CN104232106B

CN104232106B - Aligning agent for liquid crystal and its film, liquid crystal display cells and its manufacture method, the polymer containing nitrogenous heteroaromatic and compound

Info

Publication number: CN104232106B
Application number: CN201410216930.0A
Authority: CN
Inventors: 菅野尚基; 植阪裕介; 秋池利之
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2013-06-17
Filing date: 2014-05-21
Publication date: 2017-12-12
Anticipated expiration: 2034-05-21
Also published as: JP6361168B2; TWI599612B; TW201500467A; KR102096370B1; CN104232106A; JP2015026052A; KR20140146527A

Abstract

The present invention provides a kind of aligning agent for liquid crystal and its film, liquid crystal display cells and its manufacture method, the polymer containing nitrogenous heteroaromatic and compound.The liquid crystal display cells that the present invention provides deterioration caused by a kind of use less and reliability is high.Contain the polymer (P) with the specific structure represented by following formula (1A) in the aligning agent for liquid crystal of the present invention.

Description

Aligning agent for liquid crystal and its film, liquid crystal display cells and its manufacture method, contain nitrogenous virtue The polymer and compound of fragrant race's heterocycle

Technical field

The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display cells, liquid crystal display cells manufacturer Method, polymer and compound, more particularly to be suitable for manufacturing polymer stabilizing orientation (Polymer Sustained Alignment, PSA) mode liquid crystal display element technology.

Background technology

Generally, liquid crystal display cells include between a pair of oppositely disposed substrates：Liquid crystal layer comprising liquid crystal molecule；And liquid Brilliant alignment films, it is configured in a manner of clamping liquid crystal layer, is required state of orientation by liquid crystal molecule control.In addition, in the past, Liquid crystal display cells are just in different a variety of type of drive such as developing electrode structure or the physical property of used liquid crystal molecule.Example Such as, former vertical orientated (the Multi-Domain Vertical of known more quadrants as vertical alignment mode Alignment, MVA) by using the thrust formed in liquid crystal panel, the collapse direction for limiting liquid crystal molecule comes type panel Realize the expansion at visual angle.However, according to which, the deficiency of transmitance and contrast caused by thrust is inevitable, separately Outside, the slow unfavorable condition of response speed of liquid crystal molecule be present.

In recent years, in order to solve the problems, such as MVA type panels, it is proposed that polymer stabilizing is orientated (Polymer Sustained Alignment, PSA) new drive pattern of the pattern as the orientation for controlling liquid crystal molecule.PSA patterns are following technology：Will Photopolymerization monomer is mixed into liquid crystal material in advance, after assembling liquid crystal cells, is applied a pair of electrodes clamping liquid crystal layer Light irradiation is carried out to liquid crystal cells in the state of making alive, thus photopolymerization monomer polymerization is controlled to the molecule of liquid crystal molecule Orientation.According to the technology, there is the advantages of expansion or high-speed response that can realize visual angle.In addition, in recent years, to PSA type The further high-speed response of liquid crystal panel is studied, and the technology attempts will have any one of 1 alkenyl and fluorine alkenyl Mono-functional's liquid crystal compounds (hereinafter also referred to " alkenyl system liquid crystal ") be directed into liquid crystal layer (for example, referring to patent text Offer 1~patent document 3).

[prior art literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2010-285499 publications

[patent document 2] Japanese Patent Laid-Open 9-104644 publications

[patent document 3] Japanese Patent Laid-Open 6-108053 publications

The content of the invention

In recent years, it is aobvious to be used for PC (personal computer) etc. not only as beforely for liquid crystal display cells Show terminal, but also for such as LCD TV or auto-navigation system (car navigation system), mobile phone, intelligence The multiple uses such as phone (smartphone), information display (information display).Due to as described above multi-purpose Wayization, it is desirable to which deterioration caused by using less and the high liquid crystal display cells of reliability, it is expected to be used to obtain this liquid crystal display The material of element.

It is further appreciated that, in the liquid crystal display cells using alkenyl system liquid crystal, the high speed of response speed can be realized, but On the other hand, light irradiation when being polymerize by photopolymerization monomer, the liquid crystal cells phase with being free of alkenyl system liquid crystal in liquid crystal layer Than the fall of voltage retention becomes big.For the aspect that the reliability of liquid crystal display cells improves, also needed after light irradiation Maintain high voltage retention.

The present invention be in view of the problem and formed, main purpose for provide it is a kind of be used to obtain use caused by deteriorate Less and the high liquid crystal display cells of reliability aligning agent for liquid crystal.

Present inventor et al. is actively studied to complete the problem of prior art as described above, is as a result found, By making to have the polymer of specific structure to contain in aligning agent for liquid crystal, the problem is can solve the problem that, so as to complete the present invention. Specifically, following aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display cells, liquid crystal display member are provided by the present invention Manufacture method, polymer and the compound of part.

For an aspect of of the present present invention to provide a kind of aligning agent for liquid crystal, it contains the specific knot represented by with following formula (1A) The polymer (P) of structure.

[changing 1]

(in formula (1A), R²For divalent organic group, X¹For nitrogenous heteroaromatic；Wherein, multiple R in formula²Can with identical, Can also be different, multiple X¹Can be with identical, can also be different；Q¹For nitrogen-atoms, carbon atom or silicon atom, Y¹For hydrogen atom or carbon The alkyl of number 1~5；In Q¹In the case of nitrogen-atoms, t=2 and s=0, in Q¹In the case of silicon atom, t=3 and s=0, In Q¹In the case of carbon atom, t is 2 or 3, and s=3-t.)

Structure represented by the formula (1A) is preferably the structure represented by following formula (1).

[changing 2]

(in formula (1), R²And X¹It is identical with the formula (1A) implication；" * " represents associative key.)

Another aspect of the invention is provide the liquid crystal orientation film that is formed using the aligning agent for liquid crystal and including this The liquid crystal display cells of liquid crystal orientation film.Additionally, it is provided a kind of manufacture method of liquid crystal display cells, it includes：By the liquid Brilliant alignment agent is respectively coated on the conducting film of a pair of substrates with conducting film, is then heated and is formed the step of film Suddenly；Across the liquid crystal layer comprising liquid crystal compounds, by a pair of substrates formed with the film with the film to side The step of formula configuration is to form liquid crystal cells；And to the conductive intermembranous state for applying voltage possessed by the pair of substrate Under to the liquid crystal cells carry out light irradiation the step of.

[The effect of invention]

According to the aligning agent for liquid crystal of the present invention, deterioration caused by using can be obtained less and the high liquid crystal aligning of reliability Film.In addition, the liquid crystal display cells of the present invention and using the present invention manufacture method come the liquid crystal display cells that manufacture due to With the liquid crystal orientation film formed using the aligning agent for liquid crystal, so quality deterioration caused by use is few, reliability is excellent It is different.

Brief description of the drawings

Fig. 1 is the figure of the electrode pattern of ELD for representing to use in embodiment and comparative example.

Fig. 2 is the figure of the electrode pattern of ELD for representing to use in embodiment.

Fig. 3 is the figure of the electrode pattern of ELD for representing to use in embodiment.

The explanation of symbol：

1：ITO electrode

Embodiment

The aligning agent for liquid crystal of the present invention not only includes the polymer (P) with specific structure and is used as component of polymer, and Include the other compositions optionally and arbitrarily allocated.

＜ polymer (P) ＞

The polymer (P) of the present invention is the polymer for having the structure represented by following formula (1A).

[changing 3]

The polymer (P) is preferably the polymer with the structure represented by following formula (1).

[changing 4]

In the formula (1A) and formula (1), Q¹For the R in the case of nitrogen-atoms or carbon atom²Divalent organic group can for example arrange Lift：Divalent alkyl；There is-O- ,-NH- ,-CO-O- ,-CO-NH- ,-CO- ,-S- ,-SO between carbon-carbon bond in alkyl₂-、-Si (CH₃)₂-、-O-Si(CH₃)₂-、-O-Si(CH₃)₂The divalent base of the functional groups such as-O-；Alkyl and-O- ,-NH- ,-CO-O- ,-CO- NH-、-CO-、-S-、-SO₂-、-Si(CH₃)₂-、-O-Si(CH₃)₂-、-O-Si(CH₃)₂The divalent that the functional groups such as-O- link Base；At least one hydrogen atom in alkyl is taken through the halogen atom such as fluorine atom or chlorine atom, bromine atoms, iodine atom or hydroxyl etc. The divalent base in generation etc..In addition, Q¹R in the case of for silicon atom²Divalent organic group except such as Q can be enumerated¹For nitrogen-atoms or carbon R in the case of atom²Concrete example beyond ,-O- ,-CO-O- etc. can also be enumerated.

Herein, " alkyl " in this specification can be with saturation, can also be unsaturated, refers to comprising chain alkyl, ester ring type The implication of alkyl and aromatic hydrocarbyl.In addition, so-called " chain alkyl ", refers to do not have cyclic structure on main chain, but only by The straight-chain alkyl and branch-like alkyl that chain structure is formed.So-called alicyclic type hydrocarbon, refer to that only there is the knot of ester ring type hydrocarbon Structure is as ring structure, without the alkyl of aromatic ring structure.Wherein, it is not necessarily required to be only made up of the structure of ester ring type hydrocarbon, Also the alkyl in one part with chain structure is included.So-called " aromatic hydrocarbyl ", refers to aromatic ring structure as ring The alkyl of structure.Wherein, be not necessarily required only to be made up of aromatic ring structure, can also in one part have chain structure or The structure of ester ring type hydrocarbon.

R²In divalent alkyl be preferably carbon number 1~20, more preferably carbon number 1~10, especially preferably carbon number 1~6.Make For the concrete example of the alkyl, chain alkyl can for example be enumerated：Methylene, ethylidene, glyceryl, fourth diyl, penta diyl, dihexyl Deng alkane diyl, ethenylidene, allylidene etc.；Alicyclic type hydrocarbon is such as can enumerate cyclohexylidene；Aromatic hydrocarbyl is for example Phenylene etc. can be enumerated.Wherein, preferably chain alkyl or alicyclic type hydrocarbon, more preferably alkane diyl.

X¹As long as nitrogenous heteroaromatic in ring skeleton the aromatic rings comprising the nitrogen-atoms of more than 1.Cause This, the hetero atom beyond nitrogen-atoms and nitrogen-atoms can also be included in ring skeleton only comprising nitrogen-atoms as hetero atom (oxygen atom, sulphur atom etc.).X¹In the concrete example of nitrogenous heteroaromatic can for example enumerate：Pyrrole ring, imidazole ring, pyrazoles Ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, indole ring, benzimidazole ring, purine ring, quinoline ring, isoquinolin Ring, naphthyridines ring, quinoxaline (quinoxaline) ring, phthalazines ring, triazine ring, azatropylidene (azepine) ring, diazepine ring, a word used for translation Pyridine ring, azophenlyene (phenazine) ring, coffee quinoline (phenanthroline) ring, oxazole ring, thiazole ring, carbazole ring, Thiadiazole, Benzothiazole ring, phenthazine (phenothiazine) ring, oxadiazoles ring etc..In addition, X¹Can form the ring of the illustration Carbon atom on be imported with the ring of substituent.The substituent is such as can enumerate halogen atom, alkyl, alkoxy.

In these rings, X¹Ring skeleton be preferably pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, rattle away Piperazine ring, pyrazine ring, benzimidazole ring, naphthyridines ring, phthalazines ring, quinoxaline ring, triazine ring, azatropylidene ring, diazepine ring or Azophenlyene ring, more preferably pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring or pyrazine ring.

In addition, in nitrogenous heteroaromatic, with R²Binding site be not particularly limited.Such as X¹Nitrogenous virtue In the case that fragrant race's heterocycle is 5 Yuans rings, described and R²Binding site can enumerate 1- positions, 2- positions or 3- positions, in the situation of 6 Yuans rings Under, 1- positions, 2- positions, 3- positions or 4- positions can be enumerated.

For the viewpoint of liquid crystal orientation film and the reliability of liquid crystal display cells, the Q in the formula (1A)¹Preferably nitrogen Atom.Y¹Preferably hydrogen atom, methyl or ethyl.

Structure represented by the formula (1A) is preferably the structure represented by following formula (1-1A).

[changing 5]

(in formula (1-1A), in Q¹In the case of nitrogen-atoms or carbon atom, R³For the alkane diyl of carbon number 1~5, in Q¹For In the case of silicon atom, R³For the alkane diyl of singly-bound or carbon number 1~5；R⁴For the alkane diyl of singly-bound or carbon number 1~5, A¹For Singly-bound ,-O- ,-CO-, *¹-COO-、*¹-OCO-、*¹- CONH- or *¹-NHCO-(“*¹" represent and R³Associative key)；Wherein, exist R³In the case of singly-bound, A¹For-O- or *¹-OCO-；Multiple R in formula³Can be with identical, can also be different, multiple R⁴Can phase Together, can also be different, multiple A¹Can be with identical, can also be different；X¹、Q¹、Y¹, t and s it is identical with the formula (1A) implication；“*” Represent associative key.)

Structure represented by the formula (1) is preferably the structure represented by following formula (1-1).

[changing 6]

(in formula (1-1), R³、R⁴、A¹It is identical with the formula (1-1A) implication respectively；X¹It is identical with the formula (1) implication； " * " represents associative key.)

In the formula (1-1A) and the formula (1-1), R³And R⁴The alkane diyl of carbon number 1~5 can for example enumerate：Methylene Base, ethylidene, glyceryl, fourth diyl, penta diyl, these bases can be straight-chain or branch-like.In addition, R³And R⁴Can , can also be different with mutually identical.

In Q¹In the case of nitrogen-atoms or carbon atom, R³Preferably carbon number 1~3, more preferably carbon number 1~2.In Q¹For In the case of silicon atom, R3 is preferably singly-bound or carbon number 1~2, more preferably singly-bound.R⁴Preferably singly-bound or carbon number 1~3, more Preferably singly-bound or carbon number 1~2.

A¹For singly-bound ,-O- ,-CO-, *¹-COO-、*¹-OCO-、*¹- CONH- or *¹-NHCO-(“*¹" represent and R³Combination Key).Wherein, preferably singly-bound ,-O-, *¹-CONH-、*¹- COO- or *¹-OCO-。

The main framing of the polymer (P) can be for example enumerated by polyamic acid, poly amic acid ester, polyimides, poly- organic Siloxanes, poly- (methyl) acrylate, polyester, polyamide, cellulose derivative, bunching aldehyde derivatives, polystyrene derivative, The skeleton that poly- (styrene-phenylmaleimide) derivative etc. is formed.Using any in these skeletons, as long as Suitably selected according to the drive pattern of liquid crystal display cells or purposes etc., but wherein, be preferably selected from by polyamide At least one of group that acid, poly amic acid ester and polyimides are formed, more preferably it is selected from by polyamic acid and polyamides At least one of group that imines is formed.

＜ polyamic acids (P) ＞

Polyamic acid (hereinafter also referred to " polyamic acid (P) ") as the polymer (P) of the present invention can be by making tetracarboxylic acid Acid dianhydride is reacted and obtained with diamines.It is easy for the structure represented by the formula (1A) being directed into polymer lateral chain For aspect, synthesizing polyamides acid (P) when, it is preferable to use have the formula (1A) represented by structure diamines.

[tetracarboxylic dianhydride]

The tetracarboxylic dianhydride of polyamic acid for synthesizing the present invention can for example enumerate aliphatic tetracarboxylic dianhydride, ester ring type Tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc..As the concrete example of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydride is for example 1,2,3,4- butane tetracarboxylic acid dianhydrides etc. can be enumerated；

Ester ring type tetracarboxylic dianhydride can for example enumerate：1,2,3,4- cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxylic basic rings penta Guanidine-acetic acid dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphtho- [1,2-c] furans -1, 3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphtho- [1,2-c] furan Mutter -1,3- diketone, 3- oxabicyclos [3.2.1] octane -2,4- diketone -6- loop coils -3 '-(tetrahydrofuran -2 ', 5 '-diketone), 5- (2,5- dioxotetrahydro -3- furyls) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, 3,5,6- tri- carboxyl -2- carboxyl first Base norbornane -2: 3,5: 6- dianhydride, 2, bicyclic [3.3.0] octane -2: 4 of 4,6,8- tetracarboxylics, 6: 8- dianhydride, 4,9- dioxas Three ring [5.3.1.0^2,6] hendecane -3,5,8,10- tetrones, 1,2,4,5- cyclopentanetetracarboxylic's dianhydride (1R, 2S, 4S, 5R- hexamethylenes Alkane tetracarboxylic dianhydride, 1S, 2S, 4R, 5R- cyclopentanetetracarboxylic's dianhydrides etc.), 1,2,3,4- pentamethylene tetracarboxylic dianhydrides (1R, 2R, 3R, 4R- pentamethylene tetracarboxylic dianhydride etc.) etc.；

Aromatic tetracarboxylic acid's dianhydride is such as can enumerate pyromellitic acid anhydride；In addition, Japan can also be used specially Tetracarboxylic dianhydride described in sharp JP 2010-97188 publications.In addition, the tetracarboxylic dianhydride can be used alone a kind or Two or more is applied in combination.

For the viewpoint such as the transparency and dissolubility to solvent, the tetracarboxylic dianhydride for synthesis is preferably to include alicyclic ring Formula tetracarboxylic dianhydride.In addition, ester ring type tetracarboxylic dianhydride is preferably comprising selected from the group being made up of following tetracarboxylic dianhydride At least one of：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydrochysene -2,5- dioxies Generation -3- furyls)-naphtho- [1,2-c] furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysenes -2,5- Dioxo -3- furyls)-naphtho- [1,2-c] furans -1,3- diketone, bicyclic [3.3.0] octane -2: 4 of 2,4,6,8- tetracarboxylics, 6: 8- dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,2,4,5- cyclopentanetetracarboxylic's dianhydrides, 1,2,3,4- pentamethylene tetracarboxylic acids Acid dianhydride, more preferably include selected from least one of the group that is made up of following tetracarboxylic dianhydride tetracarboxylic dianhydride (with Specific tetracarboxylic dianhydride is also referred to as down)：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, 2,4,6,8- tetracarboxylics are bicyclic [3.3.0] Octane -2: 4,6: 8- dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,2,4,5- cyclopentanetetracarboxylic's dianhydrides and 1,2, 3,4- pentamethylene tetracarboxylic dianhydrides.

At synthesizing polyamides sour (P), in the case of using the specific tetracarboxylic dianhydride, relative to for synthesizing polyamides The total amount of the tetracarboxylic dianhydride of amino acid (P), its use ratio (total amount) is preferably 10 moles of more than %, and more preferably 20 rub You are %~100 mole %, especially preferably 50 moles of %~100 mole %.

[diamines]

The diamines of polyamic acid (P) for synthesizing the present invention is preferably comprising with the structure represented by the formula (1A) Diamines.The concrete example of diamines with the structure represented by the formula (1A) can be for example enumerated represented by following formula (d-1A) Compound represented by compound etc., preferably following formula (d-1).

[changing 7]

(in formula (d-1A), R¹For singly-bound or divalent organic group；R²、X¹、Q¹、Y¹, t and s it is identical with the formula (1A) implication.)

[changing 8]

(in formula (d-1), R¹For singly-bound or divalent organic group；R²And X¹It is identical with the formula (1) implication.)

R in the formula (d-1A) and the formula (d-1)¹Divalent organic group can enumerate：-CO-、*²-OCO-(“*²" represent With the associative key of diamino-phenyl bond) and the conduct R²Divalent organic group and base for illustrating etc..R¹Preferred concrete example Such as group represented by following formula (r-1) can be enumerated.

[changing 9]

*³-A²-R⁵-A³-*⁴ (r-1)

(in formula (r-1), A²For singly-bound ,-O- ,-CO-, *³- OCO- or *³- COO-, A³For singly-bound ,-CO- or-OCO-*⁴, R⁵ For singly-bound, alkane diyl or the divalent base between the carbon-carbon bond of alkane diyl with-O- ,-CO-O- ,-CO-NH- or-CO-； “*³" and " *⁴" represent associative key；Wherein, " *³" be bonded with diamino-phenyl.)

The R of the formula (r-1)⁵In alkane diyl can be straight-chain or branch-like, preferably carbon number 1~ 8, more preferably carbon number 1~4.R⁵The preferably alkane diyl of singly-bound or carbon number 1~8, more preferably singly-bound or carbon number 1~4 Alkane diyl, especially preferably singly-bound, methylene or ethylidene；A²Preferably singly-bound ,-CO- or *³-OCO-.In addition, base "-N- (R²-X¹)₂" preferred concrete example explanation can apply the formula (1) explanation.

The preferred concrete example of compound represented by the formula (d-1) can for example enumerate following formula (da-1)~formula (da- 68) represented compound of difference etc..

[changing 10]

[changing 11]

[changing 12]

[changing 13]

[changing 14]

In addition, the Q of the formula (d-1A)¹It can such as be enumerated down for the preferred concrete example of the compound of carbon atom or silicon atom State formula (da-69)~represented compound of formula (da-80) difference etc..

[changing 15]

Diamines for synthesizing the polyamic acid (P) can be used alone with the structure represented by the formula (1) two Amine (hereinafter also referred to " specific diamines "), but can also by the diamines (hereinafter also referred to " other diamines ") beyond specific diamines with The specific diamines is used together.

Herein, other diamines can for example be enumerated：Aliphatic diamine, ester ring type diamines, aromatic diamine, diaminourea organosilicon Oxygen alkane etc..As the concrete example of these diamines, aliphatic diamine can for example be enumerated：M-xylene diamine, 1,3- propane diamine, four methylenes Base diamines, five methylene diamine, hexamethylene diamine etc.；Ester ring type diamines can for example be enumerated：Isosorbide-5-Nitrae-diaminocyclohexane, 4, Double (amino methyl) hexamethylenes of 4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine), 1,3- etc.；

Aromatic diamine can for example be enumerated：P-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl Thioether, 1,5-diaminonaphthalene, 2,2 '-dimethyl -4,4 '-benzidine, 2,2 '-bis- (trifluoromethyl) -4,4 '-diaminourea connection Benzene, 2,7- diamino-fluorenes, 4, double [4- (4- amino-benzene oxygens) phenyl] propane of 4 '-diamino-diphenyl ether, 2,2-, 9,9- are double Double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of (4- aminophenyls) fluorenes, 2,2-, double (4- aminophenyls) hexafluoros third of 2,2- Alkane, 4,4 '-(to phenylenediisopropylidene) dianils, 4,4 '-(isopropylidene of metaphenylene two) dianils, Isosorbide-5-Nitrae-bis- (4- Amino-benzene oxygen) benzene, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, DAP, 3,4- diamino-pyridines, 2,4- bis- Aminopyrimidine, 3,6- proflavins, 3,6- diaminocarbazoles, N- methyl -3,6- diaminocarbazole, N- ethyl -3,6- diaminos Base carbazole, N- phenyl -3,6- diaminocarbazole, N, N '-bis- (4- aminophenyls)-benzidine, N, N '-bis- (4- aminophenyls) - N, N '-dimethylbenzidine, Isosorbide-5-Nitrae-bis--(4- aminophenyls)-piperazine, 1- (4- aminophenyls) -2,3- dihydros -1,3,3- front threes Base -1H- indenes -5- amine, 1- (4- aminophenyls) -2,3- dihydros -1,3,3- trimethyl -1H- indenes -6- amine, 3,5- diaminobenzene first Acid, cholesteric alkyl oxy -3,5- diaminobenzene, cholesteryl epoxide -3,5- diaminobenzene, cholesteric alkyl oxy -2,4- diamino Base benzene, cholesteryl epoxide -2,4- diaminobenzene, 3,5- diaminobenzoic acid cholesterics Arrcostab, 3,5- diaminobenzoic acid courages Double (the 4- aminobenzoics acyloxy) cholestane of steroid alkenyl esters, 3,5- diaminobenzoic acid lanostane base ester, 3,6-, 3,6- are double (4- amino-benzene oxygens) cholestane, 4- (4 '-trifluoromethoxy benzoyloxy) cyclohexyl -3,5- diaminobenzoic acids ester, 4- Double (4- ((aminophenyl) methyl) benzene of (4 '-trifluoromethylbenzoyl epoxide) cyclohexyl -3,5- diaminobenzoic acid ester, 1,1- Base) -4- butyl cyclohexanes, double (4- ((aminophenyl) methyl) the phenyl) -4- heptylcyclohexanes of 1,1-, double (the 4- ((amino of 1,1- Phenoxy group) methyl) phenyl) -4- heptylcyclohexanes, double (4- ((aminophenyl) methyl) phenyl) -4- (the 4- heptyl hexamethylenes of 1,1- Base) hexamethylene, 2,4- diamino-Ns, N- diallyl anilines, 4- aminobenzyls amine, 3- aminobenzyls amine, 1,3- diaminourea -4- Double (the 4- aminobenzoics acyloxy) cholestane of octadecane epoxide benzene, 3- (3,5- diaminobenzene formyloxy) cholestane, 3,6-, with And following formula (Y-1)

[changing 16]

(in formula (Y-1), X^IAnd X^IIIt is separately singly-bound ,-O- ,-COO- or-OCO-, R^IAnd R^IIIt is separately The alkane diyl of carbon number 1~3, the integer that a is 0 or 1, b are 0~2, c are 1~20 integer, and m is 0 or 1, n are 0 or 1；Wherein, 0) a and b will not turn into simultaneously

Represented compound etc.；

Diaminourea organosiloxane can for example enumerate double (3- aminopropyls)-tetramethyl disiloxanes of 1,3- etc.；Except this with Outside, the diamines described in Japanese Patent Laid-Open 2010-97188 publications can also be used.

"-X in the formula (Y-1)^I-(R^I-X^II)_n- " represented by divalent base be preferably：The alkane two of carbon number 1~3 Base, *-O-, *-COO- or *-O-C₂H₄- O- (associative key and diamino-phenyl for wherein, being labeled with " * " are bonded).

Base "-C_cH_2c+1" concrete example can for example enumerate：Methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, just Heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, positive 16 Alkyl, n-heptadecane base, n-octadecane base, NSC 77136 base, n-eicosane base etc..2 amino in diamino-phenyl are preferred To be located at 2,4- positions or 3,5- position relative to other bases.

The concrete example of compound represented by the formula (Y-1) can for example enumerate following formula (Y-1-1)~formula (Y-1-4) point Not represented compound etc..

[changing 17]

In addition, these diamines can be used alone and a kind or two or more be applied in combination.

When synthesizing the polyamic acid (P), relative to the total amount of the diamines for synthesis, the usage amount of the specific diamines Preferably 0.1 mole of %~80 mole %, more preferably 1 mole of %~60 mole %, especially preferably 3 moles of %~50 rub You are %, particularly preferably 5 moles of %~30 mole %.

[molecular weight regulator]

, can be while using tetracarboxylic dianhydride as described above and diamines, using appropriate during synthesizing polyamides acid Molecular weight regulator synthesizes end modified type polymer.By forming the end modified type polymer, can not undermine Further improve the coating (printing) of aligning agent for liquid crystal in the case of effect of the present invention.

Molecular weight regulator can for example be enumerated：The single acid anhydride of acid, monoamine compound, monoisocyanate compound etc..It is used as these The concrete example of compound, the single acid anhydride of acid can for example be enumerated：Maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl fourth two Acid anhydrides, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.；Monoamine compound example It can such as enumerate：Aniline, cyclo-hexylamine, n-butylamine, n-pentyl amine, n-hexyl amine, n-heptyl amine, n-octylamine, n-dodecane Base amine, n-octadecane base amine etc.；Monoisocyanate compound can for example be enumerated：Phenyl isocyanate, naphthyl isocyanate etc..Relative to Used tetracarboxylic dianhydride and total 100 parts by weight of diamines, the use ratio of molecular weight regulator are preferably to be set to 20 Below parts by weight, more preferably it is set to below 10 parts by weight.

The synthesis ＞ of the specific diamines of ＜

The compound represented by compound and the formula (d-1) represented by the formula (d-1A) can be by that will organise Well-established law is appropriately combined to be synthesized.One example can be listed below method：Synthesis replaces the formula (d-1A) or the formula (d-1) In one-level amino and with nitro dinitro intermediate, then go back original system by gained dinitro intermediate using applicable Nitro carry out amination.

Synthesizing the method for the dinitro intermediate can suitably select according to the compound as target.As one Example, such as in the case of for the compound represented by the formula (d-1), following methods can be enumerated：[1] make that there is the formula (1) secondary amino compounds of the structure represented by, with can be reacted and had with the two level amino in the secondary amino compounds R¹And the method that the compound (such as acyl chlorides or carboxylic acid etc.) of dinitrophenyl is reacted；[2] make that there is " R^N-R¹-N-”(R^N Represent dinitrophenyl) represented by group and two functionality compounds with 2 functional groups, and can be with two functionality Compound is reacted and has X¹The method reacted of compound etc..

The reduction reaction of the dinitro intermediate be preferably capable in organic solvent, using such as palladium carbon, platinum oxide, The catalyst such as zinc, iron, tin, nickel are implemented.Organic solvent as used herein can for example be enumerated：Ethyl acetate, toluene, tetrahydrochysene furan Mutter, alcohol system etc..But the synthesis program of the compound represented by the compound and the formula (d-1) represented by the formula (d-1A) is simultaneously It is not limited to methods described.

The synthesis ＞ of ＜ polyamic acids

The tetracarboxylic dianhydride of synthetic reaction and the use ratio of diamines for being supplied to the polyamic acid of the present invention are preferably phase For the equivalent of amino 1 of diamines, the anhydride group of tetracarboxylic dianhydride turns into the ratio of the equivalent of 0.2 equivalent~2, more preferably turns into The ratio of the equivalent of 0.3 equivalent~1.2.In addition, the synthetic reaction of polyamic acid is preferably carried out in organic solvent.Now anti- It is preferably -20 DEG C~150 DEG C, more preferably 0 DEG C~100 DEG C to answer temperature.In addition, the reaction time is preferably 0.1 hour~24 small When, more preferably 0.5 hour~12 hours.

Herein, the organic solvent used in reaction can for example be enumerated：Aprotic polar solvent, phenol series solvent, alcohol, ketone, Ester, ether, halogenated hydrocarbon, hydrocarbon etc..As the concrete example of these organic solvents, aprotic polar solvent can for example be enumerated：N- methyl- 2-Pyrrolidone, DMA, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, six Methyl phosphoric triamide etc.；Phenol series solvent can for example be enumerated：Phenol, metacresol, xylenol, halogenation phenol etc.；

Alcohol can for example be enumerated：Methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propane diols, BDO, three second two Alcohol, glycol monoethyl ether etc.；Ketone can for example be enumerated：Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.；The ester example It can such as enumerate：Ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methoxy methyl propionate, ethoxy-c Acetoacetic ester, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate etc.；Ether can for example be enumerated：Diethyl Ether, isoamyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-n-butyl ether, glycol dimethyl ether, second Glycol ether acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetic acid esters, tetrahydrofuran etc.； Halogenated hydrocarbon can for example be enumerated：Dichloromethane, 1,2- dichloroethanes, Isosorbide-5-Nitrae-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorohenzene etc.； The hydrocarbon can for example be enumerated：Hexane, heptane, octane, benzene,toluene,xylene etc..

In these organic solvents, it is preferable to use selected from the group being made up of aprotic polar solvent and phenol series solvent In group one or more of (organic solvent of the first group), or one or more of organic solvent selected from the first group with In the group being made up of alcohol, ketone, ester, ether, halogenated hydrocarbon and hydrocarbon one or more of (organic solvent of the second group) Mixture.In the latter case, relative to the first group organic solvent and the second group organic solvent total amount, The use ratio of the organic solvent of two groups is preferably below 50 weight %, more preferably below 40 weight %, especially preferably Below 30 weight %.The usage amount (a) of organic solvent is preferably to be set to the total amount (a+b) relative to reaction solution, tetrabasic carboxylic acid two The total amount (b) of acid anhydride and diamines turns into the weight % of 0.1 weight %~50 amount.

The reaction solution for forming polyamic acid dissolving is obtained in the above described manner.The reaction solution can be supplied directly to liquid crystal The preparation of alignment agent, the preparation of aligning agent for liquid crystal can also will be available to after polyamic acid isolation contained in reaction solution, Or the polyamic acid isolated can also be available to the preparation of aligning agent for liquid crystal after purification.Taken off to polyamic acid Water closed loop and in the case of forming polyimides, the reaction solution can be supplied directly to dehydration closed-loop reaction, can also will In reaction solution dehydration closed-loop reaction, or the polyamide that will can also be isolated are available to after contained polyamic acid isolation Acid is available to dehydration closed-loop reaction after purification.The isolation of polyamic acid and purifying can be carried out according to known method.

＜ poly amic acid esters (P) ＞

Poly amic acid ester (hereinafter also referred to " poly amic acid ester (P) ") as the polymer (P) of the present invention for example can profit Obtain using the following method：[I] make by the synthetic reaction and obtain polyamic acid and the compound of hydroxyl, halogenation The method that thing, compound containing epoxy radicals etc. are reacted；[II] makes the method that tetracarboxylic acid acid diesters are reacted with diamines；And It is anti-that [III] makes tetracarboxylic acid acid diesters dihalide (tetracarboxylic acid diester dihalide) be carried out with diamines The method answered.

Herein, the compound of the hydroxyl used in method [I] can for example be enumerated：The alcohols such as methanol, ethanol, propyl alcohol；Benzene Phenols such as phenol, cresols etc..In addition, halide can for example be enumerated：Bromomethane, bromoethane, bromo-octadecane (stearyl Bromide), chloromethanes, chlorooctadecane (stearyl chloride), 1,1,1- tri- fluoro- 2- iodoethane etc., containing epoxy radicals Compound is such as can enumerate expoxy propane.The tetracarboxylic acid acid diesters used in method [II] for example can by using the alcohols, Illustrated tetracarboxylic dianhydride carries out open loop and obtained in synthesis to the polyamic acid.In addition, used in method [III] Tetracarboxylic acid acid diesters dihalide can pass through the appropriate chlorinating agents such as the tetracarboxylic acid acid diesters for making to obtain in the above described manner and thionyl chloride Reacted and obtained.The diamines used in method [II] and method [III] can be used with the knot represented by the formula (1A) The diamines of structure and other described diamines etc..In addition, poly amic acid ester can only have amic acid esters structure or amic acid knot Structure and amic acid esters structure and the partial esterification thing deposited.

＜ polyimides (P) ＞

Polyimides (hereinafter also referred to " polyamides Asia as polymer (P) contained in the aligning agent for liquid crystal of the present invention Amine (P) ") dehydration closed-loop can be carried out by the polyamic acid (P) to synthesizing in the above described manner, it is subject to imidizate and obtains.

The polyimides (P) can be complete to amic acid structure possessed by the polyamic acid (P) as its presoma Portion carries out complete acid imide compound obtained by dehydration closed-loop or a part for amic acid structure only is carried out into dehydration closed-loop And make amic acid structure and imide ring structure and the part acid imide compound deposited.Just make the electrical characteristic of liquid crystal display cells good For good viewpoint, the acid imide rate of polyimides of the invention is preferably more than 30%, and more preferably 40%~99%, especially It is preferably 50%~99%.The acid imide rate is the quantity and imide ring knot relative to the amic acid structure of polyimides Adding up to for the quantity of structure, the ratio shared by the quantity of imide ring structure is expressed as a percentage.Herein, one of imide ring It can be different imide ring to divide.

The dehydration closed-loop of polyamic acid is preferably to be carried out using following methods：The method heated to polyamic acid, Or polyamic acid is dissolved in organic solvent, dehydrating agent and dehydration closed-loop catalyst are added in the solution, is optionally entered The method of row heating.Wherein, later approach is preferably utilized.

Dehydrating agent and dehydration closed-loop catalyst are added in the solution of polyamic acid to carry out in the method for imidizate, Dehydrating agent acid anhydrides such as usable acetic anhydride, propionic andydride, TFAA.Relative to the 1 of the amic acid structure of polyamic acid Mole, the usage amount of dehydrating agent is preferably to be set to 0.01 mole~20 moles.Dehydration closed-loop catalyst for example can be used：Pyridine, The tertiary amines such as collidine (collidine), two picolins (lutidine), triethylamine.Relative to used dehydrating agent 1 Mole, the usage amount of dehydration closed-loop catalyst is preferably to be set to 0.01 mole~10 moles.What is used in dehydration closed-loop reaction has Solvent can enumerate the organic solvent illustrated as the organic solvent for synthesizing polyamides acid.The reaction of dehydration closed-loop reaction Temperature is preferably 0 DEG C~180 DEG C, more preferably 10 DEG C~150 DEG C.Reaction time is preferably 1.0 hours~120 hours, more excellent Elect as 2.0 hours~30 hours.

The reaction solution containing polyimides (P) is obtained in the above described manner.The reaction solution can be supplied directly to liquid crystal and take To the preparation of agent, aligning agent for liquid crystal is available to after dehydrating agent and dehydration closed-loop catalyst can also being removed in autoreaction solution Prepare, the preparation of aligning agent for liquid crystal is available to after can also polyimides (P) be isolated, or can also be poly- by what is isolated Acid imide (P) is available to the preparation of aligning agent for liquid crystal after purification.These purification process can be carried out according to known method.

The polyamic acid, poly amic acid ester and polyimides as polymer (P) obtained in the above described manner is preferably to work as When being made into the solution that concentration is 10 weight %, the compound of the solution viscosity with 10mPas~800mPas is more excellent Elect the compound of the solution viscosity with 15mPas~500mPas as.In addition, solution viscosity (the mPa of the polymer S) refer to for using the good solvent (such as gamma-butyrolacton, METHYLPYRROLIDONE etc.) of the polymer come the concentration for preparing For 10 weight % polymer solution, using E type rotation viscometers, the value obtained by measure at 25 DEG C.In addition, for the present invention Aligning agent for liquid crystal in contained polyamic acid, poly amic acid ester and polyimides, utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) come determine polystyrene conversion weight average molecular weight (Mw) be preferably 500~100,000, more preferably 1,000~50,000.

In addition, the polymer (P) with the skeleton beyond polyamic acid, poly amic acid ester and polyimides as main framing Can also be by synthesizing the well-established law of organic chemistry is appropriately combined.As one example, main framing is used as using polysiloxane Polymer (P) for example can by make the polysiloxane with epoxy radicals, with the formula (1A) represented by structure Carboxylic acid reacted to obtain.

For suitably obtaining the viewpoint of effect of the present invention, relative to component of polymer contained in aligning agent for liquid crystal Total amount, the content ratio of the polymer (P) in aligning agent for liquid crystal is preferably to be set to more than 5 weight %, is more preferably set to 10 More than weight %.In addition, there is no particular restriction for higher limit, can arbitrarily be set in the scope below 100 weight %.

For suitably obtaining the viewpoint of effect of the present invention, relative to component of polymer contained in aligning agent for liquid crystal Total amount, the specific structure possessed by polymer (P) be preferably be set to 1 × 10^-5Mol/g~1 × 10^-2Mol/g, it is more excellent Elect as and be set to 5 × 10^-5Mol/g~5 × 10^-3mol/g.Therefore, it is desirable that with the specific knot possessed by polymer (P) The amount of structure turns into the mode of the scope, to set the species and amount of the compound for synthetic polymer (P).

In addition, in the present invention, PSA mode liquid crystals display member is being formed using the aligning agent for liquid crystal comprising polymer (P) , can be when carrying out light irradiation to liquid crystal cells, so that photopolymerizable compound (light will not be hindered in the case of the liquid crystal orientation film of part Polymerizable monomer) the mode of photopolymerization reaction aided in from liquid crystal orientation film side, thus it is speculated that its result is：Optical polymerism chemical combination The polymerisation of thing fully carries out and obtains the improvement of reliability.

＜ other compositions ＞

The aligning agent for liquid crystal of the present invention optionally can contain other compositions.The other compositions can for example be enumerated：It is described The compound that other polymers, intramolecular beyond polymer (P) have at least one epoxy radicals (hereinafter referred to as " contains epoxy radicals Compound "), functional silanes compound etc..

[other polymers]

The other polymers can be used in improving solution properties or electrical characteristic.The other polymers, which can be enumerated, not to be had There is the polymer of the specific structure, its main framing can for example be enumerated：It is polyamic acid, poly amic acid ester, polyimides, poly- organic Siloxanes, polyester, polyamide, cellulose derivative, polyacetals, polystyrene derivative, poly- (styrene-phenyl maleic two Acid imide) derivative, poly- (methyl) acrylate etc..

In the case where other polymers are made an addition in aligning agent for liquid crystal, relative to polymerization contained in aligning agent for liquid crystal Total 100 parts by weight of thing, the allotment ratio of the other polymers is preferably more preferably 0.1 weight below 95 parts by weight Part~90 parts by weight, the parts by weight of especially preferably 0.1 parts by weight~85.

[compound containing epoxy radicals]

Compound containing epoxy radicals can be used in improving the cementability or electrical characteristic of liquid crystal orientation film and substrate surface.This Compound of the kind containing epoxy radicals can for example be enumerated：Ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propane diols two Glycidol ether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6- hexanediol diglycidyl ethers, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2,2- dibromos new penta 2 Alcohol diglycidyl ether, N, N, N ', double (N, N- the diglycidyl amino of N '-four glycidyl group-m-xylene diamine, 1,3- Methyl) hexamethylene, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl-methane, N, N- diglycidyls-benzyl Base amine, N, N- diglycidyls-aminomethyl cyclohexane, N, N- diglycidyl-cyclo-hexylamine etc. are used as preferred chemical combination Thing.In addition, what the also usable International Publication No. 2009/096598 of the example of the compound containing epoxy radicals was recorded contains epoxy The polysiloxane of base.

In the case where these epoxides are made an addition in aligning agent for liquid crystal, relative to contained in aligning agent for liquid crystal Total 100 parts by weight of polymer, the allotment ratio of these epoxides is preferably below 40 parts by weight more preferably 0.1 The parts by weight of parts by weight~30.

[functional silanes compound]

The functional silanes compound can use for the purpose for the printing for improving aligning agent for liquid crystal.This official Energy property silane compound can for example be enumerated：3- TSL 8330s, APTES, 2- amino Propyl trimethoxy silicane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- aminopropyl trimethoxy silicon Alkane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, 3- ureido-propyl trimethoxy silanes, 3- urea groups third Ethyl triethoxy silicane alkane, N- ethoxy carbonyl -3- TSL 8330s, N- tri-ethoxy silylpropyls Sanya second Base triamine, 10- trimethoxy silanes base-Isosorbide-5-Nitrae, the azepine decane of 7- tri-, 9- trimethoxy silane base -3,6- diaza nonyl acetic acid Ester, 9- trimethoxy silane base -3,6- diazas methyl pelargonate, N- benzyl -3- TSL 8330s, N- phenyl - 3- TSL 8330s, glycidoxypropyl MTMS, 2- glycidoxypropyl ethyl trimethoxies Base silane, 3- glycidoxypropyltrimewasxysilanes etc..

In the case where these functional silanes compounds are made an addition in aligning agent for liquid crystal, relative in aligning agent for liquid crystal Total 100 parts by weight of contained polymer, the allotment ratios of these functional silanes compounds be preferably below 2 parts by weight, The parts by weight of more preferably 0.02 parts by weight~0.2.

In addition, other compositions in addition to the compound, also intramolecular can be used to have at least one oxetanes The compound of base or antioxidant etc..

＜ solvents ＞

The aligning agent for liquid crystal of the present invention is prepared to the polymer (P) and optionally carrys out the other compositions of any allotment Preferably disperse or dissolve in organic solvent the liquid composition formed.

Herein, the solvent of the aligning agent for liquid crystal for preparing the present invention can for example be enumerated：METHYLPYRROLIDONE, γ- Butyrolactone, butyrolactam, DMF, DMA, 4- hydroxy-4-methyl-2-pentanones, second Glycol monomethyl ether, butyl lactate, butyl acetate, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol Ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), glycol dimethyl ether, second two Alcohol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl It is glycol monomethylether acetate, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol monomethyl ether, DIBK, isoamyl propionate, different Isoamyl butyrate, isoamyl ether, ethylene carbonate, propylene carbonate etc..These solvents can be used alone a kind or by 2 kinds with On be used in mixed way.

Solid component concentration (total weight of the composition beyond the solvent of aligning agent for liquid crystal in the aligning agent for liquid crystal of the present invention Measure shared ratio in the gross weight of aligning agent for liquid crystal) viscosity, volatility etc. is allowed for suitably to select, but preferably 1 The weight % of weight %~10 scope.That is, aligning agent for liquid crystal of the invention in a manner of aftermentioned by being coated on substrate surface, preferably To be heated, and form the film as liquid crystal orientation film or the film as liquid crystal orientation film, but now, solid into Dividing concentration, the thickness of the film becomes too small and is difficult to obtain good liquid crystal orientation film less than in the case of 1 weight %.It is another Aspect, in the case where solid component concentration is more than 10 weight %, the thickness of film becomes too much and is difficult to obtain good liquid Brilliant alignment films, the viscosity that additionally, there are aligning agent for liquid crystal increase and the tendency of coating characteristics variation.

The scope of particularly preferred solid component concentration is according to the used method in coating of liquid crystalline alignment agent on substrate It is and different.Such as using in the case of circulator method, solid component concentration is particularly preferably the weight % of 1.5 weight %~4.5 Scope.Using in the case of print process, solid component concentration is particularly preferably set to the weight % of 3 weight %~9 model Enclose, thus solution viscosity is set to 12mPas~50mPas scope.In the case of using ink-jet method, particularly preferably Solid component concentration is set to the weight % of 1 weight %~5 scope, solution viscosity is thus set to 3mPas~15mPas Scope.Temperature when preparing the aligning agent for liquid crystal of the present invention is preferably 10 DEG C~100 DEG C, more preferably 20 DEG C~80 DEG C.

＜ liquid crystal orientation films and liquid crystal display cells ＞

The liquid crystal orientation film of the present invention is formed using the aligning agent for liquid crystal prepared in this way.It is in addition, of the invention Liquid crystal display cells including the use of the present invention aligning agent for liquid crystal come the liquid crystal orientation film that is formed.Using the liquid crystal of the present invention The drive pattern of display element is not particularly limited, and can be applied to twisted nematic (twisted nematic, TN) type, super torsion Turn to row (super twisted nematic, STN) type, coplanar switching (in-plane switching, IPS) type, fringing field Switch (fringe field switching, FFS) type, vertical orientated (vertical alignment, VA) type, MVA types, The multiple drive modes such as PSA type, wherein PSA patterns can be particularly preferably applied for.

The PSA mode liquid crystals display element of the present invention is for example using the method for comprising the following steps (1)~step (3) To manufacture：

(1) aligning agent for liquid crystal of the present invention is respectively coated on the conducting film of a pair of substrates with conducting film, after And the step of being heated and forming film；

(2) across the liquid crystal layer comprising liquid crystal compounds, by a pair of substrates formed with the film with film to The step of mode configures and constructs liquid crystal cells；And

(3) light irradiation is carried out to liquid crystal cells in the state of to conductive intermembranous application voltage possessed by a pair of substrates Step.

[step (1)：The formation of film]

First, by be coated with substrate the present invention aligning agent for liquid crystal, then by coated face heated and in substrate Upper formation film.The substrate of liquid crystal display cells for example can be used：Float glass (float glass), soda-lime glass (soda The glass such as glass)；Include PET, polybutylene terephthalate, polyether sulfone, makrolon, poly- (fat Ring type alkene) etc. plastics transparency carrier.Conducting film possessed by the substrate is preferably to use nesa coating, such as can be made With：Include tin oxide (SnO₂) nesa (NESA) film (PPG register of company of U.S. trade mark), include indium oxide-tin oxide (In₂O₃-SnO₂) ito film etc..The conducting film is preferably the pattern-like conducting film for being divided into multiple regions.If it is made this Conducting film, then, can be by applying different voltage in each region when to conductive intermembranous application voltage, and makes liquid in each region The direction change of the pre-tilt angle of brilliant molecule, it thus can further expand viewing angle characteristic.In order to obtain patterned electrically conducting transparent Film, such as using following methods：After forming the nesa coating of pattern-free, by being etched by light (photo etching) come shape Into the method for pattern；Method of the shade with required pattern etc. is used when forming nesa coating.

As the method for the coating of liquid crystalline alignment agent on substrate, preferably using flexographic printing process (offset Printing method), method of spin coating (spin coating method), roll-coater method (roll coater Method) or ink jet printing method (inkjet printing method) is carried out.During coating of liquid crystalline alignment agent, in order that base The cementability of plate surface and nesa coating and film is better, can also be real to that should form the face of film in substrate surface Apply the pre-treatment for being pre-coated with functional silanes compound, functionality titanium compound etc..

It is excellent the purpose of for the sagging for preventing be coated with aligning agent for liquid crystal after aligning agent for liquid crystal is coated on substrate Elect implementation preheating (prebake conditions (prebake)) as.Prebake conditions temperature is preferably 30 DEG C~200 DEG C, more preferably 40 DEG C~150 DEG C, particularly preferably 40 DEG C~100 DEG C.The prebake conditions time is preferably 0.25 minute~10 minutes, more preferably 0.5 minute~5 Minute.Then, solvent is removed completely, for the purpose that hot-imide is carried out to amic acid structure present in polymer Optionally implement calcining (rear baking (postbake)) step.Afterwards baking temperature be preferably 80 DEG C~300 DEG C, more preferably 120 DEG C~250 DEG C.Post-bake times are preferably 5 minutes~200 minutes, more preferably 10 minutes~100 minutes.Shape in the above described manner Into the thickness of film be preferably 0.001 μm~1 μm, more preferably 0.005 μm~0.5 μm.

By being heated the film to remove organic solvent, being consequently formed as alignment films after coating of liquid crystalline alignment agent. Now, polymer contained in aligning agent for liquid crystal for polyamic acid or poly amic acid ester or with imide ring structure and , can also be by further being heated after film is formed to be dehydrated in the case of the imide amination polymer of amic acid structure Ring-closure reaction, the further film through imidizate is made., can be direct by the film after rear baking in the case of PSA patterns For implementing following step, but collapsing for control liquid crystal molecule, with simple and easy method be orientated the purpose of segmentation, also Weak friction treatment can be carried out to the film.The friction treatment can be carried out by operating as follows：Example is included using being wound with Such as nylon, artificial silk, cotton fiber cloth roller, to film towards certain orientation friction.

[step (2)：Liquid crystal cells are constructed]

Prepare 2 pieces of substrates formed with film in this way, between 2 pieces of oppositely disposed substrates of predetermined distance are spaced apart Liquid crystal layer is configured, thus manufactures liquid crystal cells.In order to manufacture liquid crystal cells, such as 2 kinds of following methods can be enumerated.First party Method known method (vacuum injection mode) before being.First, by the film on each substrate in a manner of, between substrate Such as 1 μm~5 μm of gap (cell gap), 2 pieces of substrates are oppositely disposed, using sealant by the periphery of 2 pieces of substrates Fitting, liquid-crystal composition is being injected in the cell gap that divides after being filled by substrate surface and sealant, will injected Hole seals, and thus manufactures liquid crystal cells.Second method is the method for referred to as instillation (One Drop Fill, ODF) mode. The assigned position on one of substrate in 2 pieces of substrates formed with film, the sealant of such as ultraviolet light photopolymerization is coated with, And then after several positions dropwise addition liquid-crystal compositions as defined on coated surface, by film to being bonded another piece of base in a manner of Plate, and liquid-crystal composition is spread out in the entire surface of substrate, then to the entire surface irradiating ultraviolet light of substrate, make sealant Hardening, thus manufacture liquid crystal cells., can be to the liquid crystal list that manufactures in this way using in the case of any method After member and then liquid crystal molecule used in being heated to turn into the temperature of isotropic phase, room temperature is slowly cooled down to, thus removed Flow orientation when liquid crystal is filled.

Used liquid-crystal composition preferably uses the composition comprising liquid crystal compounds and photopolymerizable compound. Liquid crystal compounds are preferably using the nematic crystal with negative dielectric anisotropy, such as can be used：Dicyanobenzenes (dicyanobenzene) it is that liquid crystal, pyridazine system liquid crystal, schiff bases (Schiff base) are liquid crystal, azoxy (azoxy) system Liquid crystal, biphenyl (biphenyl) are that liquid crystal, cyclohexylbenzene (phenyl cyclohexane) are liquid crystal, terphenyl (terphenyl) it is liquid crystal etc..In addition, for the viewpoint of response speed with regard to further speeding up PSA mode liquid crystal display elements, Liquid crystal compounds can also and with alkenyl system liquid crystal.Existing known liquid crystal can be used in the alkenyl system liquid crystal, such as can enumerate Following formula (L1-1)~represented compound of formula (L1-9) difference etc..In addition, liquid crystal compounds can be used alone a kind or Two or more is applied in combination.

[changing 18]

Photopolymerizable compound can be used, and there is acryloyl group, methylacryloyl, vinyl etc. can carry out radical polymerization The compound of the functional group of conjunction.With regard to reactivity viewpoint for, then it is preferably multi-functional, wherein more preferably have 2 with On acryloyl group and methylacryloyl at least any one.In addition, the orientation of liquid crystal molecule is just set to maintain stable sight For point, photopolymerizable compound is preferably using with least any in the cyclohexane ring and phenyl ring that add up to more than 2 Kind ring is used as the compound of liquid crystal skeleton.In addition, existing known compound can be used in this photopolymerizable compound.Relatively In the total amount of used liquid crystal compounds, the allotment ratio of photopolymerizable compound is preferably to be set to 0.1 weight %~0.5 Weight %.

In addition, liquid-crystal composition is in addition to containing the compound, such as polymerization initiators, anti-oxidant can also be contained The other compositions such as agent, ultra-violet absorber, stabilizer.The allotment amount of these other compositions can according to used other compositions come Appropriate adjustment.The thickness of liquid crystal layer is preferably to be set to 1 μm~5 μm.In addition, sealant can be used for example containing curing agent and conduct Epoxy resin of the alumina balls of sept etc..

[step (3)：Light irradiation step]

After constructing liquid crystal cells, in the state of to conductive intermembranous application voltage possessed by a pair of substrates, to liquid crystal list Member carries out light irradiation.The voltage that this place applies can be set to such as 5V~50V direct current or exchange.In addition, the light irradiated The ultraviolet and luminous ray of the usable light for example comprising 150nm~800nm wavelength, but preferably comprising 300nm~ The ultraviolet of the light of 400nm wavelength.The light source of irradiation light for example can be used：Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal Halide lamp, argon resonance lamp, xenon lamp, PRK etc..In addition, the ultraviolet in the optimal wavelength region can be by by light source With such as filter, diffraction grating (diffraction grating) and method etc. obtain.The exposure of light is preferred For 1,000J/m²Less than 200,000J/m², more preferably 1,000J/m²~150,000J/m²。

Then, Polarizer is bonded to obtain liquid crystal display cells by the outer surface of the liquid crystal cells after light irradiation. Polarizer used herein can be enumerated：The Polarizer for being referred to as the light polarizing film of " H films " and forming is clamped with cellulose acetate diaphragm Or comprising the H films Polarizer of itself, the H films are to make polyvinyl alcohol extension orientation to form while making it absorb iodine Light polarizing film.

The liquid crystal display cells of the present invention can be effectively applied to a variety of devices, such as can be used in：It is clock and watch, portable Game machine (portable game), word processor (word processor), notes type PC (note type Personal computer), auto-navigation system, video camera (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart phone, various monitors, liquid The display device of brilliant TV etc..

[embodiment]

Hereinafter, the present invention is further specifically described by embodiment, but the present invention is not by these embodiments Limitation.

In following embodiment and comparative example, the acyl of the polyimides in polymer solution is determined using following methods Amination rate, the solution viscosity of polymer solution, the weight average molecular weight of polymer and epoxide equivalent.

[the acid imide rate of polyimides]

The solution of polyimides is put into pure water, it is molten after the precipitation of gained is fully dried under reduced pressure at room temperature Solution, using tetramethylsilane as primary standard substance, determines at room temperature in deuterodimethylsulfoxide¹H- nuclear magnetic resonance (¹H- Nuclear magnetic resonance,¹H-NMR).According to gained¹H-NMR spectrum, obtained using following numerical expressions (1) Acid imide rate [%].

Acid imide rate [%]=(1-A¹¹/A¹²×α)×100...(1)

(in numerical expression (1), A¹¹It is the peak area of the proton from NH bases occurred near chemical shift 10ppm, A¹² The peak area of other protons is derived from, α is other protons relative to 1 of the NH bases in the presoma (polyamic acid) of polymer The number ratio of individual proton.)

[solution viscosity of polymer solution]

Using E type rotation viscometers, to being prepared into the solution that polymer concentration is 10 weight % using defined solvent, The solution viscosity [mPas] of polymer solution is determined at 25 DEG C.

[weight average molecular weight of polymer]

Weight average molecular weight is the polystyrene scaled value to determine using the gel permeation chromatography of following condition.

Tubing string：Eastern Cao's (Tosoh) (stock) manufacture, TSKgelGRCXLII

Solvent：Tetrahydrofuran

Temperature：40℃

Pressure：68kgf/cm²

[epoxide equivalent]

Epoxide equivalent is determined using the hydrochloric acid described in JIS C2105-methyl ethyl ketone method.

The synthesis ＞ of ＜ compounds

[embodiment 1A：The synthesis of compound (da-5)]

Compound (hereinafter also referred to compound (the da- represented by the formula (da-5) is synthesized according to following flows 1 5))。

[changing 19]

Will double (3- pyridylmethyls) amine 12.5g (62.8mmol), dichloromethane 150ml, triethylamine 15.9ml (114mmol) is mixed, while being cooled down in ice bath, while being added dropwise 3,5- dinitrobenzoyl chlorides 13.2g After (57.1mmol) is dissolved in solution obtained by dichloromethane 50ml, it is stirred at room temperature 3 hours.After reaction, acetic acid is added Ethyl ester 500ml and tetrahydrofuran 500ml, washed 4 times with distilled water 400ml.After organic layer is dried with magnesium sulfate, distillation Solvent is removed, the solid separated out is filtered, dried, obtains dinitro matrix (formula (dm-5) institute table of brown powder The compound shown) 17.7g (45.0mmol, yield 78.7%).

Then, by the dinitro matrix 17.7g (45.0mmol), 5% palladium carbon (water for containing 50%) 1.77g, tetrahydrofuran 90ml, ethanol 90ml are mixed, and installation adds the balloon for having hydrogen, under hydrogen environment, is stirred at room temperature 5 hours.Instead Ying Hou, made a return journey by diatomite filtering except palladium carbon, filtrate is concentrated and obtains compound (da-5) 12.8g of brown powder (38.3mmol, yield 85.1%).

[embodiment 2A：The synthesis of compound (da-6)]

Compound (hereinafter also referred to compound (the da- represented by the formula (da-6) is synthesized according to following flows 2 6))。

[changing 20]

By 2,4- dinitro benzene guanidine-acetic acid 11.3g (50.0mmol), double (3- pyridylmethyls) amine 9.96g (50.0mmol), dichloromethane 200ml are mixed, while being cooled down in ice bath, while addition 1- ethyls -3- (3- dimethyl Aminopropyl) carbon imidodicarbonic diamide hydrochloride 11.5g (60.0mmol), N, N- dimethyl -4-aminopyridine 1.22g (10.0mmol), it is stirred at room temperature 2 hours.After reaction, ethyl acetate 800ml is added, is washed 4 times with distilled water 400ml.Will After organic layer is dried with magnesium sulfate, distillation removes solvent, and the solid separated out is filtered, dried, obtains brown powder Dinitro matrix (compound represented by the formula (the dm-6)) 16.4g (40.3mmol, yield 80.5%) at end.

Then, by the dinitro matrix 16.4g (40.3mmol), 5% palladium carbon (water for containing 50%) 1.64g, tetrahydrofuran 80ml, ethanol 80ml are mixed, and installation adds the balloon for having hydrogen, under hydrogen environment, is stirred at room temperature 6 hours.Instead Ying Hou, made a return journey by diatomite filtering except palladium carbon, filtrate is concentrated and obtains compound (da-6) 11.5g of brown powder (33.0mmol, yield 82.0%).

[embodiment 3A：The synthesis of compound (da-37)]

Compound (hereinafter also referred to compound (the da- represented by the formula (da-37) is synthesized according to following flows 3 37))。

[changing 21]

Iminodiacetic acid 12.9g (96.7mmol), 2M sodium hydrate aqueous solutions 145ml are mixed, while in ice Cooled down in bath, 3,5- dinitrobenzoyl chlorides 22.3g (96.7mmol) is dissolved in tetrahydrofuran 30ml and obtained while being added dropwise Solution after, be stirred at room temperature 4 hours.After reaction, cooled down in ice bath, and meanwhile addition 1M watery hydrochloric acid 300ml, will The solid separated out is filtered, dried.Then, recrystallized in ethyl acetate 200ml, the solid separated out is carried out Filtering, dry, obtain dicarboxylic acids body (compound represented by the formula (dm-37-1)) 15.3g of white powder (46.7mmol, yield 48.3%).

Then, by the dicarboxylic acids body 15.3g (46.7mmol), 3- aminomethyl pyridines 10.6g (98.1mmol), dichloro Methane 200ml is mixed, while being cooled down in ice bath, while the addition acyl of 1- ethyls -3- (3- dimethylaminopropyls) carbon two Inferior amine salt hydrochlorate 21.5g (112mmol), N, N- dimethyl -4-aminopyridine 2.28g (18.7mmol), it is small to be stirred at room temperature 3 When.After reaction, ethyl acetate 800ml is added, is washed 4 times with distilled water 400ml.Organic layer is dried with magnesium sulfate, be dense Contracting, the solid of gained is recrystallized in ethyl acetate 100ml and hexane 150ml, the solid separated out is filtered, Dry, obtain dinitro matrix (compound represented by the formula (dm-37-2)) 17.5g (34.6mmol, yield of brown powder For 74.1%).

Then, by the dinitro matrix 17.5g (34.6mmol), 5% palladium carbon (water for containing 50%) 1.75g, tetrahydrofuran 70ml, ethanol 70ml are mixed, and installation adds the balloon for having hydrogen, under hydrogen environment, is stirred at room temperature 4 hours.Instead Ying Hou, made a return journey by diatomite filtering except palladium carbon, filtrate is concentrated, obtains compound (da-37) 13.5g of brown powder (30.3mmol, yield 87.6%).

[embodiment 4A：The synthesis of compound (da-67)]

Compound (hereinafter also referred to compound (the da- represented by the formula (da-67) is synthesized according to following flows 4 67))。

[changing 22]

By 2,4- dinitrobenzyl bromine 13.1g (50.0mmol), double (3- pyridylmethyls) amine 9.96g (50.0mmol), Potassium carbonate 8.29g (60.0mmol), KI 1.66g (10.0mmol), DMA 200ml are mixed, Stirred 5 hours at 100 DEG C.After reaction, ethyl acetate 600ml is added, is washed 4 times with distilled water 600ml.By organic layer with sulfuric acid Magnesium is dried, concentrated, and the solid of gained is recrystallized in ethanol 200ml, the solid separated out is filtered, done Dry, obtaining the dinitro matrix (compound represented by the formula (dm-67)) of brown powder, (41.4mmol, yield are 15.7g 82.8%).

Then, by the dinitro matrix 15.7g (41.4mmol), 5% palladium carbon (water for containing 50%) 1.57g, tetrahydrofuran 80ml, ethanol 80ml are mixed, and installation adds the balloon for having hydrogen, under hydrogen environment, is stirred at room temperature 4 hours.Instead Ying Hou, made a return journey by diatomite filtering except palladium carbon, filtrate is concentrated, obtains compound (da-67) 12.2g of brown powder (38.2mmol, yield 92.3%).

[embodiment 5A：The synthesis of compound (da-70)]

Compound (hereinafter also referred to compound (the da- represented by the formula (da-70) is synthesized according to following flows 5 70))。

[changing 23]

Pentaerythrite 102g (750mmol), triethylamine 41.8ml (300mmol), tetrahydrofuran 750ml are mixed Close, while being cooled down in ice bath, 3,5- dinitrobenzoyl chlorides 12.8g (75.0mmol) is dissolved in tetrahydrofuran while being added dropwise After solution obtained by 50ml, it is stirred at room temperature 5 hours.After reaction, ethyl acetate 1500ml is added, with distilled water 750ml Washing 4 times.Organic layer is dried with magnesium sulfate, concentrated, by the solid of gained in ethyl acetate 100ml and hexane 300ml In recrystallized, the solid separated out is filtered, dried, obtains the triol body (formula (dm-70- of brown powder 1) compound represented by) 18.9g (57.2mmol, yield 76.3%).

Then, the triol body 18.9g (57.2mmol), nicotinic acid 21.1g (172mmol), dichloromethane 250ml are carried out Mixing, while being cooled down in ice bath, while addition 1- ethyls -3- (3- dimethylaminopropyls) carbon imidodicarbonic diamide hydrochloride 39.5g (206mmol), N, N- dimethyl -4-aminopyridine 4.19g (34.3mmol), are stirred at room temperature 4 hours.After reaction, Ethyl acetate 800ml is added, is washed 4 times with distilled water 400ml.Organic layer is dried with magnesium sulfate, concentrated, by gained Solid is recrystallized in ethanol 200ml, and the solid separated out is filtered, dried, obtains the dinitro of brown powder Body (compound represented by the formula (dm-70-2)) 29.6g (45.9mmol, yield 80.4%).

Then, by the dinitro matrix 29.6g (45.9mmol), 5% palladium carbon (water for containing 50%) 2.96g, tetrahydrofuran 100ml, ethanol 100ml are mixed, and installation adds the balloon for having hydrogen, under hydrogen environment, is stirred at room temperature 4 hours. After reaction, made a return journey by diatomite filtering except palladium carbon, filtrate is concentrated, obtains compound (da-70) 23.8g of brown powder (40.7mmol, yield 88.7%).

The synthesis ＞ of ＜ polymer

[embodiment 1B：The synthesis of polyimides (PI-1)]

Using as the 2 of tetracarboxylic dianhydride, 3,5- tricarboxylic cyclopentyl acetic acid dianhydride (TCA) 100 molar parts, as diamines The molar part of p-phenylenediamine (PDA) 70,3,5- diaminobenzoic acid cholesteric Arrcostabs (HCDA) 20 molar part and compound (da- 5) 10 molar part, it is dissolved in METHYLPYRROLIDONE (NMP), carries out reacting for 6 hours at 60 DEG C, acquisition contains polyamides The weight % of amino acid 20 solution.Divide and take a small amount of gained polyamic acid solution, it is 10 weights to add NMP and polyamic acid concentration is made Measure % solution, it is measured obtained by solution viscosity be 80mPas.

Then, in the polyamic acid solution of gained, add NMP and the solution that polyamic acid concentration is 7 weight % be made, Pyridine and acetic anhydride are added respectively in units of 1.0 times moles relative to the total amount of used tetracarboxylic dianhydride, 4 hours dehydration closed-loop reactions are carried out at 110 DEG C.After dehydration closed-loop reaction, the solvent in system is subjected to solvent using new NMP Displacement (by this operation, the pyridine used in dehydration closed-loop reaction and acetic anhydride is removed to outside system；It is same as below), by The solution for the weight % of polyimides (PI-1) 26 that this acquisition is about 60% containing acid imide rate.

[embodiment 2B~embodiment 9B, synthesis example 1, synthesis example 2]

The pyridine and second used during except by the species of used tetracarboxylic dianhydride and diamines and amount and imidizate The quantitative change of acid anhydrides more as described in Table 1 beyond, be respectively synthesized polyimides in a manner of with the embodiment 1B identicals (PI-2)~polyimides (PI-11).The measurement result of the acid imide rate of the polymer of gained is shown in table 1 below in the lump In.In addition, in embodiment 7B, monoamine is used together with tetracarboxylic dianhydride and diamines in synthetic polymer.

In table 1, the numerical value in () of tetracarboxylic dianhydride represents the conjunction relative to the tetracarboxylic dianhydride for synthetic polymer Count the use ratio [molar part] of 100 molar parts.Numerical value in () of diamines and monoamine is represented relative to for synthetic polymer Tetracarboxylic dianhydride total 100 molar parts use ratio [molar part].Abbreviation in table 1 is respectively following meanings.In addition, "-" in table 1 refers to without using the compound in the column.

＜ tetracarboxylic dianhydrides ＞

TCA：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides

BODA：Bicyclic [3.3.0] octane -2: 4 of 2,4,6,8- tetracarboxylics, 6: 8- dianhydride

CB：1,2,3,4- cyclobutane tetracarboxylic dianhydride

MTDA：1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphtho- [1,2- C] furans -1,3- diketone

PMDA：Pyromellitic acid anhydride

＜ diamines ＞

PDA：P-phenylenediamine

HCDA：3,5- diaminobenzoic acid cholesteric Arrcostabs

35DAB：3,5- diaminobenzoic acids

HCODA：Cholesteric alkyl oxy -2,4- diaminobenzene

LDA：Compound represented by the formula (Y-1-4)

D-1：1,3- diaminourea -4- { 4- [trans -4- (trans -4- pentyl cyclohexyls) cyclohexyl] phenoxy group } benzene (institute State the compound represented by formula (Y-1-2))

D-2：1,3- double (3- aminopropyls)-tetramethyl disiloxanes

D-3：3,6- double (4- aminobenzoics acyloxy) cholestane

D-5：2,2 '-bis- (trifluoromethyl) -4,4 '-benzidine

D-6：4,4 '-diaminodiphenyl-methane

D-7：2,2 '-dimethyl -4,4 '-benzidine

D-8：4,4 '-diamino-diphenyl ether

da-x：Compound represented by following formula (da-x)

[changing 24]

＜ monoamines ＞

D-4：Aniline

[synthesis example 3：The synthesis of polyamic acid (PA-1)]

Using as the molar part of the 1 of tetracarboxylic dianhydride, 2,3,4- cyclobutane tetracarboxylic dianhydride (CB) 100,2 as diamines, 2 '-dimethyl -4, the molar part of 4 '-benzidine 100, it is dissolved in NMP and gamma-butyrolacton (γ BL) (NMP: γ BL=10: 90 (weight ratio)) in the mixed solvent, carry out reacting for 3 hours at 40 DEG C, obtain containing the weight % of polyamic acid (PA-1) 10 Solution.Point take a small amount of gained polyamic acid solution, it is measured obtained by solution viscosity be 180mPas.

[synthesis example 4：The synthesis of polyamic acid (PA-2)]

In addition to by the species of used tetracarboxylic dianhydride and diamines and quantitative change more as described in the table 1, carry out Operated with the identical of synthesis example 3, be derived from the solution containing the weight % of polyamic acid (PA-2) 10.Dividing takes a small amount of gained to gather Acid amides acid solution, it is measured obtained by solution viscosity be 150mPas.

[synthesis example 5：The synthesis of polysiloxane (APS-1)]

In the reaction vessel for possessing mixer, thermometer, addition funnel and the cooling tube that flows back, 2- (3,4- epoxies are put into Cyclohexyl) ethyl trimethoxy silane (ECETS) 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, in room temperature Lower mixing.Then, from addition funnel, after spending 30 minutes dropwise addition deionized water 100g, stir under reflux on one side, while 80 Carry out reacting for 6 hours at DEG C.Reaction terminate after, take out organic layer, using 0.2 weight % aqueous ammonium nitrate solutions carry out cleaning until Untill water after cleaning turns into neutral, then, distillation under reduced pressure removes solvent and water, thus with the shape of sticky transparency liquid Formula obtains reactive polysiloxane (EPS-1).The reactive polysiloxane is carried out¹H-NMR is analyzed, and is as a result being changed Near displacement study (δ)=3.2ppm, the peak value based on epoxy radicals is obtained such as theoretical strength, confirms not produce epoxy radicals in reaction Side reaction.The weight average molecular weight Mw of the reactive polysiloxane of gained be 3,500, epoxide equivalent be 180 grams/rub You are (g/mol).

Then, in 200mL three-necked flask, reactive polysiloxane (EPS-1) 10.0g is put into, as solvent Methyl iso-butyl ketone (MIBK) 30.28g, the 4- dodecyl p-methoxybenzoic acid 3.98g as reactive compounds and as urging UCAT18X (trade name, general sieve in Sanya (San-Apro) (stock) manufacture) 0.10g of agent, is stirred at 100 DEG C while entering Row reacts for 48 hours.After reaction terminates, the solution for adding ethyl acetate in the reactive mixture and obtaining is washed 3 times, used After magnesium sulfate dries organic layer, distillation removes solvent, is derived from liquid crystal aligning polysiloxane (APS-1) 9.0g. The weight average molecular weight Mw of resulting polymers is 9,900.

[embodiment 10B, embodiment 11B]

The pyridine and second used during except by the species of used tetracarboxylic dianhydride and diamines and amount and imidizate The quantitative change of acid anhydrides more as described in Table 2 beyond, be respectively synthesized polyimides in a manner of with the embodiment 1B identicals (PI-12), polyimides (PI-13).The measurement result of the acid imide rate of resulting polymers is shown in table 2 below in the lump. In addition, the explanation on each numerical value in table 2, abbreviation and "-" is identical with the table 1.

The preparation ＞ of ＜ liquid-crystal compositions

[liquid-crystal composition LC1 preparation]

For nematic crystal (Merck (Merck) company manufactures, MLC-6608) 10g, addition following formula (pc-1) institute table The weight % of photopolymerizable compound 0.3 that shows and mixed, be derived from liquid-crystal composition LC1.

[liquid-crystal composition LC2 preparation]

For nematic crystal (Merck ＆ Co., Inc. manufactures, MLC-6608) 10g, the liquid crystal represented by the formula (L1-1) is added The property weight % of the compound 5 and weight % of photopolymerizable compound 0.3 represented by following formula (pc-1) and mixed, by This obtains liquid-crystal composition LC2.

[changing 25]

[embodiment 1C]

The preparation ＞ of ＜ aligning agent for liquid crystal

The polyimides (PI-1) obtained in containing the embodiment 1B as in the solution of polymer, addition NMP with And butyl cellosolve (BC) is used as organic solvent, solvent group is made as NMP: BC=50: 50 (weight ratios), solid component concentration For 6.0 weight % solution.The solution is filtered using the filter that aperture is 1 μm, thus prepares aligning agent for liquid crystal (S1)。

The manufacture ＞ of ＜ liquid crystal cells

Using liquid crystal orientation film printing machine (Japan's description printing (stock) manufactures), by the embodiment 1C of preparation liquid crystal Alignment agent (S1) is coated on respectively on each electrode surface of 2 pieces of glass substrates with ITO electrode, and the ITO electrode is patterned For slit-shaped as shown in Figure 1 and multiple regions are divided into, (prebake conditions) is heated in 80 DEG C of heating plate 1 minute and removed molten After agent, heating (rear baking) 10 minutes, form average film thickness as 600 in 150 DEG C of heating plateFilm.For the painting Film, after the cleaning of 1 minute ultrasonic is carried out in ultra-pure water, dried 10 minutes in 100 DEG C of cleaning ovens, be derived from having into For the substrate of the film of liquid crystal orientation film.The operation is repeated, obtains a pair of (2 pieces) substrates with film.It is in addition, used The pattern of electrode is and the electrode pattern identical pattern in PSA patterns.

Then, the alumina balls for there are a diameter of 5.5 μm are added in each outer rim with film of the pair of substrate, coating Epoxy resin adhesive after, overlapping crimping, hardens bonding agent in a manner of coated surface is relative.Then, from liquid crystal injecting port To the liquid-crystal composition LC1 that the preparation is filled between a pair of substrates, then liquid crystal is noted using acrylic acid series photo-hardening bonding agent Inlet seal.Then, in the state of the conductive intermembranous application voltage to gained liquid crystal cells, with 100,000J/m²Irradiation Amount carries out light irradiation.

The evaluation ＞ of ＜ reliabilities

Using the liquid crystal cells (liquid crystal cells after light irradiation) of the manufacture, to evaluate liquid crystal orientation film (liquid crystal display Element) reliability.Evaluated as follows.First, to described liquid crystal cells, with the application time of 60 microseconds, 167 After the span of millisecond applies 5V voltage, the voltage retention (VHR1) after 167 milliseconds from applying and releasing is determined.Then, will Liquid crystal cells stand 200 hours in 80 DEG C of baking ovens under light emitting diode (Light Emitting Diode, LED) light irradiation Afterwards, stand at room temperature and naturally cool to room temperature.After cooling, to liquid crystal cells, with the application time of 60 microseconds, 167 milliseconds Span apply 5V voltage after, determine the voltage retention (VHR2) after 167 milliseconds from applying and releasing.In addition, measure dress Put is to use (stock) Dongyang Te Kenika (Toyo Technica) manufactures " VHR-1 ".This is calculated using following numerical expressions (2) When VHR rate of change (Δ VHR), the reliability of liquid crystal orientation film is evaluated according to Δ VHR.Evaluated as follows： Situations of the Δ VHR less than 1.0% is evaluated as reliability " very good (◎) ", by Δ VHR be 1.0% less than 1.5% situation is evaluated as reliability " good (o) ", is that 1.5% less than 2.0% situation, be evaluated as can by Δ VHR By property " can (Δ) ", the situation that Δ VHR is more than 2.0% be evaluated as reliability " bad (×) ".Its result is embodiment 1C In be reliability " very good ".

Δ VHR [%]=(VHR1-VHR2)/(VHR1) × 100... (2)

＜ embodiments 2C~embodiment 9C and comparative example 1, the ＞ of comparative example 2

In addition to the composition of aligning agent for liquid crystal is changed to as described in Table 3, in a manner of with embodiment 1C identicals Aligning agent for liquid crystal is prepared respectively.In addition, using each aligning agent for liquid crystal, liquid crystal cells are manufactured in a manner of with embodiment 1C identicals, And the liquid crystal cells of the manufacture are evaluated.In addition, on embodiment 3C, embodiment 4C, by used liquid crystal group Compound is changed to LC2 by LC1.These evaluation results are shown in Table 3 below.

[table 3]

As shown in table 3, it is in embodiment 1C~embodiment 9C：Even if when long under light irradiation, 80 DEG C of ambient stress Between after exposure in (200 hours), the fall of voltage retention is few, and reliability is good.On the other hand, comparative example 1, comparative example 2 In, significantly decline because assigning photostress and thermal stress, voltage retention.

And then except the pattern of the ITO electrode 1 on glass substrate is changed into fish-bone as shown in Figures 2 and 3 respectively Beyond (fish bone) shape electrode pattern, using the aligning agent for liquid crystal of the embodiment 1C~embodiment 9C, with the implementation Example 1C identical modes manufacture liquid crystal cells, are evaluated.Also show in this case and embodiment 1C~9C points of embodiment Other identical effect.

＜ embodiments 10C, embodiment 11C ＞

In addition to the composition of aligning agent for liquid crystal is changed to as described in Table 4, in a manner of with embodiment 1C identicals Aligning agent for liquid crystal is prepared respectively.In addition, using each aligning agent for liquid crystal, liquid crystal cells are manufactured in a manner of with embodiment 1C identicals, And the liquid crystal cells of the manufacture are evaluated.It the results are shown in table 4 below.

[table 4]

As shown in table 4, comprising the Q used in the formula (d-1A)¹It is the diamines of nitrogen-atoms the reality of polymer that synthesizes Apply in a 10C, be reliability " very good ".In addition, comprising using Q¹It is the diamines of carbon atom the reality of polymer that synthesizes Apply in a 11C, be the evaluation of reliability "available".And then except the pattern of the ITO electrode on glass substrate is changed into figure respectively Beyond 2 and Fig. 3 electrode pattern, using the embodiment 10C, embodiment 11C aligning agent for liquid crystal, with the embodiment 1C Identical mode manufactures liquid crystal cells, is evaluated.Also show identical result respectively in this case.

Claims

1. a kind of aligning agent for liquid crystal, it contains the polymer (P) with the specific structure represented by following formula (1A)：

In formula (1A), R²For divalent organic group, X¹For pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine Ring or pyrazine ring；Wherein, multiple R in formula²Can be with identical, can also be different, multiple X¹Can be with identical, can also be different；Q¹ For nitrogen-atoms, Y¹For hydrogen atom or the alkyl of carbon number 1~5；T=2 and s=0.

2. aligning agent for liquid crystal according to claim 1, wherein the specific structure is represented by following formula (1-1A)：

In formula (1-1A), R³For the alkane diyl of carbon number 1~5；R⁴For the alkane diyl of singly-bound or carbon number 1~5, A¹For singly-bound ,- O-、-CO-、*¹-COO-、*¹-OCO-、*¹- CONH- or *¹- NHCO-, " *¹" represent and R³Associative key；Multiple R in formula³Can , can also be different with identical, multiple R⁴Can be with identical, can also be different, multiple A¹Can be with identical, can also be different；X¹、Q¹、Y¹、 T and s is identical with the formula (1A) implication；" * " represents associative key.

3. aligning agent for liquid crystal according to claim 1, wherein the polymer (P) is selected from by polyamic acid, polyamide At least one of group that acid esters and polyimides are formed.

4. aligning agent for liquid crystal according to claim 3, wherein the polymer (P) is to make to be selected from by tetracarboxylic dianhydride, four At least one of the group that carboxylic acid diesters and tetracarboxylic acid acid diesters dihalide are formed compound, is reacted and is obtained with diamines The polymer obtained, and

The diamines includes the compound represented by following formula (d-1A)：

In formula (d-1A), R¹For singly-bound or divalent organic group；R²、X¹、Q¹、Y¹, t and s it is identical with the formula (1A) implication.

5. aligning agent for liquid crystal according to any one of claim 1 to 4, wherein the polymer (P) is made to be selected from by 2, 3,5- tricarboxylic cyclopentyl acetic acid dianhydride, bicyclic [3.3.0] octane -2 of 2,4,6,8- tetracarboxylics:4,6:8- dianhydrides, 1,2,3,4- The group that cyclobutane tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylics dianhydride and 1,2,3,4- pentamethylene tetracarboxylic dianhydrides are formed At least one of group tetracarboxylic dianhydride, the polymer for being reacted and being obtained with the diamines with the specific structure.

6. a kind of liquid crystal orientation film, it is formed using the aligning agent for liquid crystal as any one of claim 1 to 5.

7. a kind of liquid crystal display cells, it includes liquid crystal orientation film as claimed in claim 6.

8. a kind of manufacture method of liquid crystal display cells, it includes：

Aligning agent for liquid crystal as any one of claim 1 to 5 to be respectively coated on to a pair of substrates with conducting film On the conducting film, the step of being then heated and form film；

Across the liquid crystal layer comprising liquid crystal compounds, by a pair of substrates formed with the film with the film to side The step of formula configuration is to construct liquid crystal cells；And

In the state of to conductive intermembranous application voltage possessed by the pair of substrate, light irradiation is carried out to the liquid crystal cells The step of.

9. the manufacture method of liquid crystal display cells according to claim 8, it is included with an alkenyl and fluorine alkenyl The mono-functional's liquid crystal compounds of any one are as the liquid crystal compounds.

10. a kind of polymer containing nitrogenous heteroaromatic, it has the specific structure represented by following formula (1A)：

11. a kind of compound containing nitrogenous heteroaromatic, it is represented by following formula (d-1A)：

In formula (d-1A), R¹For singly-bound or divalent organic group, R²For divalent organic group, X¹For pyrrole ring, imidazole ring, pyrazole ring, triazole Ring, pyridine ring, pyrimidine ring, pyridazine ring or pyrazine ring；Wherein, multiple R in formula²Can be with identical, can also be different, multiple X¹ Can be with identical, can also be different；Q¹For nitrogen-atoms, Y¹For hydrogen atom or the alkyl of carbon number 1~5；T=2 and s=0.