CN102574811B - Diamine compound, polyamic acid, polyimide and aligning agent for liquid crystal - Google Patents
Diamine compound, polyamic acid, polyimide and aligning agent for liquid crystal Download PDFInfo
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- CN102574811B CN102574811B CN201080043007.1A CN201080043007A CN102574811B CN 102574811 B CN102574811 B CN 102574811B CN 201080043007 A CN201080043007 A CN 201080043007A CN 102574811 B CN102574811 B CN 102574811B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D241/20—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Abstract
The invention provides to can be used as forming and can obtain voltage retention high and the polyamic acid of aligning agent for liquid crystal of liquid crystal orientation film that the long-time alleviation exposing the residual charge gathered because of volts DS is at high temperature also fast and/or the novel diamine compound of the raw material of polyimide.The novel diamine compound represented with formula [1] and the aligning agent for liquid crystal comprising polyamic acid and/or the polyimide using this diamine compound to obtain, [changing 1]
in formula, X
1represent-CO-or-CONH-, X
2represent the alkylidene group of carbon number 1 ~ 5 or the non-aromatic heterocyclic of nitrogen atom, X
3what expression can be replaced by the alkyl of carbon number 1 ~ 5 contains the five-ring of 2 nitrogen-atoms or the heteroaromatic of six-ring.
Description
Technical field
The polyamic acid the present invention relates to the novel diamine compound of the raw material of the polymkeric substance that can be used as liquid crystal orientation film, using it to obtain and polyimide and aligning agent for liquid crystal.The invention still further relates to the liquid crystal display device with the liquid crystal orientation film obtained by described aligning agent for liquid crystal.
Background technology
At present, as the liquid crystal orientation film of liquid crystal display device, the so-called polyimide liquid crystal orientation film of main employing, this liquid crystal orientation film is by coating glass substrate etc. and burning till and obtain by the aligning agent for liquid crystal (also claiming liquid crystal aligning agent) that is main component with the solution of the polyimide precursors such as polyamic acid or soluble polyimide.
Liquid crystal orientation film is state of orientation in order to control liquid crystal and uses.But, along with the high-precision refinement of liquid crystal display device, require that the contrast gradient suppressing liquid crystal display device declines, reduces ghost phenomena etc., so for used liquid crystal orientation film, the characteristics such as voltage retention is high, residual charge when applying volts DS is few and/or the alleviation of residual charge gathered because of volts DS is fast are also important gradually.
In polyimide liquid crystal orientation film, the liquid crystal orientation film that time till disappearing as the ghost that produces because of volts DS is short, known use also comprise except the polyamic acid of polyamic acid or imido-the liquid crystal aligning agent of the tertiary amine of ad hoc structure liquid crystal orientation film (reference example is as patent documentation 1), use and comprise the liquid crystal orientation film (reference example is as patent documentation 2) etc. that the specific diamine compound will with pyridine skeleton etc. is used as the liquid crystal aligning agent of the soluble polyimide of raw material.In addition, time short liquid crystal orientation film till and the ghost produced because of volts DS high as voltage retention disappears, what known use also comprised minute quantity except polyamic acid or its imide amination polymer etc. is selected from the liquid crystal orientation film (reference example is as patent documentation 3) that molecule includes the compound of 1 carboxyl, molecule includes 1 acid anhydride compound and molecule include the liquid crystal aligning agent of the compound of the compound of 1 tertiary amine groups.
But, the LCD TV of large picture, fine is widely practical in recent years, liquid crystal display device in this purposes compared with mainly showing the display applications of word or still frame in the past, requirement for ghost is more strict, and require to have can under harsh environment for use the characteristic of life-time service.Therefore, the liquid crystal orientation film used needs the product that reliability is higher than ever, and about the electrical characteristic of liquid crystal orientation film, also require that not only initial characteristic is good, such as long-time exposure at high temperature also maintains good characteristic.
At first technical literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 9-316200 publication
Patent documentation 2: Japanese Patent Laid-Open 10-104633 publication
Patent documentation 3: Japanese Patent Laid-Open 8-76128 publication
The summary of invention
Invent problem to be solved
The object of the present invention is to provide to can be used as being formed and can obtain voltage retention high and the polyamic acid of aligning agent for liquid crystal of liquid crystal orientation film that the long-time alleviation exposing the residual charge gathered because of volts DS is at high temperature also fast and/or the diamine compound of the raw material of polyimide (also claiming polymkeric substance below).
In addition, the object of the present invention is to provide and can obtain the high and aligning agent for liquid crystal of the liquid crystal orientation film that the long-time alleviation exposing the residual charge gathered because of volts DS is at high temperature also fast of voltage retention and the high liquid crystal display device of the long term reliability under harsh environment for use can be tolerated.
Solve the means of problem
The present inventor studies the diamine compound that rear discovery has specific new texture to achieve these goals and conscientiously, and the aligning agent for liquid crystal comprising the polymkeric substance using this diamine compound to obtain can realize above-mentioned purpose.The present invention is based on above-mentioned discovery, there is following technology contents.
(1) diamine compound of following formula [1];
[changing 1]
In formula, X
1represent-CO-,-CONH-, X
2represent the alkylidene group of carbon number 1 ~ 5 or the non-aromatic heterocyclic of nitrogen atom, X
3what expression can be replaced by the alkyl of carbon number 1 ~ 5 contains the five-ring of 2 nitrogen-atoms or the heteroaromatic of six-ring.
(2) diamine compound as described in above-mentioned (1), described heteroaromatic is imidazole ring, pyrazine ring or pyrimidine ring.
(3) diamine compound as described in above-mentioned (1) or (2), the non-aromatic heterocyclic of described nitrogen atom is piperazine ring.
(4) polyimide that maybe obtained by this polyamic acid imidization of polyamic acid, described polyamic acid is reacted by the diamine component and tetracarboxylic dianhydride's composition making the diamine compound comprised described in any one in above-mentioned (1) ~ (3) and is obtained.
(5) polyimide that this polyamic acid imidization maybe obtains by the polyamic acid as described in above-mentioned (4), in described diamine component, the content of the diamine compound described in any one in above-mentioned (1) ~ (3) is 1 ~ 80 % by mole.
(6) polyimide that this polyamic acid imidization maybe obtains by the polyamic acid as described in above-mentioned (4), comprises carboxylic diamine compound in molecule in described diamine component.
(7) polyimide that this polyamic acid imidization maybe obtains by the polyamic acid as described in above-mentioned (6), in described diamine component, the diamines described in any one in (1) ~ (3) above-mentioned relative to 1 mole, in molecule, the content of carboxylic diamine compound is 0.01 ~ 99 mole.
(8) polyimide that this polyamic acid imidization maybe obtains by the polyamic acid as described in above-mentioned (6) or (7), in described molecule, carboxylic diamine compound is the diamines represented with following formula [2];
[changing 2]
In formula [2], X
5for the organic group with aromatic nucleus of carbon number 6 ~ 30, n is the integer of 1 ~ 4.
(9) aligning agent for liquid crystal, comprises at least one party in the polyamic acid described in any one in above-mentioned (4) ~ (8) and the polyimide that obtained by this polyamic acid imidization and solvent.
(10) aligning agent for liquid crystal as described in above-mentioned (9), 5 ~ 80 quality % in described solvent are poor solvent.
(11) liquid crystal orientation film, is obtained by the aligning agent for liquid crystal described in above-mentioned (9) or (10).
(12) liquid crystal display device, has the liquid crystal orientation film described in above-mentioned (11).
The effect of invention
Diamine compound of the present invention is the new diamines (also claiming specific diamine compound below) comprising the ad hoc structure had containing the five-ring of 2 nitrogen-atoms or the heteroaromatic of six-ring at side chain, obtains by easier method.The effect being played the jump site of electronics containing the five-ring of 2 nitrogen-atoms or the heteroaromatic of six-ring by its conjugated structure in this specific diamine compound, so the liquid crystal orientation film obtained by the polyamic acid and/or the polyimide polymer that obtain by this polyamic acid imidization that use specific diamine compound can promote that the electric charge in liquid crystal orientation film moves, the high and characteristic that alleviation that is residual charge that is that gather because of volts DS after long-time exposure at high temperature is also fast of voltage retention can be had.
Thus, the reliability with the liquid crystal display device of the liquid crystal orientation film obtained by the aligning agent for liquid crystal comprising the polyamic acid and/or polyimide polymer that employ diamine compound of the present invention of the present invention is good, is suitable for the LCD TV etc. of large picture, fine.
The mode carried out an invention
< specific diamine compound >
Specific diamine compound of the present invention represents with following formula [1].
[changing 3]
In formula, X
1represent-CO-or-CONH-, X
2represent the alkylidene group of carbon number 1 ~ 5 or the non-aromatic heterocyclic of nitrogen atom, X
3what expression can be replaced by the alkyl of carbon number 1 ~ 5 contains the five-ring of 2 nitrogen-atoms or the heteroaromatic of six-ring.
2 amino (-NH in formula [1]
2) binding site indefinite.Specifically, relative to the conjugated group (X of side chain
1), the prosposition on phenyl ring, 2 can be exemplified, 4,2,5,2,6,3,4,3,5.Wherein, from reactive viewpoint during synthesizing polyamides acid, difficulty during synthesis diamine compound is added, 2 amino binding sites particularly preferably 2,4,2,5,3,5.
In formula [1], X
1for-CO-or-CONH-.
In formula [1], X
2for the alkylidene group of carbon number 1 ~ 5 or the non-aromatic heterocyclic of nitrogen atom.
X
2during alkylidene group for carbon number 1 ~ 5, this alkylidene group can be straight-chain, also can branch-like.The carbon number of alkylidene group particularly preferably 1 ~ 3.
In addition, X
2during non-aromatic heterocyclic for nitrogen atom, as an example, pyrrolidine ring, piperidine ring, piperazine ring, pyrazolidine ring, rubane, imidazolidine ring can be exemplified.Non-aromatic heterocyclic is that the compound of five-ring or six-ring can obtain good orientation when making liquid crystal orientation film, so particularly preferably.In addition, when non-aromatic heterocyclic is containing 2 nitrogen-atoms, when making liquid crystal display device, the ionic impurity in liquid crystal orientation film interfacial adsorption liquid crystal, keeps the good electrical characteristic of liquid crystal display device, so preferably.According to above viewpoint, as the non-aromatic heterocyclic of nitrogen atom, particularly preferably piperazine ring.
If X
2with X
3in nitrogen-atoms or adjacent described nitrogen-atoms atom, be better that carbon atom combines, then the easy effect playing the residual charge accelerating to gather because of volts DS and alleviate in liquid crystal display device.
In formula [1], X
3be can by the alkyl of carbon number 1 ~ 5 replace containing the five-ring of 2 nitrogen-atoms or the heteroaromatic of six-ring.As the example containing the five-ring of 2 nitrogen-atoms or the heteroaromatic of six-ring, can exemplify imidazole ring, pyrazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, be better wherein imidazole ring, pyrazine ring or pyrimidine ring.X
3in heteroaromatic when being replaced by alkyl, the carbon number of this alkyl is better 1 ~ 3.
X in above-mentioned formula [1]
1, X
2and X
3preferred concrete combination table 1 described as follows and table 2 shown in.
[table 1]
| X 1 | X 2 | X 3 | |
| A-1 | -CO- | The alkylidene group of carbon number 1 ~ 3 | Imidazole ring |
| A-2 | -CO- | The alkylidene group of carbon number 1 ~ 3 | Pyrazine ring |
| A-3 | -CO- | The alkylidene group of carbon number 1 ~ 3 | Pyrimidine ring |
| A-4 | -CO- | Pyrrolidine ring | Imidazole ring |
| A-5 | -CO- | Pyrrolidine ring | Pyrazine ring |
| A-6 | -CO- | Pyrrolidine ring | Pyrimidine ring |
| A-7 | -CO- | Piperidine ring | Imidazole ring |
| A-8 | -CO- | Piperidine ring | Pyrazine ring |
| A-9 | -CO- | Piperidine ring | Pyrimidine ring |
| A-10 | -CO- | Piperazine ring | Imidazole ring |
| A-11 | -CO- | Piperazine ring | Pyrazine ring |
| A-12 | -CO- | Piperazine ring | Pyrimidine ring |
| A-13 | -CO- | Pyrazolidine ring | Imidazole ring |
| A-14 | -CO- | Pyrazolidine ring | Pyrazine ring |
| A-15 | -CO- | Pyrazolidine ring | Pyrimidine ring |
| A-16 | -CO- | Rubane | Imidazole ring |
| A-17 | -CO- | Rubane | Pyrazine ring |
| A-18 | -CO- | Rubane | Pyrimidine ring |
| A-19 | -CO- | Imidazolidine ring | Imidazole ring |
| A-20 | -CO- | Imidazolidine ring | Pyrazine ring |
| A-21 | -CO- | Imidazolidine ring | Pyrimidine ring |
[table 2]
| X 1 | X 2 | X 3 | |
| A-22 | -CONH- | The alkylidene group of carbon number 1 ~ 3 | Imidazole ring |
| A-23 | -CONH- | The alkylidene group of carbon number 1 ~ 3 | Pyrazine ring |
| A-24 | -CONH- | The alkylidene group of carbon number 1 ~ 3 | Pyrimidine ring |
| A-25 | -CONH- | Pyrrolidine ring | Imidazole ring |
| A-26 | -CONH- | Pyrrolidine ring | Pyrazine ring |
| A-27 | -CONH- | Pyrrolidine ring | Pyrimidine ring |
| A-28 | -CONH- | Piperidine ring | Imidazole ring |
| A-29 | -CONH- | Piperidine ring | Pyrazine ring |
| A-30 | -CONH- | Piperidine ring | Pyrimidine ring |
| A-31 | -CONH- | Piperazine ring | Imidazole ring |
| A-32 | -CONH- | Piperazine ring | Pyrazine ring |
| A-33 | -CONH- | Piperazine ring | Pyrimidine ring |
| A-34 | -CONH- | Pyrazolidine ring | Imidazole ring |
| A-35 | -CONH- | Pyrazolidine ring | Pyrazine ring |
| A-36 | -CONH- | Pyrazolidine ring | Pyrimidine ring |
| A-37 | -CONH- | Rubane | Imidazole ring |
| A-38 | -CONH- | Rubane | Pyrazine ring |
| A-39 | -CONH- | Rubane | Pyrimidine ring |
| A-40 | -CONH- | Imidazolidine ring | Imidazole ring |
| A-41 | -CONH- | Imidazolidine ring | Pyrazine ring |
| A-42 | -CONH- | Imidazolidine ring | Pyrimidine ring |
The synthetic method > of < specific diamine compound
The method manufacturing the specific diamine compound that formula of the present invention [1] represents is not particularly limited, and as preferred method, can exemplify following method.
[changing 4]
Specific diamine compound of the present invention is by synthesizing the dinitro compound represented with formula [3], then the nitroreduction had by dinitro compound becomes amino to obtain.The method that dinitro compound reduces is not particularly limited, usually has and use palladium carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminum oxide, platinum sulfide carbon etc. as catalyzer at ethyl acetate, toluene, tetrahydrofuran (THF), two
the method of being undertaken by hydrogen, hydrazine, hydrogenchloride etc. in alkane, alcohols equal solvent.X in formula [3]
1, X
2and X
3definition identical with the definition of formula [1].
The dinitro compound represented with formula [3] can by making-X
2-X
3be situated between with X
1the method etc. be combined with dinitrobenzene obtains, such as X
1when for amido linkage (-CONH-), can exemplify and make dinitrobenzoyl chloride and contain X
2and X
3the aminocompound method of reacting in the presence of base.In addition, X
1when for reverse amido linkage (-HNCO-), can exemplify and make containing amino oil of mirbane and containing X
2and X
3the acyl chlorides method of reacting in the presence of base.
As above-mentioned dinitrobenzoyl chloride, 3,5 dinitrobenzoylchloride, 3,5-dinitrobenzoic acids, 2,4-dinitrobenzoyl chlorides, 3,5-dinitrobenzene methyl chlorides, 2,4-dinitrobenzene methyl chlorides can be exemplified; As containing amino oil of mirbane, 2,4-dinitraniline, 3,5-dinitranilines, 2,6-dinitranilines etc. can be exemplified.The acquisition difficulty of raw material, reaction can be considered, select one or more to use.
< polymkeric substance >
Polymkeric substance of the present invention is the reaction of diamine component and tetracarboxylic dianhydride by comprising specific diamine compound and the polyamic acid obtained and the polyimide making this polyamic acid dehydration closed-loop and obtain.These polyamic acids and polyimide all can be used as the polymkeric substance for obtaining liquid crystal orientation film.
In the liquid crystal orientation film using polymkeric substance of the present invention to obtain, containing of specific diamine compound in above-mentioned diamine component is proportional higher, then voltage retention is higher, and the alleviation of the residual charge gathered because of volts DS after long-time exposure is at high temperature also faster.
In order to improve above-mentioned characteristic, be better that more than 1 % by mole of diamine component is specific diamine compound.Be more preferably more than 5 % by mole of diamine component for specific diamine compound, be more preferably more than 10 % by mole further.
Can be 100 % by mole of diamine component be specific diamine compound, but from the angle of uniform applicability during coating of liquid crystalline aligning agent, specific diamine compound it be better less than 80 % by mole of diamine component, is more preferably less than 40 % by mole.
Carboxylic diamine compound > in < molecule
In the present invention, as diamine component, when using carboxylic diamine compound in molecule while using specific diamine compound, the heteroaromatic containing 2 nitrogen-atoms that above-mentioned specific diamine compound has is combined by the electrostatic interaction such as salify or the hydrogen bond carboxyl that carboxylic diamine compound has in molecule, thus between carboxyl and nitrogenous heteroaromatic, the movement of electric charge occurs.Therefore, move to nitrogenous heteroaromatic position electric charge can efficiently in the molecule of multipolymer, intermolecular movement, consequently, the aligning agent for liquid crystal at this moment obtained plays the high and long-time alleviation effect faster exposing the residual charge gathered because of volts DS at high temperature of voltage retention when making liquid crystal orientation film.
In molecule, the concrete structure of carboxylic diamine compound is not particularly limited, and is better the compound represented with formula [2].
[changing 5]
In formula [2], X
5for the organic group with aromatic nucleus of carbon number 6 ~ 30, n is the integer of 1 ~ 4.
To carry out concrete example to formula [2], then can exemplify the structure of following formula [3] ~ [7].
[changing 6]
In formula [3], m1 is the integer of 1 ~ 4; In formula [4], X
6for singly-bound ,-CH
2-,-C
2h
4-,-C (CH
3)
2-,-CF
2-,-C (CF
3)
2-,-O-,-CO-,-NH-,-N (CH
3)-,-CONH-,-NHCO-,-CH
2o-,-OCH
2-,-COO-,-OCO-,-CON (CH
3)-or-N (CH
3) CO-, m2 and m3 be respectively 0 ~ 4 integer and m2+m3 represent 1 ~ 4 integer; In formula [5], m4 and m5 is respectively the integer of 1 ~ 5; In formula [6], X
7for straight chain or the branched alkyl groups of carbon number 1 ~ 5, m6 is the integer of 1 ~ 5; In formula [7], X
8for singly-bound ,-CH
2-,-C
2h
4-,-C (CH
3)
2-,-CF
2-,-C (CF
3)
2-,-O-,-CO-,-NH-,-N (CH
3)-,-CONH-,-NHCO-,-CH
2o-,-OCH
2-,-COO-,-OCO-,-CON (CH
3)-or-N (CH
3) CO-, m7 be the integer of 1 ~ 4.
In the structure of formula [3] ~ [7], be better that in formula [3], m1 is the structure of the integer of 1 ~ 2, X in formula [4]
6for singly-bound ,-CH
2-,-C
2h
4-,-C (CH
3)
2-,-O-,-CO-,-NH-,-N (CH
3)-,-CONH-,-NHCO-,-COO-or-OCO-and m2 and m3 be the structure of integer 1, X in formula [7]
8for singly-bound ,-CH
2-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH
2o-,-OCH
2-,-COO-or-OCO-and m7 be the structure of the integer of 1 ~ 2.
As the object lesson of the diamine compound represented with formula [3] ~ formula [7], the compound of following formula [8] ~ formula [18] can be exemplified.
[changing 7]
[changing 8]
In formula [17], X
9for singly-bound ,-CH
2-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH
2o-,-OCH
2-,-COO-or-OCO-; In formula [18], X
10for singly-bound ,-CH
2-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH
2o-,-OCH
2-,-COO-or-OCO-.
[other diamine compound]
In the present invention, only otherwise destroy effect of the present invention, except carboxylic diamine compound in specific diamine compound and above-mentioned molecule, can also and with other diamine compound as diamine component.Below, its object lesson is exemplified:
Ursol D, 2,3,5,6-tetramethyl-para-phenylene diamine, 2,5-dimethyl-p-phenylenediamine, mphenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamino benzylalcohol, 2,4-diamino benzylalcohol, 4,6-diaminoresorcinol, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-benzidine, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 2,2 '-diamino-diphenyl ether, 2,3 '-diamino-diphenyl ether, diaphenylsulfone, 3,3 '-sulfonyldianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4 '-diamino diphenyl sulfide, 3,3 '-diamino diphenyl sulfide, 4,4 '-diamino-diphenyl amine, 3,3 '-diamino-diphenyl amine, 3,4 '-diamino-diphenyl amine, 2,2 '-diamino-diphenyl amine, 2,3 '-diamino-diphenyl amine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diamino benzophenone, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2 '-diamino benzophenone, 2,3 '-diamino benzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, two (3-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, Isosorbide-5-Nitrae-bis-(3-aminophenyl) butane, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminobenzyl) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] pentanoic, 4,4 '-[1,3-phenylene two (methylene radical)] pentanoic, 3,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] pentanoic, 3,4 '-[1,3-phenylene two (methylene radical)] pentanoic, 3,3 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] pentanoic, 3,3 '-[1,3-phenylene two (methylene radical)] pentanoic, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N '-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamide), N, N '-(1,3-phenylene) two (4-aminobenzamide), N, N '-(Isosorbide-5-Nitrae-phenylene) two (3-AB), N, N '-(1,3-phenylene) two (3-AB), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyl) terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, two (4-aminophenyl) anthracene of 9,10-, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 2,2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane, two (4-amino-benzene oxygen) propane of 1,3-, two (3-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (3-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (3-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (3-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octane of 1,8-, two (3-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (3-amino-benzene oxygen) nonane of 1,9-, two (4-amino-benzene oxygen) decane of 1,10-, two (3-amino-benzene oxygen) decane of 1,10-, two (4-amino-benzene oxygen) undecane of 1,11-, two (3-amino-benzene oxygen) undecane of 1,11-, two (4-amino-benzene oxygen) dodecane of 1,12-, two (3-amino-benzene oxygen) dodecane of 1,12-.Also can exemplify two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-diaminobutane, 1,5-1,5-DAP, 1，6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1,11-diamino undecane, 1,12-diamino dodecane etc.
In addition, also can exemplify and there is alkyl, containing fluoroalkyl, aromatic nucleus, aliphatics ring, heterocycle and their diamine compounds of cyclic substituents of being formed as two amine side chains.As the object lesson of this diamine compound, the diamine compound represented with following formula [DA1] ~ formula [DA26] can be exemplified.
[changing 9]
In formula [DA1] ~ formula [DA5], R
1for the alkyl of carbon number less than more than 1 22 or containing fluoroalkyl.
[changing 10]
In formula [DA6] ~ formula [DA9], R
2represent-COO-,-OCO-,-CONH-,-NHCO-,-CH
2-,-O-,-CO-or-NH-, R
3represent the alkyl of carbon number less than more than 1 22 or contain fluoroalkyl.
[changing 11]
In formula [DA10] ~ formula [DA11], R
4represent-O-,-OCH
2-,-CH
2o-,-COOCH
2-or-CH
2oCO-, R
5represent the alkyl of carbon number less than more than 1 22, alkoxyl group, containing fluoroalkyl or fluoroalkoxy.
[changing 12]
In formula [DA12] ~ formula [DA14], R
6represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH
2-,-CH
2oCO-,-CH
2o-,-OCH
2-or-CH
2-, R
7represent the alkyl of carbon number less than more than 1 22, alkoxyl group, containing fluoroalkyl or fluoroalkoxy.
[changing 13]
In formula [DA15] and formula [DA16], R
8represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH
2-,-CH
2oCO-,-CH
2o-,-OCH
2-,-CH
2-,-O-or-NH-, R
9represent fluorine-based, cyano group, trifluoromethyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl.
[changing 14]
[changing 15]
[changing 16]
In addition, the diamino siloxanes etc. represented with following formula [DA27] can also be exemplified.
[changing 17]
In formula [DA27], m is the integer of 1 ~ 10.
Other diamine compound can use a kind or be mixed with two or more according to the characteristic such as liquid crystal aligning, voltage preserving property, Accumulating charge when making liquid crystal orientation film.
< tetracarboxylic dianhydride >
The tetracarboxylic dianhydride reacting to obtain polyamic acid of the present invention with diamine component is not particularly limited.Below, its preferred object lesson is exemplified:
Pyromellitic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) ether, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) sulfone, two (3,4-dicarboxyphenyi) methane, two (3, the 4-dicarboxyphenyi) propane of 2,2-, two (3, the 4-dicarboxyphenyi) propane of 1,1,1,3,3,3-hexafluoro-2,2-, two (3,4-dicarboxyphenyi) dimethylsilane, two (3,4-dicarboxyphenyi) diphenyl silane, 2,3,4,5-pyridine tetracarboxylic dianhydride, two (3, the 4-dicarboxyphenyi) pyridine of 2,6-, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,3-phenylbenzene-1,2,3,4-tetramethylene tetracarboxylic dianhydride, the two adjacent benzene tertacarbonic acid's dianhydride (Japanese: オ キ シ ジ Off タ Le テ ト ラ カ Le ボ Application Suan bis-No water thing) of oxygen, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-suberane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 3,4-dicarboxyl-1-cyclohexyl succsinic acid dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthyl succsinic acid dianhydride, two rings [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, two rings [4.3.0] nonane-2,4,7,9-tetracarboxylic dianhydride, two rings [4.4.0] decane-2,4,7,9-tetracarboxylic dianhydride, two rings [4.4.0] decane-2,4,8,10-tetracarboxylic dianhydride, three rings [6.3.0.0<2,6>] undecane-3,5,9,11-tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, 4-(2,5-dioxotetrahydro furans-3-base)-1,2,3,4-naphthane-1,2-dicarboxylic acid dianhydride, two rings [2.2.2] pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-hexanaphthene-1,2-dicarboxylic acid dianhydride, Fourth Ring [6.2.1.1.0.2.7] dodecane-4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tri-carboxyl norbornane-2:3,5:6 dicarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride etc.
Tetracarboxylic dianhydride can use a kind or be mixed with two or more according to the characteristic such as liquid crystal aligning, voltage preserving property, Accumulating charge when making liquid crystal orientation film.
When obtaining polyamic acid of the present invention by the reaction of tetracarboxylic dianhydride and diamine component, known synthetic method can be used.Be generally the method that tetracarboxylic dianhydride and diamine component are reacted in organic solvent.Tetracarboxylic dianhydride carries out than being easier in organic solvent with the reaction of diamine component, and do not generate in by product favourable.
As the organic solvent of the reaction for tetracarboxylic dianhydride and diamine component, as long as the polyamic acid that solubilized generates, be not particularly limited.Below, its object lesson is exemplified:
DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolactone, Virahol, methoxymethyl amylalcohol, kautschin, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methylcyclohexane, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, Diethylene Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentaacetic acid ester, butyl butyric ester, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, hexyl ether, two
alkane, normal hexane, Skellysolve A, octane, Anaesthetie Ether, pimelinketone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methylethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diglyme, 4-hydroxy-4-methyl-2-pentanone etc.They can be used alone, also can be used in combination.In addition, even the solvent that polyamic acid dissolves cannot be made, in the scope that the polyamic acid generated can not be separated out, can be mixed in above-mentioned solvent and use.
In addition, the moisture in organic solvent hinders polyreaction, also can cause the polyamic acid hydrolysis generated, so organic solvent is better use the solvent after dehydrating as far as possible.
When tetracarboxylic dianhydride and diamine component are reacted in organic solvent, can exemplify to stir makes diamine component be dispersed or dissolved in organic solvent and the solution that obtain, then directly interpolation tetracarboxylic dianhydride or the method for adding again after tetracarboxylic dianhydride is dispersed or dissolved in organic solvent; On the contrary, diamine component is added into makes tetracarboxylic dianhydride be dispersed or dissolved in organic solvent and the method for the solution obtained; Alternately add the method etc. of tetracarboxylic dianhydride and diamine component, any one method wherein can be used.In addition, when tetracarboxylic dianhydride or diamine component comprise multiple compounds, can react under the state be pre-mixed, also can react successively respectively, can also make to react respectively and obtain low-molecular weight mixing after carry out reaction to make high molecular body.
At this moment polymerization temperature can select the arbitrary temp of-20 DEG C ~ 150 DEG C, is better in the scope of-5 DEG C ~ 100 DEG C.In addition, reaction can be carried out with arbitrary concentration, if but concentration is too low, then be difficult to the polymkeric substance obtaining high molecular, if excessive concentration, then the viscosity of reaction solution is excessive, is difficult to stir, so the total concn in the reaction soln of tetracarboxylic dianhydride and diamine component is better 1 ~ 50 quality %, be more preferably 5 ~ 30 quality %.Initial reaction stage can carry out in higher concentrations, then add organic solvent.
In the polyreaction of polyamic acid, the ratio of the total mole number of tetracarboxylic dianhydride and the total mole number of diamine component is better 0.8 ~ 1.2.Same with common polyreaction, this mol ratio is more close to 1.0, then the molecular weight of the polyamic acid generated is larger.
Polyimide of the present invention is the polyimide making above-mentioned polyamic acid dehydration closed-loop and obtain, and can be used as the polymkeric substance for obtaining liquid crystal orientation film.
In polyimide of the present invention, the dehydration closed-loop rate (imide rate) of acid amides acidic group is not necessary for 100%, at random can adjust according to purposes or object.
As the method making polyamic acid imidization, can exemplify direct-fired for the solution of polyamic acid hot-imide, the catalyzer imidization adding catalyzer in the solution of polyamic acid.
Make polyamic acid in the solution hot-imide time temperature be 100 DEG C ~ 400 DEG C, being better 120 DEG C ~ 250 DEG C, is better carry out while being expelled to outside system by the water generated by imidization reaction.
The catalyzer imidization of polyamic acid by adding basic catalyst and acid anhydrides in the solution of polyamic acid ,-20 DEG C ~ 250 DEG C, be better that 0 DEG C ~ 180 DEG C stirrings are carried out.The amount of basic catalyst, mole to count 0.5 ~ 30 times of acid amides acidic group, is better 2 ~ 20 times, and the amount of acid anhydrides, mole to count 1 ~ 50 times of acid amides acidic group, is better 3 ~ 30 times.As basic catalyst, can exemplify pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc., wherein pyridine has the alkalescence being suitable for carrying out reacting, so preferably.In addition, as acid anhydrides, diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc. can be exemplified, wherein, if use diacetyl oxide, then react the purifying after terminating easily, so preferably.The imide rate of catalyzer imidization is adopted to control by regulating catalytic amount and temperature of reaction, reaction times.
When reclaiming from the reaction soln of polyimide or polyimide the polyamic acid or polyimide that generate, reaction soln is dropped in poor solvent and lose it and precipitate.As the poor solvent for precipitating, methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc. can be exemplified.Drop into poor solvent and the polymkeric substance that precipitates can after filtered and recycled under normal pressure or decompression normal temperature or heat drying.In addition, if the polymkeric substance making precipitation reclaim is dissolved in organic solvent again, repeats the operation that 2 ~ 10 times redeposition reclaims, then can reduce the impurity in polymkeric substance.As poor solvent at this moment, can exemplify such as alcohols, ketone, hydrocarbon etc., if use the poor solvent being selected from their more than 3 kinds, then purification efficiency improves further, so preferably.
Operability when considering by the painting film strength of its acquisition and form film, the homogeneity of film, polyamic acid contained by aligning agent for liquid crystal of the present invention and the molecular weight of polyimide are to pass through GPC (gel permeation chromatography, Gel Permeation Chromatography) to haggle over be 5000 ~ 1000000 to the weight-average molecular weight that measures of method, is more preferably 10000 ~ 150000.
< aligning agent for liquid crystal >
Aligning agent for liquid crystal of the present invention is the coating fluid for the formation of liquid crystal orientation film, is to be dissolved in for the formation of the macromolecule component of polymer tunicle the solution obtained in solvent.Here, described macromolecule component comprises at least one polymkeric substance in above-mentioned polymkeric substance of the present invention.At this moment, the content of macromolecule component is better 1 quality % ~ 20 quality % in aligning agent for liquid crystal, is more preferably 3 quality % ~ 15 quality %, particularly preferably 3 ~ 10 quality %.
In the present invention, described macromolecule component can be all polymkeric substance of the present invention, only otherwise destroy effect of the present invention, also can comprise other polymkeric substance.When macromolecule component comprises other polymkeric substance, its content is better 0.05 ~ 4 mass parts relative to 1 mass parts polymkeric substance of the present invention, is more preferably 0.1 ~ 3 mass parts.
Other polymkeric substance above-mentioned can exemplify and such as use the diamine compound beyond above-mentioned specific diamine compound as the diamine component reacted with tetracarboxylic dianhydride's composition and the polyimide etc. that maybe obtained by this polyamic acid imidization of the polyamic acid obtained.
The solvent used in aligning agent for liquid crystal of the present invention is better the organic solvent that macromolecule component is dissolved, and below exemplifies its object lesson:
N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolactone, 1,3-dimethyl-imidazolinone, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, pimelinketone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone etc.They can be used alone, also can be used in combination.
Aligning agent for liquid crystal of the present invention can comprise composition than that described above.As its example, the solvent having film uniformity when making coating of liquid crystalline aligning agent and surface smoothness to improve or compound, the compound etc. that the adaptation of liquid crystal orientation film and substrate is improved.
As the solvent making film uniformity and surface smoothness improve, can exemplify for the low poor solvent of the solvability of the macromolecule component in aligning agent for liquid crystal.As the object lesson of poor solvent, following compound can be exemplified:
Such as, Virahol, methoxymethyl amylalcohol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, Diethylene Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentaacetic acid ester, butyl butyric ester, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, two hexyl ethers, 1-hexanol, normal hexane, Skellysolve A, octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methylethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic ester, propylene glycol-1-single ethyl ether-2-acetic ester, dipropylene glycol, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent etc. of low surface tension.
These poor solvents can use a kind, also can be used in combination multiple.When using poor solvent as above, poor solvent is better 5 ~ 80 quality % of the solvent entirety contained by aligning agent for liquid crystal, is more preferably 20 ~ 60 quality %.
As the compound making film uniformity and surface smoothness improve, fluorine class tensio-active agent, siloxane type surfactants, nonionic surfactant etc. can be exemplified.
More particularly, such as eftop EF301 can be exemplified, EF303, EF352 (Tuo Kaimu goods Co., Ltd. (ト mono-ケ system プ ロ ダ クツ society) system), MEGAFACE F171, F173, R-30 (Dainippon Ink. & Chemicals Inc (large Japanese イ Application キ society) system), Fluorad FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ mono-エ system society) system), AashiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc.The usage ratio of these tensio-active agents is better 0.01 ~ 2 mass parts relative to macromolecule component 100 mass parts contained by aligning agent for liquid crystal, is more preferably 0.01 ~ 1 mass parts.
As the object lesson of the compound making the adaptation of liquid crystal orientation film and substrate improve, the compound containing functional silanes shown below or the compound etc. containing epoxy group(ing) can be exemplified.
Such as, 3-TSL 8330 can be exemplified, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTES of N-, ethylene glycol diglycidyl base ether, polyethylene glycol diglycidyl base ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexylene glycol diglycidyl ether, glycerine diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N '-four glycidyl group m-xylene diamine, two (N, the N-diglycidyl amino methyl) hexanaphthene of 1,3-, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
When using for improving the compound with the adaptation of substrate, its usage quantity is better 0.1 ~ 30 mass parts relative to macromolecule component 100 mass parts contained by aligning agent for liquid crystal, is more preferably 1 ~ 20 mass parts.If usage quantity is lower than 0.1 mass parts, then cannot expect the effect that adaptation improves; If higher than 30 mass parts, then liquid crystal aligning may be deteriorated.
In aligning agent for liquid crystal of the present invention, in addition to that mentioned above, as long as in the scope not destroying effect of the present invention, dielectric medium or conducting material can be added in order to change the electrical characteristic such as the specific inductivity of liquid crystal orientation film or electroconductibility, and add the cross-linked compound for improving film strength when making liquid crystal orientation film and density.
< liquid crystal orientation film liquid crystal display device >
Aligning agent for liquid crystal of the present invention can coated on substrate and after burning till, carry out orientation process by friction treatment or illumination etc., or uses as liquid crystal orientation film when not carrying out orientation process in vertical orientated purposes etc.At this moment, as long as the substrate that the substrate transparency of use is high, be not particularly limited, glass substrate or the plastic base etc. such as vinylformic acid substrate or polycarbonate substrate can be used.In addition, from the angle of work simplification, be better the substrate using the ITO electrode etc. be formed with for liquid crystal drive.In addition, in the liquid crystal display device of reflection-type, only can adopt the opaque article such as silicon wafer in the side of substrate, the electrode in this situation also can use the material of the reflected light such as aluminium.
The coating process of aligning agent for liquid crystal is not particularly limited, the method that industrial general employing is undertaken by silk screen printing, offset printing, flexographic printing, ink-jet etc.As other coating process, also have dip coating, rolling method, slot coated method, spin-coating method etc., these methods can be used as required.
Aligning agent for liquid crystal is coated after on substrate burn till by the heater meanses such as hot plate 50 DEG C ~ 300 DEG C, be better 80 DEG C ~ 250 DEG C and carry out, can film be formed after solvent is evaporated.If the thickness burning till the film of rear formation is excessive, be then disadvantageous at the power consumption aspect of performance of liquid crystal display device, if too small, then the reliability of liquid crystal display device may reduce, so be better 5 ~ 300nm, is more preferably 10 ~ 100nm.When making liquid crystal horizontal alignment or tilted alignment, the film after burning till is processed by friction or polarized UV rays irradiation etc.
Liquid crystal display device of the present invention, after being with the substrate of liquid crystal orientation film by aforesaid method by aligning agent for liquid crystal acquisition of the present invention, making liquid crystal cell, thus make liquid crystal display device by known method.
If exemplify the example that liquid crystal cell makes, can the following method of example: preparation is formed with 1 pair of substrate of liquid crystal orientation film, one piece of substrate scatters spacer, and the mode being positioned at inner side with liquid crystal aligning face bonds another block substrate, and decompression injects liquid crystal and the method for sealing; Or, the method etc. that adhesive base plate after the liquid crystal aligning face dropping liquid crystalline substance being scattered with spacer carrying out seals.The thickness of spacer is at this moment better 1 ~ 30 μm, is more preferably 2 ~ 10 μm.
As mentioned above, the reliability of the liquid crystal display device using aligning agent for liquid crystal of the present invention to make is good, is suitable for the LCD TV etc. of large picture, fine.
Embodiment
Below, exemplify embodiment and comparative example carries out more specific description to the present invention, but explanation of the present invention is not limited in these embodiments.
[synthesis of diamine compound]
< embodiment 1>
The synthesis of diamine compound (4)
[changing 18]
By compound (2) (57.00g, 455mmol) with triethylamine (46.08g, tetrahydrofuran (THF) (1000g) solution 455mmol) is cooled to less than 10 DEG C, tetrahydrofuran (THF) (500g) solution of compound (1) (100.00g, 434mmol) is dripped while noting heating.After dropping terminates, temperature of reaction is risen to 23 DEG C, react further.After confirming that reaction terminates by HPLC (high performance liquid chromatography), reaction solution is injected distilled water (9L), again the solid of separating out filtered, wash rear 2-propyl alcohol (200g) dispersion cleaning, obtain compound (3) (receipts amount: 120.6g, yield: 89%).
1h-NMR (
1h NMR (Nuclear Magnetic Resonance) spectrum) (400MHz, DMSO-d6, δ (ppm)): 9.21 (1H, t), 9.05 (2H, d), 8.97 (1H, t), 7.66 (1H, s), 7.22 (1H, s), 6.90 (1H, s), 4.05 (2H, t), 3.31 (2H, q), 2.01 (2H, tt).
Then, by the mixture of compound (3) (100.00g, 313mmol), 5% palladium carbon (water type, 10.00g, 10wt%) and DMF (2000g) in the presence of the hydrogen in 23 DEG C of stirrings.Carry out nitrogen replacement after reaction terminates, then add gac (10.00g), stir 1 hour at 23 DEG C.Then, by Filtration of catalyst and gac, heat up in a steamer filtrate, obtain coarse crystallization.Add 2-propyl alcohol (300g) to this coarse crystallization, stir 30 minutes at 23 DEG C.Carry out filtering, dry, obtain diamine compound (4) (receipts amount: 76.3g, yield: 94%).
1H-NMR(400MHz，DMSO-d6，δ(ppm))：8.05(1H，t)，7.62(1H，t)，7.16(1H，t)，6.85(1H，t)，6.16(2H，d)，5.89(1H，t)，4.82(4H，broad)，3.94(2H，t)，3.43(2H，q)，1.85(2H，tt).
< embodiment 2>
The synthesis of diamine compound (7)
[changing 19]
By compound (5) (24.00g, 195mmol) with triethylamine (19.72g, tetrahydrofuran (THF) (500g) solution 195mmol) is cooled to less than 10 DEG C, tetrahydrofuran (THF) (142g) solution of compound (1) (42.80g, 186mmol) is dripped while noting heating.After dropping terminates, temperature of reaction is risen to 23 DEG C, react further.After confirming that reaction terminates by HPLC, reaction solution is injected distilled water (3.9L), again the solid of separating out filtered, wash rear 2-propyl alcohol (240g) dispersion cleaning, obtain compound (6) (receipts amount: 51.3g, yield: 87%).
1H-NMR(400MHz，DMSO-d6，δ(ppm))：9.87(1H，broad)，9.10(2H，d)，8.97(1H，t)，8.57(1H，d)，8.50(1H，t)，4.65(2H，s)，2.84(3H，s).
Then, by compound (6) (45.00g, 142mmol), 5% palladium carbon (water type, 4.5g, 10wt%) and Isosorbide-5-Nitrae-two
the mixture of alkane (675g)/DMF (200g) is in the presence of the hydrogen in 70 DEG C of stirrings.Carry out nitrogen replacement after reaction terminates, then add gac (4.5g), stir 1 hour at 70 DEG C.Then, by Filtration of catalyst and gac, heat up in a steamer filtrate, obtain coarse crystallization.To crude product 2-propyl alcohol (100g) the dispersion cleaning of gained, thus obtain diamine compound (7) (receipts amount: 33.7g, yield: 92%).
1H-NMR(400MHz，DMSO-d6，δppm)：8.60(1H，t)，8.42(1H，m)，8.38(1H，d)，6.22(2H，d)，5.92(1H，t)，4.84(4H，s)，4.43(2H，d)，2.43(3H，s).
< embodiment 3>
The synthesis of diamine compound (10)
[changing 20]
By compound (8) (24.00g, 146mmol) with triethylamine (14.79g, tetrahydrofuran (THF) (332g) solution 146mmol) is cooled to less than 10 DEG C, tetrahydrofuran (THF) (100g) solution of compound (1) (32.10g, 139mmol) is dripped while noting heating.After dropping terminates, temperature of reaction is risen to 23 DEG C, react further.After confirming that reaction terminates by HPLC, reaction solution is injected distilled water (3.9L), again the solid of separating out filtered, wash rear 2-propyl alcohol (200g) dispersion cleaning, obtain compound (9) (receipts amount: 47.6g, yield: 95%).
1H-NMR(400MHz，DMSO-d6，δ(ppm))：8.88(1H，t)，8.70(2H，d)，8.40(2H，t)，6.68(1H，t)，3.9(2H，broad)，3.75(4H，broad)，3.42(2H，broad).
Then, by the mixture of compound (9) (40.00g, 112mmol), 5% palladium carbon (water type, 4.00g, 10wt%) and DMF (800g) in the presence of the hydrogen in 70 DEG C of stirrings.After reaction terminates, heat up in a steamer desolventizing with after diatomite filtration catalyzer by vaporizer, obtain crude product.To crude product 2-propyl alcohol (12g) the dispersion cleaning of gained, thus obtain diamine compound (10) (receipts amount: 1.7g, yield: 68%).
1H-NMR(400MHz，DMSO-d6，δ(ppm))：8.35(2H，d)，6.63(1H，t)，5.82(1H，t)，5.75(2H，d)，4.86(4H，s)，3.70(4H，broad)，3.49(4H，broad).
< synthesis example 1>
The synthesis of diamine compound (13)
[changing 21]
By compound (11) (15.22g, 142mmol) with triethylamine (15.09g, tetrahydrofuran (THF) (150g) solution 149mmol) is cooled to less than 10 DEG C, tetrahydrofuran (THF) (50g) solution of compound (1) (31.1g, 135mmol) is dripped while noting heating.After dropping terminates, temperature of reaction is risen to 23 DEG C, react further.After confirming that reaction terminates by HPLC, reaction solution is injected distilled water (1L), then the solid of separating out is filtered, washed.Then, by solid ethanol (300g) dispersion cleaning, thus compound (12) (receipts amount: 36.92g, yield: 90%) is obtained.
1H-NMR(400MHz，DMSO-d6，δ(ppm))：9.75(1H，broad)，9.10(2H，s)，8.97-8.92(1H，m)，7.40-7.22(5H，m)，4.59-4.52(2H，m).
Then, by compound (12) (36.00g, 119mmol), 5% palladium carbon (water type, 3.6g, 10wt%) and Isosorbide-5-Nitrae-two
the mixture of alkane (300g) is in the presence of the hydrogen in 60 DEG C of stirrings.After reaction terminates, heat up in a steamer desolventizing with after diatomite filtration catalyzer by vaporizer, obtain crude product.To crude product with methanol (200g) recrystallization of gained, thus obtain diamine compound (13) (receipts amount: 21.5g, yield: 72%).
1H-NMR(400MHz，DMSO-d6，δ(ppm))：8.55(1H，broad)，7.34-7.17(5H，m)，6.28(2H，s)，6.98-6.94(1H，m)，4.85-4.74(4H，broad)，4.42-4.35(2H，m).
< synthesis example 2>
The synthesis of diamine compound (16)
[changing 22]
By compound (14) (23.45g, 190mmol) with triethylamine (19.23g, tetrahydrofuran (THF) (230g) solution 277mmol) is cooled to less than 10 DEG C, tetrahydrofuran (THF) (110g) solution of compound (1) (41.68g, 180mmol) is dripped while noting heating.After dropping terminates, temperature of reaction is risen to 23 DEG C, react further.After confirming that reaction terminates by HPLC, reaction solution is injected distilled water (1.5L), then the solid of separating out is filtered, washed.Then, by solid ethanol (380g) dispersion cleaning, thus compound (15) (receipts amount: 50.82g, yield: 89%) is obtained.
1H-NMR(400MHz，DMSO-d6，δ(ppm))：9.76(1H，t)，9.09-9.02(2H，m)，8.99-8.93(1H，m)，8.50(1H，broad)，7.64-7.60(1H，m)，7.36-7.32(1H，m)，7.20-7.14(1H，m)，4.57(2H，s)，3.35(2H，s).
Then, by compound (15) (48.00g, 151mmol), 5% palladium carbon (water type, 4.8g, 10wt%) and Isosorbide-5-Nitrae-two
the mixture of alkane (490g) is in the presence of the hydrogen in 60 DEG C of stirrings.After reaction terminates, heat up in a steamer desolventizing with after diatomite filtration catalyzer by vaporizer, obtain crude product.To crude product ethanol (300g) recrystallization of gained, thus obtain diamine compound (16) (receipts amount: 27.20g, yield: 70%).
1H-NMR(400MHz，DMSO-d6，δ(ppm))：8.64(1H，t)，8.50(1H，d)，8.44(1H，d)，7.67(1H，d)，7.34(1H，q)，6.23(2H，d)，5.94(1H，s)，4.87(4H，s)，4.39(2H，d).
[synthesis of polyamic acid and polyimide]
Below illustrate that the tetracarboxylic dianhydride of use waits the abbreviation of compound.
(tetracarboxylic dianhydride)
CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride
BODA: two rings [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride
[changing 23]
(diamine compound)
DBA:3,5-diaminobenzoic acid
P-PDA: Ursol D
AP18:1,3-diamino-4-octadecyl oxygen base benzene
PCH7DAB:1,3-diamino-4-[4-(trans-4-n-heptyl cyclohexyl) phenoxy group] benzene
[changing 24]
(organic solvent)
NMP:N-N-methyl-2-2-pyrrolidone N-
BCS: ethylene glycol butyl ether
The molecular weight determination > of < polyimide
The molecular weight of the polyimide in synthesis example uses Showa Denko K. K (Showa Electricity work society) normal temperature gel permeation chromatography (GPC) device (GPC-101) processed, Xiao De Ces Co., Ltd (Shodex society) post (KD-803 processed, KD-805), measure as follows.
Column temperature: 50 DEG C
Elutriant: N, and N '-dimethyl methane amide (as additive, lithiumbromide monohydrate (LiBrH
2o) be 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) is 30mmol/L, and tetrahydrofuran (THF) (THF) is 10mL/L).
Flow velocity: 1.0ml/ minute
Calibration curve making standard model: (East ソ mono-society of TOSOH Co., Ltd) TSK standard polyethylene oxide processed (molecular weight about 900000,150000,100000,30000) or Polymer Laboratory company (Port リ マ mono-ラ ボ ラ ト リ mono-society) polyoxyethylene glycol processed (molecular weight about 12000,4000,1000).
The mensuration > of < imide rate
The imide rate of the polyimide in synthesis example measures as follows.
20mg polyimide powder is added NMR sample hose (wasteland's science Co., Ltd. (wasteland's science society) NMR sampling tube standard type φ 5 processed), add 0.53ml deuterated dimethyl sulfoxide (DMSO-d6,0.05%TMS (tetramethylsilane) melange), apply ultrasonic wave and make it dissolve completely.By NEC De Tamu Co., Ltd. (Japanese Electricity デ mono-タ system society) NMR tester (JNW-ECA500) processed to the proton N MR of this measured in solution 500MHz.For imide rate, to derive from the proton of unchanged structure before and after imidization for reference proton, use the integrated value at the peak of this proton and derive from the integrated value of proton peak of NH base of the amido acid appeared near 9.5 ~ 10.0ppm, try to achieve imide rate by following formula.
Imide rate (%)=(1-α x/y) × 100
In above formula, x is the proton peak integrated value of the NH base deriving from amido acid, and y is the peak integrated value of reference proton, relative to the number ratio of the reference proton of NH matrix of 1 amido acid when α is polyamic acid (imide rate is 0%).
< embodiment 4>
By BODA (3.24g, 13.0mmol), p-PDA (0.65g, 6.01mmol), PCH7DAB (3.30g, diamine compound (the 4) (0.68g that obtains 8.67mmol) and in embodiment 1,2.62mmol) mixing in NMP (14.5g), 80 DEG C of reactions after 5 hours, add CBDA (0.85g, 4.34mmol) with NMP (11.9g), 40 DEG C of reactions 6 hours, obtain polyamic acid solution (A) (concentration: 24.8 quality %).The number-average molecular weight of this polyamic acid is 22800, and weight-average molecular weight is 53900.
< embodiment 5>
NMP is added in polyamic acid solution (A) (20.0g) that obtain in embodiment 4, be after 6 quality % by the concentration dilution of polyamic acid, add the diacetyl oxide (2.65g) as imidization catalyst and pyridine (2.07g), 80 DEG C of reactions 2 hours.This reaction soln is dropped in methyl alcohol (350ml), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (B).The imide rate of this polyimide is 40%, and number-average molecular weight is 18800, and weight-average molecular weight is 49500.
< embodiment 6>
By BODA (3.25g, 13.0mmol), DBA (0.52g, 3.42mmol), PCH7DAB (3.30g, diamine compound (the 4) (1.36g that obtains 8.67mmol) and in embodiment 1,5.24mmol) mixing in NMP (15.5g), 80 DEG C of reactions after 5 hours, add CBDA (0.85g, 4.34mmol) with NMP (12.7g), 40 DEG C of reactions 6 hours, obtain polyamic acid solution (C) (concentration: 24.8 quality %).The number-average molecular weight of this polyamic acid is 24100, and weight-average molecular weight is 55500.
< embodiment 7>
NMP is added in polyamic acid solution (C) (20.1g) that obtain in embodiment 6, be after 6 quality % by the concentration dilution of polyamic acid, add the diacetyl oxide (2.66g) as imidization catalyst and pyridine (2.07g), 80 DEG C of reactions 2 hours.This reaction soln is dropped in methyl alcohol (350ml), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (D).The imide rate of this polyimide is 40%, and number-average molecular weight is 19900, and weight-average molecular weight is 51500.
< embodiment 8>
By BODA (3.15g, 12.6mmol), p-PDA (1.01g, 9.34mmol), AP18 (1.25g, 3.32mmol) and the diamine compound (7) (1.10g, 4.28mmol) that obtains mixing in NMP (8.35g) in embodiment 2,80 DEG C of reactions after 5 hours, add CBDA (0.85g, 4.34mmol) with NMP (6.83g), 40 DEG C of reactions 6 hours, obtain polyamic acid solution.The number-average molecular weight of this polyamic acid is 21500, and weight-average molecular weight is 52400.
NMP is added in the polyamic acid solution obtained (20.0g), be after 6 quality % by the concentration dilution of polyamic acid, add the diacetyl oxide (2.65g) as imidization catalyst and pyridine (2.07g), 80 DEG C of reactions 2 hours.This reaction soln is dropped in methyl alcohol (350ml), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (E).The imide rate of this polyimide is 40%, and number-average molecular weight is 18100, and weight-average molecular weight is 48700.
< embodiment 9>
By BODA (3.22g, 12.9mmol), DBA (0.79g, 5.19mmol), PCH7DAB (3.22g, 8.46mmol) and the diamine compound (7) (0.92g, 3.58mmol) that obtains mixing in NMP (13.5g) in embodiment 2,80 DEG C of reactions after 5 hours, add CBDA (0.85g, 4.34mmol) with NMP (11.0g), 40 DEG C of reactions 6 hours, obtain polyamic acid solution.The number-average molecular weight of this polyamic acid is 23700, and weight-average molecular weight is 54000.
NMP is added in the polyamic acid solution obtained (20.1g), be after 6 quality % by the concentration dilution of polyamic acid, add the diacetyl oxide (2.65g) as imidization catalyst and pyridine (2.07g), 80 DEG C of reactions 2 hours.This reaction soln is dropped in methyl alcohol (350ml), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (F).The imide rate of this polyimide is 40%, and number-average molecular weight is 19900, and weight-average molecular weight is 49800.
< embodiment 10>
By BODA (2.97g, 11.9mmol), p-PDA (0.70g, 6.47mmol), PCH7DAB (3.06g, diamine compound (the 10) (0.51g that obtains 8.04mmol) and in embodiment 3,1.7lmmol) mixing in NMP (12.6g), 80 DEG C of reactions after 5 hours, add CBDA (0.85g, 4.34mmol) with NMP (10.3g), 40 DEG C of reactions 6 hours, obtain polyamic acid solution (G) (concentration: 26.1 quality %).The number-average molecular weight of this polyamic acid is 21200, and weight-average molecular weight is 52100.
< embodiment 11>
NMP is added in polyamic acid solution (G) (20.0g) that obtain in embodiment 10, be after 6 quality % by the concentration dilution of polyamic acid, add the diacetyl oxide (2.67g) as imidization catalyst and pyridine (2.05g), 80 DEG C of reactions 2 hours.This reaction soln is dropped in methyl alcohol (360ml), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (H).The imide rate of this polyimide is 40%, and number-average molecular weight is 18100, and weight-average molecular weight is 48500.
< synthesis example 3>
By BODA (3.22g, 12.9mmol), p-PDA (0.65g, 6.00mmol), PCH7DAB (3.26g, diamine compound (the 13) (0.62g that obtains 8.57mmol) and in synthesis example 1,2.56mmol) mixing in NMP (15.2g), 80 DEG C of reactions after 5 hours, add CBDA (0.84g, 4.28mmol) with NMP (11.1g), 40 DEG C of reactions 6 hours, obtain polyamic acid solution (I) (concentration: 24.6 quality %).The number-average molecular weight of this polyamic acid is 22100, and weight-average molecular weight is 53200.
< synthesis example 4>
NMP is added in polyamic acid solution (I) (20.1g) that obtain in synthesis example 3, be after 6 quality % by the concentration dilution of polyamic acid, add the diacetyl oxide (2.68g) as imidization catalyst and pyridine (2.04g), 80 DEG C of reactions 2 hours.This reaction soln is dropped in methyl alcohol (350ml), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (J).The imide rate of this polyimide is 41%, and number-average molecular weight is 18400, and weight-average molecular weight is 49100.
< synthesis example 5>
By BODA (3.29g, 13.2mmol), p-PDA (0.67g, 6.14mmol), PCH7DAB (3.34g, diamine compound (the 16) (0.68g that obtains 8.77mmol) and in synthesis example 2,2.79mmol) mixing in NMP (15.0g), 80 DEG C of reactions after 5 hours, add CBDA (0.86g, 4.39mmol) with NMP (11.5g), 40 DEG C of reactions 6 hours, obtain polyamic acid solution (K) (concentration: 25.0 quality %).The number-average molecular weight of this polyamic acid is 22600, and weight-average molecular weight is 54900.
< synthesis example 6>
NMP is added in polyamic acid solution (K) (20.0g) that obtain in synthesis example 5, be after 6 quality % by the concentration dilution of polyamic acid, add the diacetyl oxide (2.65g) as imidization catalyst and pyridine (2.08g), 80 DEG C of reactions 2 hours.This reaction soln is dropped in methyl alcohol (320ml), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (L).The imide rate of this polyimide is 40%, and number-average molecular weight is 18900, and weight-average molecular weight is 49200.
The reaction conditions (mol of each composition) of embodiment 4 ~ 11 and synthesis example 3 ~ 6 (synthesis of polyamic acid and polyimide) and imide rate gather and are shown in table 3 and table 4.
[table 3]
[table 4]
[the preparation evaluation of aligning agent for liquid crystal]
< embodiment 12>
Add NMP (10.2g) and BCS (20.0g) in polyamic acid solution [A] (10.0g) that obtain in embodiment 4, stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [1].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
[making of liquid crystal cell]
Aligning agent for liquid crystal obtained above [1] is spun on the ito surface of the substrate of 3cm × 4cm (vertical × horizontal) band ITO electrode, carry out 80 DEG C of 5 minutes burn till and the burning till of the heated air circulation type baking oven 1 hour of 210 DEG C, make the polyimide coating film of thickness 100nm.
The substrate of this band liquid crystal orientation film is carried out friction treatment by the friction gear of roller footpath 120mm, Artificial Fibers cloth with the condition of rotating speed 300rpm, roller gait of march 20mm/ second, intrusion 0.3mm, obtains the substrate of band liquid crystal orientation film.
Prepare the substrate of 2 pieces of these band liquid crystal orientation films, after the liquid crystal aligning face of 1 piece scattering the pearl shape spacer of 6 μm wherein, printing and sealing agent from the upper side.The another 1 piece of substrate prepared, towards inner side is made sealant cures, makes sylphon after the contrary mode of frictional direction bonds with liquid crystal orientation film.Inject liquid crystal MLC-6608 (Merck Japanese firm (メ Le Network ジ ャ パ Application society) system) to this sylphon by decompression injection method, obtain the nematic liquid crystal box of antiparallel orientations.
[evaluation of voltage retention]
Liquid crystal cell obtained above is applied at the temperature of 80 DEG C to the voltage 60 μ s of 4V, the voltage after measuring 16.67ms and after 1667ms, what degree voltage can remain to calculates as voltage retention (%).Result is shown in table 5.
[the slow result appraisal of residual charge]
10V volts DS 30 minutes are applied to the liquid crystal cell after voltage retention measures, makes its short circuit measure the current potential produced in liquid crystal cell between 1800 seconds afterwards in 1 second.And the residual charge (V) measured after 50 seconds and after 1000 seconds.Measure and use Dongyang science and technology Co., Ltd. (East Yang テ Network ニ カ society) make 6254 type liquid crystal evaluation of physical property devices.Result is shown in table 6.
[evaluation after high temperature placement]
Liquid crystal cell after being measured by residual charge, after being set as that the high temperature groove of 100 DEG C places 7 days, carries out the mensuration of voltage retention and residual charge.Result is shown in table 5 described later and table 6.
For the aligning agent for liquid crystal obtained in following embodiment 13 ~ 19 and comparative example 1 ~ 4, also use these aligning agent for liquid crystal to carry out the making of liquid crystal cell similarly to Example 12, then carry out the evaluation of each liquid crystal cell.Their result gathers and is shown in table 5 and table 6.
< embodiment 13>
Add NMP (36.3g) in polyimide powder [B] (5.1g) that obtain in embodiment 5, within 40 hours, make it dissolve 70 DEG C of stirrings.In this solution, add NMP (18.1g) and BCS (25.6g), stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [2].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< embodiment 14>
Add NMP (10.2g) and BCS (20.0g) in polyamic acid solution [C] (10.0g) that obtain in embodiment 6, stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [3].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< embodiment 15>
Add NMP (30.3g) in polyimide powder [D] (5.0g) that obtain in embodiment 7, within 40 hours, make it dissolve 70 DEG C of stirrings.In this solution, add NMP (14.8g) and BCS (33.8g), stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [4].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< embodiment 16>
Add NMP (33.0g) in polyimide powder [E] (5.1g) that obtain in embodiment 8, within 40 hours, make it dissolve 70 DEG C of stirrings.In this solution, add NMP (17.1g) and BCS (29.8g), stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [5].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< embodiment 17>
Add NMP (34.5g) in polyimide powder [F] (5.2g) that obtain in embodiment 9, within 40 hours, make it dissolve 70 DEG C of stirrings.In this solution, add NMP (16.5g) and BCS (30.3g), stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [6].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< embodiment 18>
Add NMP (15.6g) and BCS (17.1g) in polyamic acid solution [G] (10.0g) that obtain in embodiment 10, stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [7].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< embodiment 19>
Add NMP (35.5g) in polyimide powder [H] (5.0g) that obtain in embodiment 11, within 40 hours, make it dissolve 70 DEG C of stirrings.In this solution, add NMP (17.8g) and BCS (25.1g), stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [8].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< comparative example 1>
Add NMP (18.8g) and BCS (12.2g) in polyamic acid solution [I] (10.0g) that obtain in synthesis example 3, stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [9].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< comparative example 2>
Add NMP (38.6g) in polyimide powder [J] (4.7g) that obtain in synthesis example 4, within 40 hours, make it dissolve 70 DEG C of stirrings.In this solution, add NMP (19.4g) and BCS (15.8g), stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [10].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< comparative example 3>
Add NMP (17.5g) and BCS (15.3g) in polyamic acid solution [K] (10.4g) that obtain in synthesis example 5, stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [11].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
< comparative example 4>
Add NMP (34.5g) in polyimide powder [L] (4.5g) that obtain in synthesis example 6, within 40 hours, make it dissolve 70 DEG C of stirrings.In this solution, add NMP (17.2g) and BCS (18.8g), stir 2 hours at 25 DEG C, thus obtain aligning agent for liquid crystal [12].There are not the abnormal conditions such as muddiness or precipitation in this aligning agent for liquid crystal, confirms that macromolecule component dissolves equably.
[table 5]
[table 6]
The possibility that industry utilizes
The aligning agent for liquid crystal comprising diamine compound of the present invention can obtain the high and liquid crystal orientation film that the long-time alleviation exposing the electric charge gathered because of volts DS is at high temperature also fast of voltage retention when making liquid crystal orientation film.In addition, the liquid crystal display device that the long term reliability that can tolerate under harsh environment for use is high can also be provided.Thus can be used for the liquid crystal display device etc. of TN element, STN element, TFT liquid crystal cell and vertical orientating type and horizontally oriented type (IPS).
Quote the announcement of full content as specification sheets of the present invention of the specification sheets of No. 2009-170396, the Japanese patent application that on July 21st, 2009 files an application, claims and specification digest here.
Claims (11)
1. the diamine compound of following formula [1];
[changing 1]
In formula, X
1represent-CO-or-CONH-, X
2represent alkylidene group or the piperazine ring of carbon number 1 ~ 5, X
3the imidazole ring that expression can be replaced by the alkyl of carbon number 1 ~ 5 or pyrazine ring.
2. diamine compound as claimed in claim 1, is characterized in that, described X
2for piperazine ring.
3. the polyimide that maybe obtained by this polyamic acid imidization of polyamic acid, it is characterized in that, described polyamic acid reacts by making the diamine component of the diamine compound comprised described in claim 1 or 2 and tetracarboxylic dianhydride's composition and obtains.
4. the polyimide that maybe obtained by this polyamic acid imidization of polyamic acid as claimed in claim 3, it is characterized in that, in described diamine component, the content of the diamine compound described in claim 1 or 2 is 1 ~ 80 % by mole.
5. the polyimide that maybe obtained by this polyamic acid imidization of polyamic acid as claimed in claim 3, is characterized in that, comprise carboxylic diamine compound in molecule in described diamine component.
6. the polyimide that maybe this polyamic acid imidization obtained of polyamic acid as claimed in claim 5, it is characterized in that, in described diamine component, relative to the diamines described in 1 mole of claim 1 or 2, in molecule, the content of carboxylic diamine compound is 0.01 ~ 99 mole.
7. the polyimide that this polyamic acid imidization maybe obtains by the polyamic acid as described in claim 5 or 6, it is characterized in that, in described molecule, carboxylic diamine compound is the diamines represented with following formula [2];
[changing 2]
In formula [2], X
5for the organic group with aromatic nucleus of carbon number 6 ~ 30, n is the integer of 1 ~ 4.
8. aligning agent for liquid crystal, is characterized in that, comprises at least one party in the polyamic acid described in any one in claim 3 ~ 7 and the polyimide that obtained by this polyamic acid imidization and solvent.
9. aligning agent for liquid crystal as claimed in claim 8, it is characterized in that, 5 ~ 80 quality % in described solvent are poor solvent.
10. liquid crystal orientation film, is characterized in that, is obtained by the aligning agent for liquid crystal described in claim 8 or 9.
11. liquid crystal display device, is characterized in that, have liquid crystal orientation film according to claim 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009170396 | 2009-07-21 | ||
| JP2009-170396 | 2009-07-21 | ||
| PCT/JP2010/062109 WO2011010619A1 (en) | 2009-07-21 | 2010-07-16 | Diamine compound, polyamic acid, polyimide, and liquid crystal aligning agent |
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| CN102574811A CN102574811A (en) | 2012-07-11 |
| CN102574811B true CN102574811B (en) | 2015-09-09 |
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| JP (1) | JP5729299B2 (en) |
| KR (2) | KR20120037493A (en) |
| CN (1) | CN102574811B (en) |
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| JP5541454B2 (en) * | 2009-09-16 | 2014-07-09 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| TWI417317B (en) * | 2010-07-21 | 2013-12-01 | Daxin Materials Corp | Aromatic diamine compound, polyamic acid and polyimide prepared using the same and liquid crystal alignment agent |
| WO2012014898A1 (en) * | 2010-07-26 | 2012-02-02 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN102558096B (en) * | 2010-12-30 | 2015-01-21 | 达兴材料股份有限公司 | Aromatic diamine compound, polyamic acid and polyimide prepared from aromatic diamine compound, and liquid crystal aligning agent |
| CN103492462B (en) * | 2011-03-07 | 2016-01-20 | 日产化学工业株式会社 | Composition, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display device |
| WO2012121257A1 (en) * | 2011-03-07 | 2012-09-13 | 日産化学工業株式会社 | Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| TWI452088B (en) * | 2011-04-14 | 2014-09-11 | Daxin Materials Corp | Liquid crystal aligning agent |
| KR101990302B1 (en) * | 2011-05-18 | 2019-06-18 | 주식회사 동진쎄미켐 | Diamine Compound, Method for Preparing the same, Liquid Crystal Alignment Agent, Liquid Crystal Alignment Film and Liquid Crystal Display Device |
| TWI633128B (en) * | 2011-05-27 | 2018-08-21 | 日產化學工業股份有限公司 | Composition, liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element |
| TWI499656B (en) * | 2011-07-14 | 2015-09-11 | Nissan Chemical Ind Ltd | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| KR101947855B1 (en) * | 2012-01-18 | 2019-02-13 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| TWI508998B (en) * | 2012-10-03 | 2015-11-21 | Chi Mei Corp | Liquid crystal aligning agent and its application |
| TWI494347B (en) * | 2012-12-25 | 2015-08-01 | Taiwan Textile Res Inst | Dinitro monomer, diamine monomer, polyimide and modified polyimide |
| JP6384663B2 (en) * | 2014-10-16 | 2018-09-05 | 日産化学株式会社 | Polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| KR102034364B1 (en) * | 2015-03-27 | 2019-11-08 | 도쿄 오카 고교 가부시키가이샤 | Energy-sensitive resin composition |
| JP6627595B2 (en) * | 2015-06-11 | 2020-01-08 | Jnc株式会社 | Liquid crystal alignment agent for forming liquid crystal alignment film for photo alignment, liquid crystal alignment film, and liquid crystal display device using the same |
| EP3330320B1 (en) | 2015-08-07 | 2019-04-24 | Tokyo Ohka Kogyo Co., Ltd. | Polyimide precursor composition |
| CN108369359B (en) * | 2015-10-07 | 2021-07-27 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| TWI687457B (en) * | 2016-08-24 | 2020-03-11 | 奇美實業股份有限公司 | Liquid crystal alignment agent and use thereof |
| WO2018066494A1 (en) * | 2016-10-07 | 2018-04-12 | シャープ株式会社 | Liquid crystal aligning agent for tft substrates and method for producing liquid crystal display panel |
| CN114207086A (en) | 2019-08-08 | 2022-03-18 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same |
| CN114958393B (en) * | 2022-06-16 | 2023-09-05 | 长沙道尔顿电子材料有限公司 | Polyamic acid liquid crystal orientation agent with nitrogen-containing aromatic ring structure, liquid crystal orientation film and preparation method thereof |
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| CN101452153A (en) * | 2007-12-06 | 2009-06-10 | Jsr株式会社 | Liquid crystal oriented agent and liquid crystal display element |
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| JP3613421B2 (en) * | 1996-05-31 | 2005-01-26 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| JP3650982B2 (en) * | 1996-10-02 | 2005-05-25 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| US20070082965A1 (en) * | 2002-11-28 | 2007-04-12 | Jsr Corporation | Photocuring resin composition, medical device using same and method for manufacturing same |
| KR101737122B1 (en) * | 2008-01-25 | 2017-05-17 | 닛산 가가쿠 고교 가부시키 가이샤 | Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same |
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| KR20170110172A (en) | 2017-10-10 |
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