 6, 8 Tetracarboxylic acid, Bicyclo [ 4, 3, 0] nonane 2, 4, 7, 9 tetracarboxylic acid, bicyclo [4,

4, 0] decane— 2, 4, 7, 9 Tetra-force nolevonic acid, bicyclo [4, 4, 0] decane—2, 4, 8, 1 0 tetracarboxylic acid, tricyclo [6. 3. 0. 0 <2, 6>] Undecane 3, 5, 9, 11—Tetracarboxylic acid, 1, 2, 3, 4 Butanetetracarboxylic acid, Bicyclo [2, 2, 2] Otato 7— 3, 5, 6 Tetracarboxylic acid, tetracyclo [6, 2, 1, 1, 0, 2, 7] dode force — 4,

Examples include tetracarboxylic acids such as 5, 9, and 10 tetracarboxylic acids. Furthermore, these dicarboxylic acid tetrahalides and dianhydrides of tetracarboxylic acids can be mentioned. [0018] Particularly for liquid crystal alignment film applications, alicyclic tetracarboxylic acids and their dianhydrides and their dicarboxylic acid diacid halides are particularly preferred from the viewpoint of transparency of the coating film. , 4-cyclobutanetetracarboxylic acid, 2, 3, 5-tricarboxycyclopentyl acetic acid, 3, 4 dicarboxy 1, 2, 3, 4 tetrahydro 1 naphthalene succinic acid, bicyclo [3, 3, 0] octane 2, 4 6, 8 Tetracarboxylic acids, dihalides of these tetracarboxylic acids, and dianhydrides of tetracarboxylic acids are preferred! /.

[0019] The tetracarboxylic acid and its derivatives exemplified above are used singly or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding characteristics, accumulated charges, etc. in the case of forming a liquid crystal alignment film. It ’s the power to do.

The diamine used for the polyamic acid synthesis reaction is not particularly limited.

[0020] Specifically, p-phenylene diamine, 2, 3, 5, 6 tetramethylolene p-phenylene diamine, 2, 5 dimethyl-p phenylene diamine, m phenylene diamine, 2, 4 dimethylenole m hua Direndiamine, 2,5 Diaminotonolene, 2,6 Diaminotonolene, 2,5 Diaminophenol, 2,4 Diaminophenol, 3,5 Diaminophenol, 3,5-Diaminoben Ziralkanol, 2,4 Diaminobenzil alcohol, 4,6 Diaminoresorenocinol, 4,4'-Diaminobiphenyl, 3, 3, 1-Dimethyl-4,4'-Diaminobiphenyl, 3, 3, -Dimethoxy 4, 4'-diaminobiphenyl, 3, 3, -dihydroxy 4, 4 'diaminobiphenyl, 3, 3, monodicarboxy 4,4'—diaminobiphenyl, 3, 3'—difluoro 4,4'— Biphenyl, 3, 3, Itori 1,4'-diaminobiphenyl, 3, 4, 1-diaminobiphenyl, 3, 3, 1-diaminobiphenyl, 2, 2, 1-diaminobiphenyl, 2, 3'-diaminobiphenyl, 4, 4 '-Diaminodiphenylmethane, 3, 3' -diaminodiphenylmethane, 3, 4 '-diaminodiphenylmethane, 2, 2' -diaminodiphenylmethane, 2, 3 '-diaminodiphenylmethane, 4, 4' -diamino Diphenyl ether, 3, 3'-Diamino diphenylenoate, 3, 4, Diaminodiethanolate, 2, 2, Diaminodiphenol ether, 2, 3'-Diaminodiphenyl ether, 4, 4 'Sulfo Dildianiline, 3,3, monosulfonyldianiline, bis (4-aminophenol) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane Emissions, dimethyl chromatography bis (3-Aminofue two Honoré) silane, 4, 4 'Chiojianirin, 3, 3' Chiojianirin, 4, 4 'Jiaminojifue two Noreamine, 3, 3'-diaminodiphenylamine, 3, 4'-diaminodiphenylamine, 2, 2'-diaminodiphenylamine, 2, 3'-diaminodiphenylamine, N-methyl (4 , 4'-diaminodiphenyl) amine, N-methyl (3,3, -diaminodiphenyl) amine, N-methyl (3,4,2-diaminodiphenyl) amine, N-methyl (2,2, -diaminodiphenyl) amine ) Amin, N-methinole (2,3'-diaminodiphenenole) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene,

2, 2'-Daminobenzophenone, 2,3'-Daminobenzophenone, 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-aminophenolinole) ethane, 1,2 Bis (3 1,3-bis (4-aminophenol) propane, 1,3-bis (3-aminophenylene) propane, 1,4-bis (4-aminophenol) butane, 1, 4 —Bis (3-aminophenol) butane, bis (3,5-deethyl-4-aminophenol) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene 1, 4-bis (4-aminophenole) benzene, 1,3-bis (4-aminophenolino) benzene, 1,4-bis (4-aminobenzinole) benzene, 1,3-bis (4-aminophenoxy) benzene, 4, 4 '-[1,4-phenolate Bis (methylene)] dianiline, 4, 4,-[1,3-Fenylenebis (methylene)] dianiline,

3, 4, 1 [1, 4 Phenylylenebis (methylene)] guanylin, 3, 4, 1 [1, 3—Phenylene bis (methylene)] guanylin, 3, 3, 1 [1, 4 Lenbis (methylene)] dianiline, 3, 3, 1 [1,3-phenylenebis (methylene)] dianiline, 1,4 phenylenebis [(4-aminophenenole) methanone], 1,4 phenylenebis [ (3-aminophenol) methanone], 1,3-phenylenebis [(4-aminophenolinole) methanone], 1,3-phenylenebis [(3-aminophenolinole) methanone], 1,4 Bilenbis (4-aminobenzoate), 1,4-Phenylenebis (3-aminobenzoate), 1,3-Phenylenebis (4-aminobenzoate), 1,3-Phenylenebisbis (3-aminophenol) Zoate), bis (4-aminophenol) terephthalate, bis (3-aminophenol) ) 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, I (1,4 fuyure ) Bis (3-aminobenzamide), N, N '-(l, 3-phenylene) bis (3-aminobenzamide), N, N, monobis (4-aminophenyl) terephthalamide, N , N, monobis (3-aminophenyl) terephthalamide, N, N, monobis (4-aminophenyl) isophthalamide, N, N, —bis (3 aminophenyl) isophthalamide, 9, 10 bis (4 aminophenyl) ) Anthracene, 4, 4'-bis (4 aminophenoxy) diphenyl sulfone, 2, 2 'bis [4— (4-aminophenoxy) phenol] propane, 2, 2, monobis [4— (4 aminophenoxy) Phenyl] hexafluoropropane, 2,2,1-bis (4-aminominophenole) hexafluoropropane, 2,2,1bis (3-aminophenoxy) hexafluoropropane, 2, 2 , Bis (3 amino-4 methylphenino ) Hexafluoropropane, 2, 2, 1 bis (4 aminophenol), bread, 2, 2, 1 bis (3 aminophenol) propane, 2, 2, 1 bis (3 amino-4-methylphenyl) ) Propane, 3,5-Diaminobenzoic acid, 2,5-Diaminobenzoic acid, 1,3-bis (4 aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4bis (4 aminophenoxy) ) Butane, 1,4 bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) Xanthone, 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 one (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, etc .; Cycloaliphatic diamines such as (4 aminocyclohexyl) methane, bis (4 amino-3-methylcyclohexyl) methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6 diamino Hexane, 1,7 Diaminoheptane, 1,8-Diaminooctane, 1,9-Diaminononane, 1,10 Diaminodecane, 1,11-Diaminoundeca And aliphatic diamines such as 1,12-diaminedodecane.

Further, diamines having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a complex ring, and a macrocyclic substituent comprising them in the diamine side chain can be exemplified. Ingredients Specifically, diamines represented by the following formulas [A1] to [A20] can be exemplified. _C [0022] [Chemical Formula 6]

[A4] [A 5]

(In the formulas [A1] to [A5], R represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)

[0023] [Chemical 7]

(In the formulas [A6] to [A9], R is CO ○, OC ○, C〇NH, NHCO, CH, ○, CO, or

twenty two

NH represents R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkyl group)

[Chemical 8]

(In the formula [A10] and [Al l], R represents 〇, OCH, CH〇, COOCH, or CHOC〇〇.

Four ?. ? . R represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, or a fluorine-containing alkyl group.

Five

Group or fluorine-containing alkoxy group)

[Chemical 9]

(In the general formulas [A12] to [A14], R represents COO, OCO, CONH, NHCO, COOCH, C

6 2

H OCO, CH 0, OCH, or CH, R is alkyl having 1 to 22 carbon atoms

2 2 2 2 7

Group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group)

[Chemical 10]

(In the formulas [A15] and [A16], R represents COO, OCO, CONH, NHCO, COOCH, CH

8 2

OCO, CH 0, OCH, CH, 0, or NH, R is a fluorine group, cyan group, trif

2 2 2 2 9

Fluoromethyl group, nitro group, azo group, formyl group, acetyl group, acetoxy group, hydroxyl group, Or a carboxyl group)

[0027] [Chemical 11]

Furthermore, diaminosiloxanes represented by the following formula [A21] can also be mentioned.

[0028] [Chemical 12]

H ₂ N— iCH ₂ ) 3- -Si-0 + -Si— iCH ₂ ) ₃ -H ₂ [A 2 1] (In the formula [A21], m represents an integer of! -10)

The above-mentioned jamines can be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.

[0029] Use of a raw material having a hydroxyl group or a carboxyl group among the above-described raw materials for synthesizing a polyamic acid can increase the reaction efficiency between the polyamic acid or polyimide and a crosslinkable compound described later. Specific examples of such raw materials include 2,5 diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzol alcohol, 2,4 diaminophenol. Nyl alcohol, 3,3'-dihydroxy 4,4'-diaminobiphenyl, 3,3'-dicarboxy 4,4'-diaminobiphenyl, 3,5-diaminobenzoic acid, 2,5 diaminobenzoic acid, formula [A22 ] To [A25] and the like.

[0030] [Chemical 13]

(In the formulas [A22] to [A25], R represents COO, OCO, CONH, NHCO, CH, 0, CO, or Represents NH)

[0031] [Chemical 14]

(In the formulas [A26] and [A27], R represents COO, OCO, CONH

11, NHCO, COOCH

2, C

H represents O OCO, CH 0, OCH, CH, 0, or NH, and R represents a hydroxyl group or a carboxy group.

2 2 2 2 12

(Indicates a synole group)

[0032] The organic solvent used for synthesizing the polyamic acid is not particularly limited as long as the produced polyamic acid can be dissolved. Specific examples include N, N dimethylenoformamide, N, N dimethylacetamide, N methyl 2-pyrrolidone, N methylcaprolatatam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ Butyrolatatone, isopropyl alcohol, methoxymethyl pentanol mononole, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethino ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl bitanol, ethino recanole bittone, ethylene glycol Ethylene glycol mononomonoacetate, ethylene glycol monoisopropinoreateolate, ethylene glycol monobutinoleate tenole, propylene glycolate, Pyreneglycol Monoacetate, Propylene Glycol Nole Monomethinoateol, Propylene Glycololate tert Butinoleetenole, Dipropylene Glycol Monomethyl Ether, Diethylene Glycol, Diethylene Glycol Monoacetate, Diethylene Glycolno Resin Methylenoate Ethanol, Dipropylene Glycol Nore Monoacetate Monomethinoreethenole, Dipropyleneglycolenomonomethinoreatenore, Dipropyleneglycol Cole monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monomono propinoate 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, dihexinole Ethereal, di-xane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, milk Ethyl acetate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, 3-methoxypropion Examples thereof include ethyl acetate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Further, even a solvent that does not dissolve the polyamic acid may be used by mixing with the above solvent within a range where the produced polyamic acid does not precipitate. In addition, since water in the organic solvent inhibits the polymerization reaction and further causes the resulting polyamic acid to hydrolyze, it is preferable to use a dehydrated and dried organic solvent as much as possible.

As a method of reacting tetracarboxylic acid and its derivative with diamine in an organic solvent when synthesizing polyamic acid, the solution in which diamine is dispersed in an organic solvent is stirred, and the tetracarboxylic acid and dicarboxylic acid are stirred. A method in which the derivative is added as it is or after being dispersed or dissolved in an organic solvent, and conversely, a method in which diamine is added to a solution in which tetracarboxylic acid and its derivative are dispersed or dissolved in an organic solvent, tetracarboxylic acid and its Examples thereof include a method of alternately adding a derivative and diamine. Any of these methods may be used. In addition, when tetracarboxylic acid and its derivatives or diamines are composed of a plurality of types of compounds, they may be reacted in a premixed state or individually, or they may be reacted individually, and further reacted individually. May be mixed to form a high molecular weight product. [0034] The temperature at which the polyamic acid is synthesized is a force capable of selecting an arbitrary temperature of -20 ° C to 150 ° C, and preferably -5 ° C to 100 ° C. Also, the reaction can be performed at any concentration. If the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the reaction solution becomes too viscous and uniform stirring is difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction may be performed at a high concentration, and then an organic solvent may be added.

[0035] In the synthesis of the polyamic acid, the ratio of the number of moles of the diamine component to the number of moles of the tetracarboxylic acid and its derivative is 0.8 to 1.2; A force of 1 is preferable. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.

As a method for imidizing polyamic acid, heat imidization by heating, catalyst imidization using a catalyst is generally used, catalyst imidation force S in which an imidization reaction proceeds at a relatively low temperature, S It is preferable that the molecular weight of the resulting polyimide does not decrease.

[0036] Catalytic imidation can be performed by stirring polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is 120 to 250 ° C, preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization proceeds, but if it is too high, the molecular weight of the polyimide may decrease. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times that of the amic acid group, and the amount of the acid anhydride is !! to 50 mol times, preferably 3 to 30 mole times. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it is difficult to completely remove the reaction after the reaction is completed.

[0037] 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 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.

[0038] The organic solvent is not limited as long as it dissolves the polyamic acid. Specific examples include N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolatatam, dimethylsulfoxide, tetramethyl. Urea, dimethinolesnorephone, hexamethinoresnorexoxide, γ-butyrolatatone, etc. The imidization rate by catalytic imidation is controlled by the control force S by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0039] The produced polyimide can be obtained by charging the reaction solution into a poor solvent and collecting the produced precipitate. In this case, the poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polyimide deposited in a poor solvent and filtered can be powdered by filtering at normal temperature or reduced pressure at room temperature or by heating. The polyimide powder can also be purified by repeating the steps of dissolving the polyimide powder in an organic solvent and reprecipitating 2 to 10 times. It is preferable to carry out this purification process when impurities cannot be removed by a single precipitation recovery operation!

Yes

[0040] The molecular weight of the specific polyimide used in the present invention is not particularly limited, but is preferably 2,000 to 200,000 in terms of weight average molecular weight from the viewpoints of handling and stability of characteristics when a film is formed, and more Preferably, it is 4,000-50,000. It is determined by molecular weight (also GPC (genore- nomi-emission chromatography).

[0041] <Component (ii): Specific crosslinkable compound>

In addition to the polymer component described above, the liquid crystal aligning agent of the present invention has the following formula in the molecule.

And a crosslinkable compound having at least two oxetane groups represented by [1] (hereinafter referred to as a specific crosslinkable compound).

[0042] [Chemical 15]

[0043] It is known that an oxetane group reacts with a carboxyl group or a hydroxyl group in the presence of heat or an acid catalyst. Therefore, a specific crosslinkable compound reacts with a carboxyl group or a hydroxyl group contained in polyamic acid or polyimide to form a film crosslinked between polymers. further, The oxetane group causes a self-polymerization reaction in addition to the reaction with a carboxyl group or a hydroxyl group. In particular, since the oxetane group has a higher nucleophilicity than the epoxy group, a polymer having a high final conversion and a high degree of polymerization can be obtained. That is, the liquid crystal alignment film obtained by using the liquid crystal aligning agent of the present invention is a film having high heat resistance due to a polymer formed by cross-linking between polymers and self-polymerization of oxetane groups.

[0044] Further, since the oxetane group has a four-membered ring structure, when it reacts with a carboxyl group or a hydroxyl group and when it self-polymerizes, a methylene group is present at the bonding site compared to an epoxy group that has a three-membered ring structure One more. Therefore, the film obtained from the liquid crystal aligning agent of the present invention has high toughness when stretched as compared with a film using an epoxy-based crosslinkable compound, so that the stretchability of the polymer by rubbing is inhibited. It is hard to be done.

Therefore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is more stable to the heat of the pretilt angle than the liquid crystal alignment film containing no crosslinkable compound or the liquid crystal alignment film containing an epoxy crosslinkable compound. And the liquid crystal orientation does not deteriorate even under weak rubbing conditions.

In the liquid crystal aligning agent of the present invention, the number of oxetane groups possessed by the specific crosslinkable compound is not particularly limited as long as it is 2 or more, but is preferably 2 to 50, more preferably 2 ~ 20.

Further, the specific structure of the specific crosslinkable compound is not particularly limited, and examples thereof include a compound represented by the following formula [2].

[0046] [Chemical 16]

In the formula [2], X represents N, NH, CO, 0, S, SO, Si. Cinolesesquioxane, polysiloxa

1 2

Or an organic group having 1 to 20 carbon atoms, and the organic group may contain a heteroatom (N, 0, S, Si). Furthermore, the organic group having 1 to 20 carbon atoms of X may include an organic group having a cyclic structure. Specifically, cyclopropane ring, cyclobutane ring, cyclo Pentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cyclohe Ptadecane ring, cyclodecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene Ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidin ring Quinoline ring, pyrazoline ring, isoquinoline ring, force rubazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, virazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthorin Ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, atalidine ring, oxazole ring, piperazine ring, piperidine ring, dioxane ring, morpholine ring, azepine ring, diazepine ring, naphthyridine ring , Phenazine ring and phthalazine ring. X and X are each independently a single bond, NH, CO, 0, S, SO, or charcoal.

2 3 2 represents an organic group having a prime number !!-20, and the organic group may contain a heteroatom (N, 0, S, Si).

[0048] Y and Y are each independently an organic compound having a carbon number;! To 20, preferably 1 to 15 carbon atoms.

1 2

In the organic group, a hetero atom (N, 0, S, Si) may be contained.

m and n each independently represents an integer of 0 to 20, preferably 0 to 15; and m + n represents an integer of 2 to 20, preferably 2 to 15;

In the specific crosslinkable compound represented by the formula [2], X force N, NH, CO 2, 0, silsesquioxane, polysiloxane, or an organic group having 1 to 10 carbon atoms is preferable. The organic group may contain heteroatoms (N, O), and the carbon number of X;! To 10 organic groups include cyclohexane ring, benzene ring, naphthalene Ring, fluorene ring, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, force rubazole ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, or quinoxaline ring An organic group having may be contained. In addition, X and X, Each independently NH, CO, COO, OCO, 0, CONH, or NHCO, and Y and Ύ are each independently an alkyl group having 1 to 10 carbon atoms, m, n Respectively

2

Independently, it represents an integer of 0 to 20, and m + n is an integer of 2 to 20.

[0050] In the formula [2], when X is silsesquioxane, examples thereof include the general formula [

Examples include a structure selected from S 1] to [S4].

[0051] [Chemical 17]

[s]

S OlLO / LOOZdT / lDd zz 8 ^ 8CS0 / 800Z OAV In the formula [2], when X is polysiloxane, examples of the polysiloxane

2

Includes a polysiloxane having at least one structure selected from the group consisting of general formulas [P 1], [P2], [P3], and [P4].

[Chemical 18]

R, R, R, R and R in the formulas [P 1] to [P4] are each independently a hydrogen atom or a hydroxyl group

1 2 3 4 5

, A group having 1 to 10 carbon atoms, a group selected from an alkyl group, an alkoxy group, an aliphatic ring group, or an aromatic ring group.

[0053] Preferable specific examples of the formula [2] include structures of the following formulas [3] to [8].

[0054] [Chemical 19]

In the formula [3], X and X are each independently a single bond, NH, CO, 0, S, SO, or

2 3 2 Indicates an organic group having 2 to 2 carbon atoms,! ~ 20, and the organic group may contain a heteroatom (N, 0, S, Si). Y and Y are independent of each other. Carbon number;! ~ 20, preferably charcoal

1 2

A prime number;! To 15 represents an organic group, and the organic group may include a heteroatom (N, 0, S, Si). Z is a single bond, NH, N (CH), NHCO, CONH, NHCONH, CO, C 00, 0, S, SO, CF, C (CF), Si (CH), OSi (CH), Si (CH) 0, OSi (C

2 2 3 2 3 2 3 2 3 2

H) 0 or an alkyl group having 1 to 10 carbon atoms; m and n are each independently 0 to 5

3 2

, Preferably an integer of 0 to 3, and m + n is an integer of 2 to 10, preferably an integer of 2 to 6.

[0056] In the specific crosslinkable compound represented by the formula [3], X and X forces are preferred.

2 3 Each independently NH, CO, COO, OCO, 0, CONH, or NHCO, Z force single bond, CH, C (CH), NH, N (CH), NHCO, CONH, CO, COO, 0, SO,

2 3 2 3 2

C (CF), Si (CH), OSi (CH), Si (CH) 0, OSi (CH) 0, or carbon number;

3 2 3 2 3 2 3 2 3 2

An alkyl group having 5 and Y and Y each independently having 1 to 10 carbon atoms;

1 2

M and n are each independently an integer of 0 to 5, preferably an integer of 0 to 3, and m + n is an integer of 2 to; an integer of 10 and preferably an integer of 2 to 6.

[0057] [Chemical 20]

In the formula [4], X is MH, N (CH), NHCO, CONH, NHCONH, CO, COO, O

13

CO, 0, S, SO, CF, C (CF), Si (CH), OSi (CH), Si (CH) 0, or OS

2 2 3 2 3 2 3 2 3 2

i (CH 3) 2 O, Y and Y each independently represent an alkyl group having carbon atoms;! -10

3 2 1 2

An alkyl group having 1 to 5 carbon atoms is preferred.

In the specific crosslinkable compound represented by the formula [4], X 1 NH, N (CH

13

), NHCO, CONH, CO, COO, OCO, 0, SO, C (CF), Si (CH), OSi (C

2 3 2 3 2

H), Si (CH) 0, or OSi (CH) O, and Y and Y are each independently

3 2 3 2 3 2 1 2

It is a 1 to 10 prime alkyl group.

[0059] [Chemical 21]

X in the formula [5] is N, an aliphatic ring having 1 to 20 carbon atoms, an aromatic ring having 1 to 20 carbon atoms, or charcoal An alkylene having 1 to 20 prime atoms, preferably N, an aliphatic ring having 1 to 15 carbon atoms, an aromatic ring having 1 to 15 carbon atoms, or an aromatic ring having 1 to 15 carbon atoms, or an alkylene having 1 to 15 carbon atoms, more preferably , X is N, an aliphatic ring having 1 to 10 carbon atoms, an aromatic ring having 1 to 10 carbon atoms, or an alkylene having 1 to 10 carbon atoms.

Y and Y in the formula [5] each represents an alkyl group having! To 10 carbon atoms, preferably,

1 2

Each is an alkyl group having 1 to 5 carbon atoms.

M and n in the formula [5] represent an integer of 0 to 20, and m + n is an integer of 2 to 20. Preferably, m and n are integers from 0 to 15, and m + n is an integer from 2 to 15. More preferably, m and n represent an integer of 0 to 0, and m + n is an integer of 2 to 10;

Thus, preferred combinations of X, Y, Y, m, and n are as follows.

1 1 2

[0060] In Formula [5], X, N, an aliphatic ring having 1 to 20 carbon atoms, an aromatic ring having 1 to 20 carbon atoms, or an alkylene having 1 to 20 carbon atoms, and Y and Y are each carbon. Number ;! ~ 10 alkyl groups

1 2

M and n are integers from 0 to 20, and m + n is an integer from 2 to 20.

Preferably, X is N, an aliphatic ring having 1 to 15 carbon atoms, an aliphatic ring having 1 to 15 carbon atoms, an aromatic ring having 15 carbon atoms or an alkylene having 1 to 15 carbon atoms, and Y and Y each have 1 to 5 alkyl

1 2

M, n is an integer from 0 to 15; and m + n is an integer from 2 to 15;

More preferably, X is N, an aliphatic ring having 1 to 10 carbon atoms, an aliphatic ring having 1 to 10 carbon atoms, an aromatic ring having 10 carbon atoms or an alkylene having 1 to 10 carbon atoms, and Y and Y are each a carbon number. ;! ~ 5 al

1 2

M, n is an integer from 0 to 10 and m + n is an integer from 2 to 10;

Specific examples of the aliphatic ring having 1 to 20 carbon atoms and the aromatic ring having 1 to 20 carbon atoms in X above are given below.

[0061] Examples of the aliphatic ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclodecane ring, a cyclododecane ring, and a cyclotridecane. Ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, norbornene ring And adamantane ring.

[0062] Examples of the aromatic ring include decahydronaphthalene ring, benzene ring, naphthalene ring, tetrahydro Naphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, azole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline Ring, force rubazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, virazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, cinnoline ring, phenanthorin ring, indole ring, quinoxaline ring, Benzothiazole ring, phenothiazine ring, oxadiazole ring, atalidine ring, oxazole ring, piperazine ring, piperidin ring, dioxane ring, morpholine ring, azepine ring, diazepine ring, naphthyridine ring, phenazine , And a phthalazine ring.

Among these, preferably, a cyclobutane ring, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, an anthracene ring, a pyrrole ring, an imidazole ring, an oxazole ring , Thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, canolevazole ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, piperazine ring, piperidine ring . More preferably, a cyclohexane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, pyrrole ring, imidazole ring, pyridine ring, pyrimidine ring, canolebazole ring, pyridazine ring, triazine ring, triazol ring. Ring, pyrazine ring, benzimidazole ring, piperazine ring, piperidine ring.

[0064] [Chemical 22]

In formula [6], Y and Y are each independently an alkyl group having 1 to 10 carbon atoms, preferably

1 2

An alkyl group having 1 to 5 carbon atoms is shown, and n is an integer of 1 to 10, preferably an integer of 1 to 5.

[0065] [Chemical 23]

In the formula [7], Y and それぞれ are each independently an alkyl group having from 10 to 10 carbon atoms, preferably

1 2

A C1-C5 alkyl group is shown, (eta) is an integer of 1-10, Preferably an integer of 1-5 is shown.

[Chemical 24]

In formula [8], Υ and Υ are each independently an alkyl group having 1 to 10 carbon atoms, preferably carbon

1 2

A prime number is an alkyl group having 1 to 5, and η is an integer of 1 to 10, preferably an integer of 1 to 5. More specific specific crosslinkable compounds include compounds of the formulas [9] to [; 19].

[Chemical 25]

[0068] [Chemical 26]

[0069] [Chemical 27]

The said compound is an example of a specific crosslinkable compound, It is not limited to these. Further, the specific crosslinkable compound contained in the liquid crystal aligning agent of the present invention may be one kind or a combination of two or more kinds.

[0070] (Liquid crystal aligning agent)

In the liquid crystal aligning agent of the present invention, the content of the component (B) (specific crosslinkable compound) is 0. with respect to 100 parts by mass of the component (A) (polymer component) made of polyamic acid and / or polyimide. It is more preferably 0.;! To 100 parts by mass in order that a crosslinking reaction that preferably proceeds to 150 parts by mass proceeds to produce the desired film curability and does not deteriorate the orientation of the liquid crystal. , In particular;! ~ 50 parts by weight.

[0071] The liquid crystal aligning agent of the present invention is not particularly limited, but it is usually necessary to form a uniform thin film of 0.01 to 1.0 m on the substrate when preparing the liquid crystal alignment film. Therefore, the coating solution preferably contains an organic solvent that dissolves these components in addition to the components (A) and (B). When the liquid crystal aligning agent of the present invention contains the organic solvent, from the viewpoint of forming a uniform thin film by coating, the content of the organic solvent is liquid crystal alignment. In the treatment agent, it is preferably 90 to 99% by mass, more preferably 92 to 97% by mass. On the other hand, the content of component (A) is preferably 0.4 to 9.9% by mass, particularly preferably 0.5 to 9.9% by mass, and the content of component (B) is preferably 0. ;! ~ 9.6 mass%, particularly preferably 0.;! ~ 9.5 mass%. These contents can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.

[0072] Specific examples of the organic solvent to be contained in the liquid crystal aligning agent of the present invention include organic solvents used in the above-described synthesis reaction of polyamic acid. Particularly preferred are N 2, N dimethylformamide, N, N dimethylacetamide, N methyl 2-pyrrolidone, dimethyl sulfoxide, and γ-butyrolatatone. These organic solvents may be used alone or in combination of two or more.

[0073] In addition, in an organic solvent, for the purpose of improving the uniformity of the coating film, ethilce mouth solve, butyno cerero sonoreb, ethinorecanolebitonore, butinorecanolebitonore, diethyleneglyconoresi Ethenoleethenore, Diethyleneglycolenomethinoretinotenole, Diethyleneglycolenoremo Nobuchinoleetenore, Ethinorecanolebitonoreacetate, Ethyleneglycolanol, Ethyleneglycolmonohexylether, 1-methoxy-2- Propanol, 1 Ethoxy-2-Prono Norole, 1-Butoxy-1-2-Prono Norole, 1-Phenoxy 2-Prono Norole, Propyrendalol Monoacetate, Propylene Glycol Diacetate, Propylene Glycol Monore 1 Monomethinoreate Nore 2 —Acetate, propylene glycol Nole 1-monoethyl chinoleatenole 2-acetate, dipropylene glycolenole, dipropyleneglycololemonomethinoleatenore, dipropyleneglycolenolechinenoleatenore, 4-hydroxy-4-methyloyl 2-pentanone, 2- (2-ethoxy It is preferable to contain a solvent having a low surface tension, such as propoxy) propanol, methyl lactate ester, lactate ester, lactate η propyl ester, lactic acid η butyl ester, lactate isoamyl ester. These solvents are usually used alone or in combination of two or more. Since these solvents generally have a low ability to dissolve polyamic acid or polyimide, it is preferably 80% by mass or less, more preferably 60% by mass or less in the organic solvent. Further, if the improvement of the uniformity of the coating is expected, 5% by mass or more in the organic solvent is preferable, and 20% by mass or more is preferable. [0074] The liquid crystal aligning agent of the present invention contains the component (A), the component (B), and the organic solvent as well as the additive component as long as the effect of the present invention is not impaired. You can be! / Examples of the additive component include a compound for improving the adhesion between the liquid crystal alignment film and the substrate, and a surfactant for improving the flatness of the coating film.

[0075] Specific examples of the compound that improves the adhesion between the coating film and the substrate include the following. For example, 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 2-Aminopropyl trimethoxysilane, 2-Aminopropyltriethoxysilane, N- (2 Aminoethyl) 3 Aminopropyl Trimethoxysilane, N— (2 aminoethyl) -3 raidpropyltriethoxysilane, N ethoxycarbonyl 3-aminoaminotrimethoxysilane, N-ethoxycarbonyl 3-aminopropyltriethoxysilane, N trie Toxisilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10 trimethoxysilyl-1,4,7 triazadecane, 10 triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-1,3 6-diazanonyl acetate, 9-triethoxysilyl-3,6 —Diazanonyl acetate, N benzil 3-Naminobenzyl trimethoxy silane, N-benzyl trifluoro 3-Namino propyl triethoxy silane, N-phenyl nitro 3-Namino phen tri silane, N phenyl 1 3 -Functional silane-containing compounds such as aminopropyltriethoxysilane, N-bis (oxyethylene) 3-aminomino trimethoxysilane, N-bis (oxyethylene) 3-aminopropyltriethoxysilane From the standpoint that the effect of improving the adhesion can be obtained and that the orientation of the liquid crystal is not deteriorated, 0.;! To 30 parts by mass is preferable with respect to 100 parts by mass of component (A). More preferably, it is 1-20 mass parts, Especially it is 1-; 10 mass parts.

[0076] Examples of the surfactant for improving the flatness of the coating film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafuk F171, F173, R-30 (above, manufactured by Dainippon Ink), Florad FC430, FC431 ( (Made by Sumitomo 3EM), Asahi Guard AG710, Surflon S-382, SC101, SC 102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Shishiko). The ratio of these surfactants to be used is preferably 0.0;! To 2 parts by mass, more preferably 0.0;! To 1 part by mass with respect to 100 parts by mass of the polymer component.

[0077] <Liquid crystal alignment film / liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like. .

In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate; a plastic substrate such as an acrylic substrate or a polycarbonate substrate; In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed from the viewpoint of simplifying the process. In the case of a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum can be used.

[0078] The method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used according to the purpose.

Firing after applying the liquid crystal aligning agent can be performed at any temperature of 100 to 350 ° C, preferably 120 to 300 ° C, more preferably 150 to 250 ° C. This firing can be performed with a hot plate, a hot-air circulating furnace, an infrared furnace, or the like.

[0079] If the thickness of the coating 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. , More preferably 10 to! OOnm. When the liquid crystal is aligned horizontally or tilted, the baked coating film is treated with rubbing or irradiation with polarized ultraviolet rays.

[0080] 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 alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method. It is.

To give an example of liquid crystal cell preparation, a pair of substrates with a liquid crystal alignment film is prepared. A method of spraying a spacer on the liquid crystal alignment film of one substrate and bonding the other substrate so that the surface of the liquid crystal alignment film is on the inside, and injecting liquid crystal under reduced pressure, or sealing Examples thereof include a method in which a liquid crystal is dropped on the surface of the liquid crystal alignment film on which a spacer is dispersed and then the substrate is bonded and sealed. The thickness of the spacer at this time is preferably;! -30 m, more preferably 2--10 μm.

In this way, the liquid crystal display element produced using the liquid crystal aligning agent of the present invention can be a liquid crystal display device having excellent pretilt angle stability, including a TN element, STN element, TFT liquid crystal element, Furthermore, it is useful for a vertical alignment type liquid crystal display element.

Example

[0081] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention should not be construed as being limited thereto.

The abbreviations of the compounds used in this example are as follows.

(Tetracarboxylic dianhydride)

CBDA: 1, 2, 3, 4 cyclobutane tetracarboxylic dianhydride

BODA: Bicyclo [3, 3, 0] octane 2, 4, 6, 8 Tetracarboxylic dianhydride

[0082] [Chemical 28]

C B D A B O D A

(Jiamin)

p— PDA: p

DBA: 3, 5—Diaminobenzoic acid

DADPA: 4, 4'-diaminodiphenylamine

AP18: 4- (octadecyloxy) 1,3 phenylenediamine

PCH: 1,3-Diamino 4 [4 (4-heptylcyclohexyl) phenoxy] benze N

[0083] [Chemical 29]

p— PDA DBA

PCH

Crosslinkable compound) Oxetane (A): 〇 Dc-221 (manufactured by Toa Gosei Co., Ltd.) Oxetane (B): OX— SQ— H (Manufactured by Toa Gosei Co., Ltd.) Oxetane (C): OX— SC (manufactured by Toa Gosei Co., Ltd.)

[0084] [Chemical 30]

Oxetane B (OX-SQ-H)

Oxetane C (OX-SC)

(Epoxy-based crosslinkable compound)

Epoxy A: YH-434L (manufactured by Tohto Kasei)

Epoxy B: Epolide GT-401 (4-functional alicyclic epoxy resin) (manufactured by Daicel Chemical Industries); modified with epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) ε

[Chemical 31]

Epoxy A (YH-4 3 4 L)

(Organic solvent)

NMP: N-Methyl-2-pyrrolidone

BCS: Butyl Seguchi Solve

The molecular weight of polyimide in the synthesis example is

Measurement was carried out as follows using a chromatography (GPC) apparatus (SSC-7200) and a column (KD-803, KD-805) manufactured by Shodex.

Column temperature: 50 ° C

Eluent: N, N'-dimethylformamide (as additive, lithium bromide-hydrate (LiBr • HO) 30mmol / L, phosphoric acid. Anhydrous crystals (o-phosphoric acid) 30mmo Flow rate: 1.0ml / Min

Standard samples for preparing calibration curves: TSK standard polyethylene oxide (molecules !: approx. 9000,000, 150,000, 100,000, 30,000) manufactured by Tosohichi Co., Ltd. and polyethylene glycol (molecular weight approx. ).

The imidation ratio of polyimide in the synthesis example was measured as follows. Put 20 mg of polyimide powder into an NMR sample tube (NMR sampling tube standard φ5 mm, manufactured by Kusano Kagaku Co., Ltd.) and mix with deuterated dimethyl sulfoxide (DMSO-d, 0.05% TMS)

6

) 0.53 ml was added and completely dissolved by sonication. With this solution in the tube, proton NMR at 500 MHz was measured with a Japan Electronic Datum NMR measuring instrument (JNW-ECA500). The imidization rate is based on protons derived from structures that do not change before and after imidation. The proton peak integrated value and the proton peak integrated value derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm were obtained by the following formula.

Imidization rate (%) = (1— a-x / y) X IOO

In the above formula, X is the accumulated proton peak value derived from the NH group of the amic acid, y is the accumulated peak value of the reference proton, α is the aprotic group proton of the amic acid in the case of polyamic acid (imidation rate is 0%) 1 This is the ratio of the number of reference protons to one.

(Synthesis Example 1)

CBDA (5.lg, 26.Ommol), p-PDA (2.53g, 23.4mmol), AP18 (0.98g, 2.6 mmol) were mixed in NMP (81.5g) at 25 ° C. The mixture was reacted for 6 hours to obtain a polyamic acid solution (A). The number average molecular weight of this polyamic acid solution (A) was 22000, and the weight average molecular weight was 78900.

(Synthesis Example 2)

CBDA (3.04 g, 15.5 mmol), p—PDA (1.56 g, 14.4 mmol), PCH (0.61 g, 1.6 mmol) were mixed in NMP (22. Og) at 25 ° C. The mixture was reacted for 5 hours to obtain a polyamic acid solution (B). This polyamic acid solution (B) had a number average molecular weight of 25,000 and a weight average molecular weight of 94,000.

(Synthesis Example 3)

BODA (16.9 g, 68 mmol), p-PDA (8. 74 g, 81 mmol), PCH (3.43 g, 9 mmol) were mixed in NMP (100. lg) and reacted at 40 ° C for 3 hours. Thereafter, CBDA (4. lg, 21 mmol) and NMP (52.2 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution (C). The number average molecular weight of this polyamic acid (C) was 20500, and the weight average molecular weight was 76500.

(Synthesis Example 4)

BODA (150.lg, 600mmol), DBA (60.9g, 400mmol), PCH (152.2g, 4OOmmol) were mixed in NMP (1290g) and reacted at 80 ° C for 5 hours, then CBDA ( 38.8 g, 198 mmol) and NMP (320 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution (D). The number average molecular weight of this polyamic acid (D) was 24400, and the weight average molecular weight was 985,000. (Synthesis Example 5)

After adding NMP to the polyamic acid solution (C) (130.3 g) obtained in Synthesis Example 3 and diluting to 6% by mass, acetic anhydride (15.6 g) and pyridine (12. lg) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (1600 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder.

(E) was obtained. The imidation ratio of this polyimide was 54%, the number average molecular weight was 18300, and the weight average molecular weight was 45300.

[0089] (Synthesis Example 6)

After adding NMP to the polyamic acid solution (D) (60.2 g) obtained in Synthesis Example 4 and diluting to 6% by mass, acetic anhydride (3.9 g) and pyridine (49.6 g) were added as imidization catalysts. And reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (7700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder.

(F) was obtained. The imidation ratio of this polyimide was 57%, the number average molecular weight was 23,000, and the weight average molecular weight was 80,200.

(Synthesis Example 7)

After adding NMP to the polyamic acid solution (D) (101.2 g) obtained in Synthesis Example 4 and diluting to 6% by mass, acetic anhydride (21.3 g) and pyridine (16.5 g) were used as imidization catalysts. In addition, the mixture was reacted at 90 ° C for 3 hours. This reaction solution was poured into methanol (1300 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder.

(G) was obtained. The imidation ratio of this polyimide was 81%, the number average molecular weight was 20400, and the weight average molecular weight was 63000.

[0090] (Example 1)

To the polyamic acid solution (A) (6.00 g) obtained in Synthesis Example 1, oxetane (A) (0.1 g), NMP (4.76 g), and BCS (2.53 g) were added and stirred. A liquid crystal aligning agent [1] was obtained. The liquid crystal alignment treatment agent [1] obtained above is spin-coated on the ITO surface of the substrate with 3cm x 4cm ITO electrode, and heat-treated at 80 ° C for 5 minutes and at 230 ° C for 30 minutes to apply polyimide with a film thickness of lOOnm. A membrane was obtained. The coating surface is rubbed with a roll diameter of 120mm and a rayon cloth rubbing device under the conditions of a rotation speed of 70 Orpm, a moving speed of 40mm / sec, and an indentation amount of 0.3mm. A substrate with a liquid crystal alignment film was obtained. Prepare two substrates with a liquid crystal alignment film, sandwich the 50 m spacer with the liquid crystal alignment film surface on the inside, combine them so that the rubbing direction is reversed, and bond the periphery with a sealant. An empty cell was prepared. Liquid crystal ZLI-2293 (manufactured by Merck & Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an antiparallel aligned nematic liquid crystal cell.

[0091] For this liquid crystal cell, the pretilt angle (degrees) at the initial stage after the liquid crystal injection and after the heat treatment at 120 ° C for 5 hours was measured with a pretilt angle measuring device (Model PA S-301, manufactured by ELSICON). ) At room temperature. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal without alignment failure was uniformly aligned in any liquid crystal cell.

[0092] In addition, with respect to a liquid crystal cell manufactured in the same manner as described above except that the indentation amount of the rubbing treatment was set to 0.1 mm, the pre-retinoic angle after the heat treatment at 120 ° C for 5 hours at the initial stage after the liquid crystal injection. Was measured. When the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope under these liquid crystal cells, the liquid crystal without alignment failure was uniformly aligned in any liquid crystal cell.

Table 1 shows the measurement results of the pretilt angle.

[0093] (Example 2)

Oxetane (A) (0.06 g), NMP (4.05 g), and BCS (2.35 g) were added to the polyamic acid solution (A) (6.05 g) obtained in Synthesis Example 1, and the mixture was stirred. An alignment agent [2] was obtained. Using the obtained liquid crystal alignment treatment agent [2], a liquid crystal cell was prepared in the same manner as in Example 1, and the heat treatment was performed at 120 ° C. for 5 hours at the initial stage after the liquid crystal was injected at an indentation amount of 0.3 mm. The subsequent pretilt angle was measured. Regarding the liquid crystal cell in the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal without alignment failure was uniformly aligned in any liquid crystal cell.

[0094] Further, with respect to a liquid crystal cell produced in the same manner as described above except that the amount of push-in was 0.1 mm, the pretilt angle was measured at the initial stage after liquid crystal injection and after heat treatment at 120 ° C for 5 hours. As a result of confirming the alignment uniformity of the liquid crystal cells by observation with a polarizing microscope, the liquid crystal cells were aligned uniformly without any alignment failure. Table 1 shows the measurement results of the pretilt angle.

[Example 3]

To the polyamic acid solution (A) (6.OOg) obtained in Synthesis Example 1, oxetane (B) (0.03 g), NMP (3.61 g), and BCS (2.21 g) were added and stirred to obtain a liquid crystal. An alignment agent [3] was obtained. Using the obtained liquid crystal alignment treatment agent [3], a liquid crystal cell was prepared in the same manner as in Example 1, and heat treatment was performed at 120 ° C. for 5 hours at the initial stage after injecting the liquid crystal at an indentation amount of 0.3 mm. The subsequent pretilt angle was measured. Regarding the liquid crystal cell in the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal without alignment failure was uniformly aligned in any liquid crystal cell.

[0096] Further, with respect to the liquid crystal cell produced in the same manner as described above except that the indentation amount was set to 0.1 mm, the pretilt angle was measured at the initial stage after the liquid crystal injection and after the heat treatment for 5 hours at 120 ° C. As a result of confirming the alignment uniformity of the liquid crystal by observation with a polarizing microscope, the liquid crystal without alignment failure was uniformly aligned in any liquid crystal cell.

Table 1 shows the measurement results of the pretilt angle.

[Example 4]

To the polyamic acid solution (B) (6.OOg) obtained in Synthesis Example 2, oxetane (A) (0.12 g), NMP (3.61 g), and BCS (2.4 g) were added and stirred to obtain a liquid crystal. An alignment agent [4] was obtained.

Using the obtained liquid crystal alignment treatment agent [4], a liquid crystal cell was produced in the same manner as in Example 1, and heat treatment was performed at 120 ° C. for 5 hours at the initial stage after injecting the liquid crystal at an indentation amount of 0.3 mm. The subsequent pretilt angle was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope.

Table 1 shows the measurement results of the pretilt angle.

[Example 5]

To the polyamic acid solution (B) (6.02 g) obtained in Synthesis Example 2, oxetane (B) (0.03 g), NMP (2.41 g), and BCS (2. lOg) were added and stirred. An alignment agent [5] was obtained. The obtained liquid crystal aligning agent [5] was used! /, And a liquid crystal cell was prepared in the same manner as in Example 1, and the initial stage after liquid crystal injection at a rubbing treatment push amount of 0.3 mm at 120 ° C. for 5 hours Heat treatment The subsequent pretilt angle was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal without alignment failure was uniformly aligned in any liquid crystal cell.

Table 1 shows the measurement results of the pretilt angle.

[0099] (Comparative Example 1)

NMP (3.06 g) and BCS (2.12 g) were added to the polyamic acid solution (A) (6.00 g) obtained in Synthesis Example 1 and stirred to obtain a liquid crystal aligning agent [6].

A liquid crystal cell was prepared using the obtained liquid crystal aligning agent [6] in the same manner as in Example 1, and heat treatment was performed at 120 ° C for 5 hours at the initial stage after injecting the liquid crystal at a pushing amount of rubbing treatment of 0.3 mm. The subsequent pretilt angle was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope.

Table 1 shows the measurement results of the pretilt angle.

[0100] (Comparative Example 2)

NMP (2.01 g) and BCS (1.99 g) were added to the polyamic acid solution (B) (6. Olg) obtained in Synthesis Example 2 and stirred to obtain a liquid crystal aligning agent [7].

The obtained liquid crystal alignment treatment agent [7] was used! A liquid crystal cell was prepared in the same manner as in Example 1 and the initial stage after liquid crystal injection at a rubbing treatment push amount of 0.3 mm, at 120 ° C for 5 hours. The pretilt angle after the heat treatment was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope.

Table 1 shows the measurement results of the pretilt angle.

[0101] (Comparative Example 3)

Epoxy (A) (0. l lg), N MP (4. 75 g), and BCS (2.52 g) were added to the polyamic acid solution (A) (6.00 g) obtained in Synthesis Example 1 and stirred. A liquid crystal aligning agent [8] was obtained.

A liquid crystal cell was prepared using the obtained liquid crystal aligning agent [8] in the same manner as in Example 1, and the initial stage after injecting the liquid crystal at a rubbing amount of 0.3 mm, after heat treatment at 120 ° C. for 5 hours. The pretilt angle was measured. In the initial state of this liquid crystal cell! A so-called fluid alignment was observed in which the liquid crystal was aligned in the direction in which the crystals flowed. Furthermore, this flow orientation did not disappear at each stage after the heat treatment, and in addition, a disclination line was generated by the heat treatment. Because of such alignment failure, the pretilt angle of this liquid crystal cell could not be measured.

[0102] Further, the initial tilt after the liquid crystal injection of the liquid crystal cell produced in the same manner as described above except that the push amount was 0.1 mm and the pretilt angle after the heat treatment at 120 ° C for 5 hours were measured. In the state, flow orientation was observed. Even after the heat treatment, the flow orientation did not disappear, and in addition, a discrimination line was generated. Therefore, the pretilt angle could not be measured.

Table 1 shows the measurement results of the pretilt angle.

[0103] (Comparative Example 4)

Epoxy (A) (0.06 g), N MP (4.03 g), BCS (2.34 g) were added to the polyamic acid solution (A) (6.05 g) obtained in Synthesis Example 1 and stirred. A liquid crystal aligning agent [9] was obtained.

Using the obtained liquid crystal alignment treatment agent [9], a liquid crystal cell was prepared in the same manner as in Example 1, and the initial stage after injecting the liquid crystal at a rubbing amount of 0.3 mm, after heat treatment at 120 ° C. for 5 hours. The pretilt angle was measured. In the early liquid crystal cell, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. The liquid crystal with no alignment failure was uniformly aligned, but a disclination line was generated after heating at 120 ° C for 5 hours. did. For this reason, it was impossible to measure the pretilt angle of the liquid crystal cell after heating at 120 ° C for 5 hours.

[0104] Further, the initial tilt after the liquid crystal injection of the liquid crystal cell produced in the same manner as described above except that the indentation amount was 0.1 mm and the pretilt angle after the heat treatment at 120 ° C for 5 hours were measured. In the state, flow orientation was observed. Even after the heat treatment, the flow orientation did not disappear, and in addition, a discrimination line was generated. Therefore, the pretilt angle could not be measured.

Table 1 shows the measurement results of the pretilt angle.

[0105] (Comparative Example 5)

To the polyamic acid solution (A) (6.00 g) obtained in Synthesis Example 1, epoxy (B) (0.06 g), N MP (4.02 g), and BCS (2.35 g) were added and stirred. A liquid crystal aligning agent [10] was obtained. Using the obtained liquid crystal aligning agent [10]! /, A liquid crystal cell was prepared in the same manner as in Example 1, and the initial stage after injecting the liquid crystal at a rubbing amount of 0.3 mm, at 120 ° C. for 5 hours. The pretilt angle after the heat treatment was measured. When the initial liquid crystal cell was observed for the alignment uniformity of the liquid crystal by observation with a polarizing microscope, the liquid crystal without alignment defects was uniformly aligned. After heating at 120 ° C for 1S for 5 hours, a disclination line was generated. Therefore, the pretilt angle of the liquid crystal cell after heating at 120 ° C. for 5 hours could not be measured.

[0106] Further, the initial tilt after the liquid crystal injection of the liquid crystal cell produced in the same manner as described above except that the indentation amount was 0.1 mm and the pretilt angle after the heat treatment at 120 ° C for 5 hours were measured. In the state, flow orientation was observed. Even after the heat treatment, the flow orientation did not disappear, and in addition, a discrimination line was generated. Therefore, the pretilt angle could not be measured.

Table 1 shows the measurement results of the pretilt angle.

[Example 6]

To the polyimide powder (E) obtained in Synthesis Example 5 (2.91 g), ΝΜΡ (17 · lg) was added and stirred at 80 ° C. for 40 hours for dissolution. To this solution, oxetane (A) (0.60 g), ΝΜΡ (12.2 g), and BCS (25.7 g) were added and stirred to obtain a liquid crystal aligning agent [11].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [11] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.

[0108] Further, for the liquid crystal cell produced in the same manner as described above except that the indentation amount was set to 0.1 mm, the pretilt angle was measured at the initial stage after liquid crystal injection and after heat treatment at 120 ° C for 5 hours. As a result of confirming the alignment uniformity of the liquid crystal cells by observation with a polarizing microscope, the liquid crystal cells were aligned uniformly without any alignment failure.

[Example 7]

NMP (18.0 g) was added to the polyimide powder (E) (3.05 g) obtained in Synthesis Example 5, and the temperature was adjusted to 80 ° C. And stirred for 40 hours to dissolve. To this solution, oxetane (A) (0.31 g), NMP (6.65 g), and BCS (28. Og) were added and stirred to obtain a liquid crystal aligning agent [12].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [12] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.

[0110] Further, with respect to the liquid crystal cell produced in the same manner as described above except that the indentation amount was set to 0.1 mm, the pretilt angle was measured at the initial stage after the liquid crystal injection and after the heat treatment at 120 ° C for 5 hours. As a result of confirming the alignment uniformity of the liquid crystal cells by observation with a polarizing microscope, the liquid crystal cells were aligned uniformly without any alignment failure.

Table 1 shows the measurement results of the pretilt angle.

[0111] (Example 8)

To the polyimide powder (E) (3.00 g) obtained in Synthesis Example 5, ΝΜΡ (17.6 g) was added and stirred at 80 ° C. for 40 hours for dissolution. To this solution, oxetane (A) (0.15 g), NMP (5.51 g), and BCS (26.3 g) were added and stirred to obtain a liquid crystal aligning agent [13].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [13] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.

[0112] Further, with respect to the liquid crystal cell produced in the same manner as described above except that the indentation amount was 0.1 mm, the pretilt angle was measured at the initial stage after liquid crystal injection and after heat treatment at 120 ° C for 5 hours. As a result of confirming the alignment uniformity of the liquid crystal cells by observation with a polarizing microscope, the liquid crystal cells were aligned uniformly without any alignment failure.

Table 1 shows the measurement results of the pretilt angle. [0113] (Example 9)

To the polyimide powder (F) obtained in Synthesis Example 6 (3.12 g), 18.4 g was added and stirred at 80 ° C. for 40 hours for dissolution. To this solution, oxetane (A) (0.31 g), NMP (6.80 g) and BCS (28.6 g) were added and stirred to obtain a liquid crystal aligning agent [14].

[0114] A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [14] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.

Table 1 shows the measurement results of the pretilt angle.

[0115] (Example 10)

To the polyimide powder (F) obtained in Synthesis Example 6 (3.04 g), ΝΜΡ (17.9 g) was added and stirred at 80 ° C. for 40 hours for dissolution. To this solution, oxetane (A) (0.15 g), NMP (5.51 g), and BCS (26.6 g) were added and stirred to obtain a liquid crystal aligning agent [15].

A liquid crystal cell was prepared in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [15] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.

Table 1 shows the measurement results of the pretilt angle.

[0116] (Example 11)

NMP (17.5 g) was added to the polyimide powder (G) (2.98 g) obtained in Synthesis Example 7, and dissolved by stirring at 80 ° C. for 40 hours. To this solution, oxetane (A) (0.30 g), NMP (6.61 g), and BCS (27.3 g) were added and stirred to obtain a liquid crystal aligning agent [16].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [16] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Then press the rubbing process The pretilt angle was measured at the initial stage after liquid crystal injection at a depth of 0.3 mm and after heat treatment at 120 ° C for 5 hours. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell. The liquid crystal was uniformly aligned.

Table 1 shows the measurement results of the pretilt angle.

[Example 12]

NMP (17.7 g) was added to the polyimide powder (G) (3. Olg) obtained in Synthesis Example 7, and stirred at 80 ° C. for 40 hours for dissolution. To this solution, oxetane (C) (0.15 g), ΝΜΡ (5.41 g) and BCS (26.3 g) were added and stirred to obtain a liquid crystal aligning agent [17].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [17] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell. The liquid crystal was uniformly aligned.

Table 1 shows the measurement results of the pretilt angle.

[0118] (Comparative Example 6)

To the polyimide powder (E) obtained in Synthesis Example 5 (2.91 g), ΝΜΡ (17 · lg) was added and stirred at 80 ° C. for 40 hours for dissolution. NMP (4.18 g) and BCS (26.3 g) were added to this solution and stirred to obtain a liquid crystal aligning agent [18].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [18] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.

Table 1 shows the measurement results of the pretilt angle.

[0119] (Comparative Example 7) To the polyimide powder (F) (3.05 g) obtained in Synthesis Example 6, ΝΜΡ (17 · 9 g) was added and stirred at 80 ° C. for 40 hours for dissolution. NMP (4.46 g) and BCS (25.4 g) were added to this solution and stirred to obtain a liquid crystal aligning agent [19].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [19] was used and the liquid crystal was changed to MLC-6608 (manufactured by Merck Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.

Table 1 shows the measurement results of the pretilt angle.

[0120] (Comparative Example 8)

NMP (17.7 g) was added to the polyimide powder (G) (3.00 g) obtained in Synthesis Example 7, and stirred at 80 ° C. for 40 hours for dissolution. To this solution, NMP (4.35 g) and BCS (25. lg) were added and stirred to obtain a liquid crystal aligning agent [20].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [20] was used and the liquid crystal was MLC-6608 (manufactured by Merck & Japan). Next, the pretilt angle after the liquid crystal injection at the indentation amount of 0.3 mm and the heat treatment at 120 ° C. for 5 hours was measured. Regarding the liquid crystal cell at the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, there was no alignment failure in any liquid crystal cell.

Table 1 shows the measurement results of the pretilt angle.

[0121] (Comparative Example 9)

To the polyimide powder (F) (3. Olg) obtained in Synthesis Example 6, ΝΜΡ (17.7 g) was added and stirred at 80 ° C. for 40 hours for dissolution. Epoxy (A) (0.60 g), NMP (8.80 g), and BCS (30. Og) were added to this solution and stirred to obtain a liquid crystal aligning agent [21].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [21] was used and the liquid crystal was MLC-6608 (manufactured by Merck & Japan). Next, in the initial stage after injecting the liquid crystal at a pushing amount of rubbing treatment of 0.3 mm, the plethys after the heat treatment at 120 ° C. for 5 hours. The tilt angle was measured. In the initial state of the liquid crystal cell, so-called fluid alignment was observed in which the liquid crystal was aligned in the direction in which the liquid crystal flowed when the liquid crystal was injected. Furthermore, this flow orientation was not canceled at each stage after the heat treatment, and in addition, a discrimination line was generated by the heat treatment. Because of such alignment failure, it was not possible to measure the pretilt angle of this liquid crystal senore.

[0122] Further, the initial tilt after the liquid crystal injection of the liquid crystal cell produced in the same manner as described above except that the indentation amount was 0.1 mm and the pretilt angle after the heat treatment at 120 ° C for 5 hours were measured. In the state, flow orientation was observed. Even after the heat treatment, the flow orientation did not disappear, and in addition, a discrimination line was generated. Therefore, the pretilt angle could not be measured.

Table 1 shows the measurement results of the pretilt angle.

[0123] (Comparative Example 10)

To the polyimide powder (F) (3.00 g) obtained in Synthesis Example 6, ΝΜΡ (17.5 g) was added and stirred at 80 ° C. for 40 hours to dissolve. Epoxy (A) (0.30 g), NMP (6.71 g), and BCS (27.5 g) were added to this solution and stirred to obtain a liquid crystal aligning agent [22].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [22] was used and the liquid crystal was MLC-6608 (manufactured by Merck Japan). Subsequently, the pretilt angle after the heat treatment at 120 ° C. for 5 hours was measured in the initial stage after the liquid crystal injection at a rubbing treatment push amount of 0.3 mm. Regarding the liquid crystal cell in the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal was uniformly aligned with any liquid crystal cell.

[0124] Further, the initial tilt after the liquid crystal injection of the liquid crystal cell produced in the same manner as described above except that the push amount was set to 0.1 mm and the pretilt angle after the heat treatment at 120 ° C for 5 hours were measured. In the state, flow orientation was observed. Even after the heat treatment, the flow orientation did not disappear, and in addition, a discrimination line was generated. Therefore, the pretilt angle could not be measured.

Table 1 shows the measurement results of the pretilt angle.

[0125] (Comparative Example 11) To the polyimide powder (F) (3.03 g) obtained in Synthesis Example 6, ΝΜΡ (17.8 g) was added and stirred at 80 ° C. for 40 hours for dissolution. Epoxy (A) (0.15 g), NMP (5.60 g), and BCS (26.3 g) were added to this solution and stirred to obtain a liquid crystal aligning agent [23].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [23] was used and the liquid crystal was MLC-6608 (manufactured by Merck Japan). Subsequently, the pretilt angle after the heat treatment at 120 ° C. for 5 hours was measured in the initial stage after the liquid crystal injection at a rubbing treatment push amount of 0.3 mm. Regarding the liquid crystal cell in the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal was uniformly aligned with any liquid crystal cell.

[0126] Further, the initial tilt after the liquid crystal injection of the liquid crystal cell produced in the same manner as described above except that the indentation amount was 0.1 mm and the pretilt angle after the heat treatment at 120 ° C for 5 hours were measured. In the state, flow orientation was observed. Even after the heat treatment, the flow orientation did not disappear, and in addition, a discrimination line was generated. Therefore, the pretilt angle could not be measured.

Table 1 shows the measurement results of the pretilt angle.

[Comparative Example 12]

To the polyimide powder (F) obtained in Synthesis Example 6 (2.93 g), ΝΜΡ (17 · lg) was added, and dissolved by stirring at 80 ° C. for 40 hours. Epoxy (B) (0.30 g), NMP (5.50 g), and BCS (25.7 g) were added to this solution and stirred to obtain a liquid crystal aligning agent [24].

A liquid crystal cell was produced in the same manner as in Example 1 except that the obtained liquid crystal aligning agent [24] was used and the liquid crystal was MLC-6608 (manufactured by Merck Japan). Subsequently, the pretilt angle after the heat treatment at 120 ° C. for 5 hours was measured in the initial stage after the liquid crystal injection at a rubbing treatment push amount of 0.3 mm. Regarding the liquid crystal cell in the initial stage and after each heat treatment, the alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. As a result, the liquid crystal was uniformly aligned with any liquid crystal cell.

[0128] Further, the initial tilt after the liquid crystal injection of the liquid crystal cell produced in the same manner as described above except that the indentation amount was 0.1 mm and the pretilt angle after the heat treatment at 120 ° C for 5 hours were measured. In the state, flow orientation was observed. Flow orientation does not disappear even after heat treatment. A discretion line occurred. Therefore, the pretilt angle could not be measured.

Table 1 shows the measurement results of the pretilt angle.

[table 1]

One: Not evaluated

* 1: Flow alignment was observed in the liquid crystal cell by observation with a polarizing microscope.

* 2: Flow alignment and disclination line were observed in the liquid crystal cell by polarizing microscope observation.

* 3: Discrimination lines were observed in the liquid crystal cell by polarizing microscope observation. (Each pretilt angle is an average value obtained by measuring the center of the liquid crystal cell and the upper and lower lcm points.) From the above results, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has a specific cross-linking. In comparison with Examples 1 to 12 containing a reactive compound and a crosslinkable compound! /, Comparative Example;! To 2 and Comparative Examples 6 to 8, the orientation of the liquid crystal was not changed, and The pretilt angle after high-temperature treatment changed by less than 1 degree, and the stability of the pretilt angle was greatly improved. On the other hand, when the epoxy-based crosslinkable compound was used instead of the specific crosslinkable compound in the present invention as in Comparative Examples 3-5 and 9-9; In particular, in these comparative examples, alignment failure occurred when the indentation amount of the rubbing treatment was low.

Industrial applicability

By using the liquid crystal aligning agent of the present invention, a liquid crystal alignment film excellent in the stability of the pretilt angle of the liquid crystal can be obtained. In addition, since the liquid crystal display element having this liquid crystal alignment film has excellent reliability, it is useful for TN elements, STN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2006-297244, filed on November 1, 2006, are hereby incorporated herein by reference. It is something that is incorporated.

Claims

The liquid crystal aligning agent containing the following (A) component and (B) component. Component (A): at least one polymer selected from the group consisting of polyamic acid and polyimide. Component (B): a crosslinkable compound having at least two oxetane groups represented by the following formula [1] in the molecule.

[Chemical 1]

[2] The liquid crystal aligning agent according to claim 1, wherein the component (B) is a compound represented by the following formula [2].

[Chemical 2]

(In the formula [2], X represents N, NH 2 CO 3, 0, S, SO, Si, cinoresesquioxane, polysiloxa

1 2

twenty three

2

, 〇, S, Si) may be included Y and Y are each independently a carbon number;

1 2

[3] The liquid crystal aligning agent according to claim 1, wherein the component (B) is a compound represented by the following formula [3]. [Chemical 3]

1 2

3 2 2

C (CF), Si (CH), OSi (CH), Si (CH) 0, OSi (CH) 0, or carbon number;

3 2 3 2 3 2 3 2 3 2

10 represents an alkyl group, m and n each independently represent an integer of 0 to 10 and m + n represents an integer of 2 to 10;

2. The liquid crystal aligning agent according to claim 1, wherein the component (B) is a compound represented by the following formula [4].

[Chemical 4]

(In the formula [4], X is NH, N (CH), NHCO, CONH, NHCONH, CO, COO, OC

13

0, 0, S, SO, CF, C (CF), Si (CH), OSi (CH), Si (CH) 0, or OSi (

2 2 3 2 3 2 3 2 3 2

3 2 1 2

)

2. The liquid crystal aligning agent according to claim 1, wherein the component (i) is a compound represented by the following formula [5].

[Chemical 5]

(In the formula [5], is N, an aliphatic ring having 1 to 20 carbon atoms, an aromatic ring having 1 to 20 carbon atoms, or alkylene having 1 to 20 carbon atoms, and Y and Y are each a carbon number; ! ~ 10 alkyl groups

1 2

M and n are integers from 0 to 20, and m + n is an integer from 2 to 20. )

[6] The liquid crystal alignment treatment according to any one of claims 1 to 5, wherein the content of the component (B) is 0.;! To 150 parts by mass with respect to 100 parts by mass of the component (A). Agent.

[7] The liquid crystal aligning agent according to any one of [6] to [6], further containing an organic solvent.

8. The liquid crystal aligning agent according to claim 7, wherein the organic solvent contains 5 to 80% by mass of a solvent having a low surface tension in the total organic solvent.

[9] A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 8.

10. A liquid crystal display device having the liquid crystal alignment film according to claim 9.