CN103641805B - Diamines and polyamic acid or the polyimide obtained by this polyamic acid imidization - Google Patents

Diamines and polyamic acid or the polyimide obtained by this polyamic acid imidization Download PDF

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CN103641805B
CN103641805B CN201310655823.3A CN201310655823A CN103641805B CN 103641805 B CN103641805 B CN 103641805B CN 201310655823 A CN201310655823 A CN 201310655823A CN 103641805 B CN103641805 B CN 103641805B
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liquid crystal
polyamic acid
polyimide
diamines
aligning agent
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CN103641805A (en
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野田尚宏
小田拓郎
筒井皇晶
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Nissan Chemical Corp
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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
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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
    • 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 the diamines that following formula [2] represents, and by making the polyamic acid that the diamine component containing this diamines and tetracarboxylic dianhydride's composition react and obtain or the polyimide obtained by this polyamic acid imidization:

Description

Diamines and polyamic acid or the polyimide obtained by this polyamic acid imidization
The application is international application no is PCT/JP2009/067424, international filing date be after the PCT international application on October 6th, 2009 enters China's stage national applications number be 200980140403.3 title be the divisional application of Chinese patent application of " liquid crystal display device of aligning agent for liquid crystal and this aligning agent for liquid crystal of use ".
Technical field
The present invention relates to liquid crystal display device aligning agent for liquid crystal used, liquid crystal orientation film and liquid crystal display device.
Background technology
Now, as the liquid crystal orientation film of liquid crystal display device, main use is burnt till through coating with the aligning agent for liquid crystal that the polyimide precursors such as polyamic acid or soluble polyamide imide liquor are principal constituent and obtained, so-called polyimide system liquid crystal orientation film.
Liquid crystal orientation film not only controls the state of orientation of liquid crystal, also has impact to the characteristic of liquid crystal display device.Especially, along with the high resolving power of liquid crystal display device, suppress the characteristic of the reduction of the contrast gradient of liquid crystal display device or minimizing afterimage phenomena increasingly important.
In polyimide system liquid crystal orientation film, the known liquid crystal orientation film having a kind of image retention extinction time produced by volts DS short, the aligning agent for liquid crystal that this liquid crystal orientation film uses also contains ad hoc structure tertiary amine (for example, see patent documentation 1) except polyamic acid or containing except the polyamic acid of imino-; Also have a kind of liquid crystal aligning process film, its aligning agent for liquid crystal used contains the soluble polyimide (for example, see patent documentation 2) using in raw material and have the specific diamines of pyridine skeleton etc.
In addition, in polyimide system liquid crystal orientation film, also have a kind of voltage retention high and the liquid crystal orientation film that image retention extinction time that is that produced by volts DS is short, the aligning agent for liquid crystal that this liquid crystal orientation film uses except polyamic acid or its imide amination polymer etc., also very little containing the compound (for example, see patent documentation 3) be selected from containing the compound containing 1 tertiary amino in the compound containing 1 acid anhydride in the compound of 1 carboxylic acid group, molecule and molecule in molecule.
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 No. 8-76128 public Reported
Although the facture to liquid crystal display afterimage phenomena up to now can shorten image retention extinction time, not talkative only this is exactly sufficient.
Summary of the invention
The present invention in view of the foregoing, its objective is and provide a kind of aligning agent for liquid crystal, this aligning agent for liquid crystal can obtain following liquid crystal orientation film: even if film stripping or cutting not easily occur during friction, voltage retention is high and applies to liquid crystal cell the savings that volts DS also not easily causes initial stage electric charge.
The present inventor conducts in-depth research for achieving the above object, and result completes the present invention.That is, the present invention has following main points.
(1) aligning agent for liquid crystal, it contains at least one polymkeric substance of the polyimide being selected from polyamic acid and obtained by this polyamic acid imidization, described polyamic acid is reacted by the diamine component and tetracarboxylic dianhydride's composition making the diamines represented containing following formula [1] and is obtained
In formula, X represents the alkylidene group ,-OCH of singly-bound, carbon number 1 ~ 3 2-,-CH 2oCO-,-NHCO-,-CONH-or-COOCH 2-, Y represents Sauerstoffatom or sulphur atom, and pentacyclic any hydrogen atom can be replaced by the alkyl of carbon number 1 ~ 5.
(2) aligning agent for liquid crystal as described in (1), wherein, the Y of formula [1] is Sauerstoffatom.
(3) aligning agent for liquid crystal as described in (1), wherein, the Y of formula [1] is sulphur atom.
(4) aligning agent for liquid crystal according to any one of (1) ~ (3), wherein, the X of formula [1] is-CH 2oCO-,-NHCO-or-COOCH 2-.
(5) aligning agent for liquid crystal as described in (1), wherein, the X of formula [1] is-CH 2oCO-,-NHCO-or-COOCH 2-, Y is Sauerstoffatom.
(6) aligning agent for liquid crystal according to any one of (1) ~ (5), wherein, pentacyclic any hydrogen atom of formula [1] is by methyl substituted.
(7) liquid crystal orientation film, obtains by using the aligning agent for liquid crystal according to any one of (1) ~ (6).
(8) liquid crystal display device, the liquid crystal orientation film that it possesses described in (7).
(9) diamines that represents of following formula [2]:
In formula, any hydrogen atom of furan nucleus can be replaced by the alkyl of carbon number 1 ~ 5.
(10) diamines as described in (9), wherein, any hydrogen atom of furan nucleus can by methyl substituted.
(11) polyamic acid or the polyimide that obtained by this polyamic acid imidization, described polyamic acid reacts by making the diamine component containing the diamines described in (9) or (10) and tetracarboxylic dianhydride's composition and obtains.
Aligning agent for liquid crystal of the present invention can obtain following liquid crystal orientation film: even if film stripping or cutting not easily occur during friction, voltage retention is high and applies to liquid crystal cell the savings that volts DS also not easily causes initial stage electric charge.By using this liquid crystal orientation film, can the good liquid crystal display of manufacturing characteristics.
Embodiment
Aligning agent for liquid crystal of the present invention contains at least one polymkeric substance being selected from the polyamic acid that diamine component and tetracarboxylic dianhydride's composition by making the diamines represented containing following formula [1] react and obtain and the polyimide obtained by this polyamic acid imidization.By using this diamines, even if in friction treatment necessary in liquid crystal aligning process, film when also can alleviate friction is peeled off or is cut, and the voltage retention of gained liquid crystal orientation film is high, even and if apply to liquid crystal cell the savings that volts DS also not easily causes initial stage electric charge.
The diamines > of < formula [1]
There is no particular limitation for the synthetic method of the diamines that formula [1] represents, such as, synthesize by making it convert amino method to ordinary method reduction nitro after synthesis following formula [S1] dinitro compound that represents.
X in above formula [1] and formula [S1] represents the alkylidene group ,-OCH of singly-bound, carbon number 1 ~ 3 2-,-CH 2oCO-,-NHCO-,-CONH-or-COOCH 2-.
In addition, the Y in above formula [1] and formula [S1] represents Sauerstoffatom or sulphur atom.
In addition, any hydrogen atom of Y to be the five-ring (hereinafter also referred to furan nucleus) of Sauerstoffatom or Y the be five-ring (hereinafter also referred to thiphene ring) of sulphur atom can be replaced by the alkyl of carbon number 1 ~ 5.The replacement radix of furan nucleus or thiphene ring being preferably 0 ~ 2, being more preferably without replacing.Thus, the patience that better rubs can be obtained.
In above formula [1] and formula [S1], the position that X is incorporated into furan nucleus or thiphene ring is not particularly limited, but preferably in two or three-digit.
X is used to be-CH 2the voltage retention of liquid crystal orientation film when being formed as liquid crystal display that the diamines of OCO-or-NHCO-obtains uprises.Moreover, if use X to be-CH 2the diamines of OCO-, then can obtain the liquid crystal display that liquid crystal aligning is excellent, electric charge is not easily put aside, thus better.
In the diamines that formula [1] represents, on phenyl ring, there is no particular limitation in each substituent position.Consider from the angle as liquid crystal aligning during liquid crystal orientation film, position or contraposition between 2 amino position relationships are preferably, and consider from the polyamic acid or the deliquescent angle of polyimide to organic solvent improving polymerisation reactivity or gained, position between being more preferably.2 amino position relationships be between position, when being 1,3-diaminobenzene structure, the position of X, preferably at 4 or 5, particularly from the angle that the effect or be easy to that can improve amino nucleophilicity is synthesized, is more preferably 5.
In the diamines that formula [1] represents, X is incorporated into the position of cis-diene ring (hereinafter also referred to furan nucleus or thiphene ring), and there is no particular limitation, angularly consider from the complexity, the reactivity that obtain raw material, suitably select described combination according to object.
When Y is Sauerstoffatom, the concrete example of (during for furan nucleus) is as follows, but is not limited thereto.
(in above formula, X represents the alkylidene group ,-OCH of singly-bound, carbon number 1 ~ 3 2-,-CH 2oCO-,-NHCO-,-CONH-or-COOCH 2-, R represents the alkyl of carbon number 1 ~ 5, and n represents the integer of 0 ~ 3).
In above formula [T1] ~ formula [T6], X is preferably-CH 2oCO-or-NHCO-, R are preferably the alkyl of carbon number 1 ~ 3, and n is preferably the integer of 0 or 1.In addition, in above formula, from polyamic acid or solvent solubility, the liquid crystal aligning of polyimide, the patience that rubs, savings electric charge (hereinafter also referred to RDC), the structure of preferred formula [T2] or formula [T5].
Especially preferred be there is the structure of formula [T2] or formula [T5], X is-CH 2the integer that the alkyl that OCO-or-NHCO-, R are carbon number 1 ~ 3, n are 0 or 1.Linking group X is used to be-CH 2the words voltage retention of the diamines of OCO-or-NHCO-uprises, and particularly uses linking group X to be-CH 2the words liquid crystal aligning of the diamines of OCO-is good especially, is therefore preferred.
When Y is sulphur atom, the concrete example of (during for thiphene ring) is as follows, but is not limited thereto.
(in above formula, X represents the alkylidene group ,-OCH of singly-bound, carbon number 1 ~ 3 2-,-CH 2oCO-,-NHCO-,-CONH-or-COOCH 2-, R represents the alkyl of carbon number 1 ~ 5, and n represents the integer of 0 ~ 3).
In above formula [U1] ~ formula [U6], X is preferably-CH 2oCO-or-NHCO-, R are preferably the alkyl of carbon number 1 ~ 3, and n is preferably the integer of 0 or 1.
In addition, in above formula, from polyamic acid or solvent solubility, the liquid crystal aligning of polyimide, the patience that rubs, savings electric charge (hereinafter also referred to RDC), the structure of preferred formula [U2] or formula [U5].
Especially preferred be there is the structure of formula [U2] or formula [U5], X is-CH 2the integer that the alkyl that OCO-or-NHCO-, R are carbon number 1 ~ 3, n are 0 or 1.Linking group X is used to be-CH 2the words voltage retention of the diamines of OCO-or-NHCO-uprises, and particularly uses linking group X to be-CH 2the words liquid crystal aligning of the diamines of OCO-is good especially, is therefore preferred.
The synthesis > of < diamines
The nitro that reduces after the dinitro matrix that specific diamine compound of the present invention is represented by synthesis type [S1] makes it convert amino to synthesize.There is no particular limitation for the method for reduction dinitro compound, can exemplify 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 in alkane, alcohol system equal solvent, carry out the method for reducing with hydrogen, hydrazine, hydrogenchloride etc.X in following formula [S1] represents the alkylidene group ,-OCH of singly-bound, carbon number 1 ~ 3 2-,-CH 2oCO-,-NHCO-,-CONH-or-COOCH 2-, Y represents Sauerstoffatom or sulphur atom, and pentacyclic any hydrogen atom can be replaced by the alkyl of carbon number 1 ~ 5.
The synthetic method of dinitro matrix is different according to linking group.
Be-CH at X 2during OCO-, such as, can obtain dinitro matrix by the condensation reaction of dinitrobenzene benzylalcohol and furancarboxylic acid or thiophene carboxylic acid.There is no particular limitation for method of condensing, reacts in the presence of base can obtain dinitro matrix [S4] by making dinitrobenzene benzylalcohol [S2] and carboxyl acyl chloride [S3].Also can exemplify the method etc. using alcohol and carboxylic acid reaction under the existence of other dehydrating condensation agent.
When X is-NHCO-, such as, can obtain dinitro matrix by the condensation reaction of dinitraniline and furancarboxylic acid or thiophene carboxylic acid.There is no particular limitation for method of condensing, reacts in the presence of base can obtain dinitro matrix [S7] by making dinitraniline [S5] and carboxyl acyl chloride [S6].Also can exemplify the method etc. making amine and carboxylic acid reaction under the existence of other dehydrating condensation agent.
Be-COOCH at X 2-time, such as, can obtain dinitro matrix by the condensation reaction of dinitrobenzoic acid and furfuralcohol or thiophen(e)alcohol.There is no particular limitation for method of condensing, reacts in the presence of base can obtain dinitro matrix [S10] by making dinitrobenzoyl chloride [S8] and alcohol [S9].Also can exemplify the method etc. making alcohol and carboxylic acid reaction under the existence of other dehydrating condensation agent.
By the good alkyl of reagent or addition being in advance used in addition alkyl in furan nucleus or thiphene ring, the furan nucleus (or thiphene ring) of attached side chain can be obtained.
< diamine component >
The diamines that above formula [1] represents and tetracarboxylic dianhydride react and can obtain polyamic acid, make this polyamic acid imidization obtain polyimide.In the present invention, during synthesizing polyamides acid, diamine component used can be used alone the diamines that formula [1] represents, also can combinationally use and be selected from the one kind or two or more of other diamines.
As diamine component, the polyamic acid that the diamines represented containing formula [1] can improve gained and the polyimide that makes this polyamic acid imidization and obtain are to the solvability of organic solvent.What is more, even if the friction patience of the liquid crystal orientation film obtained by the aligning agent for liquid crystal containing this polyamic acid or polyimide is excellent, voltage retention is high and apply to liquid crystal cell the savings that volts DS also not easily produces initial stage electric charge.For obtaining such characteristic, the diamines that formula [1] represents is preferably 10 ~ 100mol% of the diamine component total amount used in the synthesis of polyamic acid, is more preferably 20 ~ 100mol%, is particularly preferably 30 ~ 100mol%.
In above-mentioned diamine component, the diamines that the diamines represented with formula [1] combinationally uses is not particularly limited.The object lesson of these diamines is as follows.
As the example of ester ring type diamines, Isosorbide-5-Nitrae-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4 can be exemplified, 4 '-diamino-dicyclohexyl methane, 4,4 '-diamino-3,3 '-dimethyidicyclohexyl amine, isophorone diamine etc.
As the example of aromatic diamine, O-Phenylene Diamine can be exemplified, mphenylenediamine, Ursol D, 2, 4-diaminotoluene, 2, 5-diaminotoluene, 3, 5-diaminotoluene, 3, 5-diamino-N, N-diarylphenyl amine, 2, 4-diamino-N, N '-diarylphenyl amine, 1, 4-diamino-2-anisole, 2, 5-diamino-p-Xylol, 1, 3-diamino-4-chlorobenzene, 3, 5-diaminobenzoic acid, 1, 4-diamino-2, 5-dichlorobenzene, 4, 4 '-diaminostilbene, 2-diphenylethane, 4, 4 '-diamino-2, 2 '-dimethyl bibenzyl, 4, 4 '-diaminodiphenyl-methane, 3, 3 '-diaminodiphenyl-methane, 3, 4 '-diaminodiphenyl-methane, 4, 4 '-diamino-3, 3 '-dimethyl diphenylmethane, 2, 2 '-diamino , 4,4 '-diamino , 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl sulfide, DDS, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminobenzophenone, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) phenylformic acid of 3,5-, 4,4 '-bis-(4-amino-benzene oxygen) bibenzyl, two [(4-amino-benzene oxygen) methyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two (4-aminophenyl) hexanaphthene of 1,1-, α, α '-bis-(4-4 aminophenyl)-Isosorbide-5-Nitrae-diisopropylbenzene(DIPB), two (4-aminophenyl) fluorenes of 9,9-, two (3-aminophenyl) HFC-236fa of 2,2-, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 4,4 '-diamino-diphenylamine, 2，4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone-, 1,3-diamino pyrene, 1,6-diamino pyrene, 1,8-diamino pyrene, 2,7 diamin of luorene, two (4-aminophenyl) tetramethyl disiloxane of 1,3-, p-diaminodiphenyl, 2,2 '-tolidine, two (4-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, two (4-aminophenyl) pentane of 1,5-, two (4-aminophenyl) hexane of 1,6-, two (4-aminophenyl) heptane of 1,7-, two (4-aminophenyl) octane of 1,8-, two (4-aminophenyl) nonane of 1,9-, two (4-aminophenyl) decane of 1,10-, two (4-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (4-amino-benzene oxygen) decane of 1,10-, two (4-aminophenyl) third-1,3-bis-acid esters (Japanese: プ ロ パ Application-1,3-ジ オ エ ー ト), two (4-aminophenyl) fourth-Isosorbide-5-Nitrae-two acid esters, two (4-aminophenyl) penta-1,5-bis-acid esters, own-1,6-bis-acid esters of two (4-aminophenyls), two (4-aminophenyl) acid esters in heptan-1,7-bis-, two (4-aminophenyl) pungent-1,8-bis-acid esters, two (4-aminophenyl) acid esters in the ninth of the ten Heavenly Stems-1,9-bis-, two (4-aminophenyl) acid esters in the last of the ten Heavenly stems-1,10-bis-, two [4-(4-amino-benzene oxygen) phenoxy group] propane of 1,3-, Isosorbide-5-Nitrae-bis-[4-(4-amino-benzene oxygen) phenoxy group] butane, two [4-(4-amino-benzene oxygen) phenoxy group] pentane of 1,5-, two [4-(4-amino-benzene oxygen) phenoxy group] hexane of 1,6-, two [4-(4-amino-benzene oxygen) phenoxy group] heptane of 1,7-, two [4-(4-amino-benzene oxygen) phenoxy group] octane of 1,8-, two [4-(4-amino-benzene oxygen) phenoxy group] nonane of 1,9-, two [4-(4-amino-benzene oxygen) phenoxy group] decane of 1,10-etc.
As the example of hetero ring type diamines, DAP, 2 can be exemplified, 4-diamino-pyridine, 2,4-diaminostilbenes, 3,5-triazine, 2,7-diamino diphenylene-oxide, 3,6-diaminocarbazole, 2,4-diamino-6-sec.-propyl-1,3,5-triazine, 2,5-two (4-aminophenyls)-1,3,4- diazole etc.
As the example of aliphatie diamine, can 1 be exemplified, 2-diaminoethanes, 1, 3-diaminopropanes, 1, 4-diaminobutane, 1, 5-1,5-DAP, 1, 6-diamino hexane, 1, 7-diaminoheptane, 1, 8-diamino-octane, 1, 9-diamino nonane, 1, 10-diamino decane, 1, 3-diamino-2, 2-dimethylpropane, 1, 6-diamino-2, 5-dimethylhexane, 1, 7-diamino-2, 5-dimethyl heptane, 1, 7-diamino-4, 4-dimethyl heptane, 1, 7-diamino-3-methylheptane, 1, 9-diamino-5-methylheptane, 1, 12-diamino dodecane, 1, 18-diamino octadecane, 1, 2-two (the amino propoxy-of 3-) ethane etc.
As the example of aromatic-aliphatic diamines, the diamines that formula [11] represents can be exemplified.
H 2N-Ar-R 1-NH-R 2[11]
In formula, Ar is phenylene or naphthylidene, R 1for the alkylidene group of carbon number 1 ~ 5, R 2for hydrogen atom or methyl.
As the object lesson of the diamines that formula [11] represents, 3-amino-benzylamine can be exemplified, 4-amino-benzylamine, 3-Amino-N-methyl benzylamine, 4-Amino-N-methyl benzylamine, 3-amino-benzene ethamine, 4-amino-benzene ethamine, 3-Amino-N-methyl phenylethylamine, 4-Amino-N-methyl phenylethylamine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-(3-dimethylaminopropyl) aniline, 4-(3-dimethylaminopropyl) aniline, 3-(4-aminobutyl) aniline, 4-(4-aminobutyl) aniline, 3-(4-methylamino butyl) aniline, 4-(4-methylamino butyl) aniline, 3-(5-Aminopentyl) aniline, 4-(5-Aminopentyl) aniline, 3-(5-methylamino-pentyl) aniline, 4-(5-methylamino-pentyl) aniline, 2-(the amino naphthyl of 6-) methylamine, 3-(the amino naphthyl of 6-) methylamine, 2-(the amino naphthyl of 6-) ethamine, 3-(the amino naphthyl of 6-) ethamine etc.
When the diamines that formula [11] represents and the diamines that formula [1] represents share, gained polyamic acid or polyimide (be polymkeric substance hereinafter referred to as them) improve further to the solvability of organic solvent, and liquid crystal aligning excellence when using as liquid crystal orientation film, be therefore preferred.What is more, when share with the diamines (hereinafter also referred to inclination diamines) of increase liquid crystal pretilt angle described later, the effect of the tilt angle increasing liquid crystal further can be given play to.Therefore, when the tilt angle of formed objects will be obtained, even if the consumption of inclination diamines also can obtain big tilt angle less.In addition, the printing improving aligning agent for liquid crystal is also expected to.
The preferred content of the diamines that formula [11] represents is 10 ~ 80mol% of diamine component total amount, is more preferably 20 ~ 70mol%.
As the diamines (inclination diamines) of tilt angle that can increase liquid crystal, can exemplify and there is chain alkyl, perfluoroalkyl, aromatic cyclic base, aliphatic cyclic base or their diamines of substituting group, steroid class backbone radical etc. of combining.The diamines that these diamines can represent with formula [1] share.
Below illustrate the object lesson with described substituent diamines, but the present invention is not limited thereto.In addition, in illustrative formula [13] below ~ formula [38], j represents the integer of 5 ~ 20, and k represents the integer of 1 ~ 20.
In above-mentioned diamines, the diamines of formula [12] because its liquid crystal aligning is excellent preferably.The diamines of formula [19] ~ formula [26] because of manifesting of its tilt angle can be very high, so can suitably for OCB (optical compensation curved) liquid crystal alignment films (hereinafter referred to as OCB alignment films), vertically-oriented type liquid crystal alignment films (hereinafter referred to as VA alignment films).
Such as, in TN liquid crystal alignment films (tilt angle is 3 ~ 5 °), the content of the diamines of formula [12] is preferably 10 ~ 30mol% of diamine component total amount; In OCB alignment films or VA alignment films (tilt angle is 10 ~ 90 °), the content of the diamines of formula [19] ~ formula [26] is preferably 5 ~ 40mol% of diamine component total amount, but is not limited thereto.
If consider the solvability of polyamic acid or the polyimide used in aligning agent for liquid crystal of the present invention, liquid crystal aligning, pitch angle, voltage retention, the balance of each characteristics such as savings electric charge, then such as in use formula [1], when the diamines that formula [11] and formula [12] represent is polymerized, the preferred ratio of each diamine component is 10 ~ 50% (formula [1])/20 ~ 80% (formula [11])/10 ~ 30% (formula [12]) with molar ratio computing, be more preferably 20 ~ 40%/30 ~ 50%/10 ~ 30%, but be not limited thereto.
< tetracarboxylic dianhydride composition >
In the polyamic acid that aligning agent for liquid crystal of the present invention is required or polyimide, there is no particular limitation for the tetracarboxylic dianhydride's composition reacted with above-mentioned diamine component.That is, not only can use a kind of tetracarboxylic dianhydride, also can tetracarboxylic dianhydride of more than two kinds share.
In aligning agent for liquid crystal of the present invention, from the voltage retention etc. improving further liquid crystal cell, as the tetracarboxylic dianhydride reacted with aforementioned diamine component, preferably use the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure.
As the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, 1,2,3,4-tetramethylene tetracarboxylic dianhydride can be exemplified, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,4-dicarboxyl-1-cyclohexyl succsinic acid dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, [4-(2,5-dioxotetrahydro furans-3-base)-1,2,3,4-naphthane-1,2-dicarboxylic anhydrides], 1,2,3,4-butane tetracarboxylic acid dianhydride, dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, pungent-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride of cis-3,7-dibutyl rings, three rings [4.2.1.02,5] nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride, six rings [6.6.0.12,7.03,6.19,14.010,13] n-Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride etc.Wherein, use during 1,2,3,4-tetramethylene tetracarboxylic dianhydride and can obtain the alignment films of liquid crystal aligning excellence, because of but preferably.
What is more, when share with aromatic tetracarboxylic acid's dianhydride, liquid crystal aligning improves and can accelerate the minimizing of the savings electric charge of liquid crystal cell.As aromatic tetracarboxylic acid's dianhydride, pyromellitic acid dianhydride, 3 can be exemplified, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) ether dianhydride, two (3,4-dicarboxyphenyi) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.Wherein, pyromellitic acid dianhydride particularly preferably.
Consider from the balance of each characteristic such as solvability, liquid crystal aligning, voltage retention, savings electric charge of the polyamic acid of gained or polyimide, have the tetracarboxylic dianhydride of ester ring type structure or aliphatic structure and the usage rate of aromatic tetracarboxylic acid's dianhydride with the former/molar ratio computing of the latter is preferably 90/10 ~ 50/50, is more preferably 80/20 ~ 60/40.
< polyreaction >
In the present invention, there is no particular limitation for the polymerisation process of tetracarboxylic dianhydride's composition and diamine component.General by mixing in organic solvent to carry out polyreaction to obtain polyamic acid, obtain polyimide by making this polyamic acid dehydration closed-loop.
As the method that tetracarboxylic dianhydride's composition and diamine component are mixed in organic solvent, there is following methods: solution diamine component being dispersed or dissolved in organic solvent stirs, by the method that tetracarboxylic dianhydride's composition directly adds or adds after being dispersed or dissolved in organic solvent; The method of adding diamine component in the solution of organic solvent is dispersed or dissolved in conversely at tetracarboxylic dianhydride's composition; The method etc. that tetracarboxylic dianhydride's composition and diamine component alternately add.In addition, when tetracarboxylic dianhydride's composition or diamine component are made up of multiple compounds, the state that described Multiple components can be pre-mixed carries out polyreaction, also can carry out polyreaction successively respectively.
Temperature when tetracarboxylic dianhydride's composition and diamine component carry out polyreaction is in organic solvent generally 0 ~ 150 DEG C, is preferably 5 ~ 100 DEG C, is more preferably 10 ~ 80 DEG C.Temperature height then polyreaction early completes, but temperature is too high, sometimes can not obtain the polymkeric substance of high molecular.
In addition, polyreaction can be carried out by any concentration, the words that the total concentration of tetracarboxylic dianhydride's composition and diamine component is too low can be difficult to the polymkeric substance obtaining high molecular, and the viscosity of the words reaction solution of excessive concentration can become too high, be difficult to stir equably, therefore total concn is preferably 1 ~ 50 quality %, is more preferably 5 ~ 30 quality %.Also after the polyreaction initial stage carries out with high density, organic solvent can be added again.
As long as organic solvent used during above-mentioned polyreaction dissolves the polyamic acid generated, there is no particular limitation.N can be exemplified as object lesson, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethyl-urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolactone, 1,3-dimethyl-imidazolinone etc.These solvents can be used alone, also can be used in combination.Moreover, even the solvent that polyamic acid dissolves can not be made, as long as in the scope that the polyamic acid generated is not separated out, also can be mixed in above-mentioned solvent and use.In addition, the moisture in organic solvent can hinder polyreaction and then the polyamic acid of generation is hydrolyzed, and therefore organic solvent dehydrates rear use as well as far as possible.
Tetracarboxylic dianhydride's composition used in the polyreaction of polyamic acid and the ratio of diamine component are preferably 1:0.8 ~ 1:1.2 with molar ratio computing, and this mol ratio is more close to 1:1, and the molecular weight of the polyamic acid of gained is larger.Control the molecular weight of this polyamic acid, the molecular weight of the polyimide of gained after adjustable imidization.
There is no particular limitation for the molecular weight of polyamic acid of the present invention or polyimide, but when being contained in aligning agent for liquid crystal, be coated with film strength from gained and consider as the angle of the process convenience of aligning agent for liquid crystal, weight-average molecular weight is preferably 2000 ~ 200000, is more preferably 5000 ~ 50000.
The synthesis > of < polyimide
Polyimide used in aligning agent for liquid crystal of the present invention is the polyimide obtained by above-mentioned polyamic acid imidization.The imidization of polyamic acid by organic solvent, stirring 1 ~ 100 hour and carrying out under the existence of basic catalyst and acid anhydrides.
As basic catalyst, pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc. can be exemplified.Wherein, pyridine has the suitable alkalescence that reaction is carried out, because of but preferred.
In addition, as acid anhydrides, diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc. can be exemplified.Wherein, diacetyl oxide owing to being easy to after completing at imidization carry out the refining of gained polyimide, because of but preferably.
As organic solvent, solvent used when can use foregoing polyamides acid polyreaction.
The imide rate of polyimide controls by regulating catalytic amount, temperature of reaction, reaction times etc.The amount of basic catalyst is now preferably 0.2 ~ 10 times mole of acid amides acidic group, is more preferably 0.5 ~ 5 times mole.In addition, the amount of acid anhydrides is preferably 1 ~ 30 times mole of acid amides acidic group, is more preferably 1 ~ 10 times mole.Temperature of reaction preferably-20 ~ 250 DEG C, is more preferably 0 ~ 180 DEG C.
There is no particular limitation for the imide rate of the polyimide that aligning agent for liquid crystal of the present invention is used, but in order to obtain the liquid crystal orientation film of more high voltage holding ratio, imide rate preferably more than 40%, more preferably more than 60%, particularly preferably in more than 80%.
Remain the catalyzer etc. of interpolation in the polyimide solution obtained therefrom, therefore when for aligning agent for liquid crystal, polyimide preferably uses after recovery is cleaned.
The recovery of polyimide is filtered after polyimide being separated out by the solution after drop into imidization under the stirring of Weak solvent and is carried out.As Weak solvent now, methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methylethylketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene etc. can be exemplified.The washing of the polyimide reclaimed also can be carried out in this Weak solvent.Reclaim clean polyimide thus and under normal temperature, powder can be formed as after drying or heat drying under normal or reduced pressure.
This operation also can be carried out foregoing polyamides acid.Such as, when not wishing to contain solvent used in the polymerization of polyamic acid in aligning agent for liquid crystal or when for removing unreacted monomer component or impurity in reaction soln, above-mentioned precipitation recovery can be carried out and refine.
< aligning agent for liquid crystal >
Aligning agent for liquid crystal of the present invention contains the coating fluid by least one polymkeric substance in the polyamic acid of above-mentioned gained and polyimide.
If exemplify this Production Example, then the reaction soln of foregoing polyamides acid or polyimide can directly use, and also can dilute rear use, uses after the material reclaimed can also being dissolved in organic solvent again from reaction solution precipitation.In addition, dilution or again in dissolution process, can carry out the adjustment of the solvent composition for controlling the coating to substrate or adding for the additive that improves coating characteristic.Moreover the solution of the solution or polyamic acid that also can be different from above-mentioned polyimide with structure mixes or adds other resinous principle.
As above-mentioned dilution or organic solvent used in dissolution process again, as long as can dissolve the solvent of contained polymkeric substance, there is no particular limitation.As its concrete example, N can be exemplified, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl-2-pyrrolidone, NVP, dimethyl sulfoxide (DMSO), tetramethyl-urea, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolactone, 1,3-dimethyl-imidazolinone etc.Wherein, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, 1,3-dimethyl-imidazolinone, gamma-butyrolactone is preferably used.But these solvents can use a kind, and also two or more is used in combination.
As for controlling the solvent that aligning agent for liquid crystal adds the coating of substrate, ethyl cellosolve can be exemplified, ethylene glycol butyl ether, ethyl carbitol, diethylene glycol monobutyl ether, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, diethylene glycol diethyl ether, single propylene glycol acetate, propylene glycol diacetate, DPGME, 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 lactate etc.These solvents comprise the solvent that polyamic acid or polyimide can not be made separately to dissolve, as long as but in the scope that polymkeric substance is not separated out, these solvents can be mixed in aligning agent for liquid crystal of the present invention.Particularly by suitably mixing the solvent with low surface tension, film homogeneity when coating substrate can be improved, therefore this kind solvent also aligning agent for liquid crystal used in the present invention.Wherein, consider from the deliquescent angle of polyimide, ethylene glycol butyl ether, ethyl carbitol, DPGME, diethylene glycol diethyl ether are particularly preferably.
As the additive for improving coating characteristic, the silane coupling agents such as 3-amino propyl methyl diethoxy silane, 3-phenyl amino propyl Trimethoxy silane, APTES, (aminoethylaminomethyl) styroyl Trimethoxy silane can be exemplified.By adding these silane coupling agents, the adaptation of film to substrate can be improved, but the easily aggegation such as polyamic acid or polyimide when addition is excessive.Therefore, the content of silane coupling agent is preferably 0.5 ~ 10 quality % relative to the total mass of polyamic acid or polyimide, is more preferably 1 ~ 5 quality.
The solid component concentration of aligning agent for liquid crystal of the present invention, suitably can change according to the setting of the liquid crystal aligning film thickness for being formed, but be preferably 1 ~ 10 quality %.Then be difficult to be formed homogeneous and do not have defective film less than 1 quality %, than 10 quality % at most sometimes the storage stability of solution be deteriorated.Solids component mentioned here refers to from aligning agent for liquid crystal except the composition after desolventizing.In addition, there is no particular limitation for the concentration of the polyamic acid that aligning agent for liquid crystal of the present invention is used or polyimide, but consider, preferably at more than 1 quality % from the angle of the characteristic of gained liquid crystal orientation film, more preferably at more than 3 quality %, particularly preferably in more than 5 quality %.
As above the aligning agent for liquid crystal of gained preferably first filtered before coating substrate.
< liquid crystal display device >
After aligning agent for liquid crystal of the present invention can coat substrate through dry, burn till and form film.By carrying out friction treatment to this coated surface, can be used as friction liquid crystal orientation film and using.In addition, also can be used as VA (vertical orientated use) liquid crystal orientation film, the optical alignment film without friction treatment.
Now, as substrate used, as long as the substrate that the transparency is high, there is no particular limitation.Can use the plastic bases etc. such as sheet glass, vinylformic acid substrate or polycarbonate substrate, be preferred for the substrate being formed with ITO electrode etc. of liquid crystal drive from the angle that operation is simplified.In addition, for the liquid crystal display device of reflection-type, also can use the opaque materialss such as silicon wafer by the substrate only in side, electrode now also can use the material of the reflected light such as aluminium.
As the coating process of aligning agent for liquid crystal, spin-coating method, print process, ink jet method etc. can be exemplified, but from the viewpoint of the industrial flexographic printing process that widely uses of productivity, the method is also suitable for aligning agent for liquid crystal of the present invention.
Drying process after coating of liquid crystalline aligning agent is also nonessential, but the time after coating to burning till is in all unfixed situation of every block substrate or when not burning till immediately after coating, preferably includes drying process.Under the dry degree can not can be out of shape because of the carrying of substrate etc. in film shape, solvent is evaporated, to these dry means, there is no particular limitation.Such as, dry 0.5 ~ 30 minute can be exemplified on the hot-plate of 50 ~ 150 DEG C, preferably 80 ~ 120 DEG C, the preferred method of 1 ~ 5 minute.
Substrate after aligning agent for liquid crystal coating burn till preferably 100 ~ 350 DEG C, more preferably 150 ~ 300 DEG C, preferably again to carry out under the arbitrary temp of 180 ~ 250 DEG C.When there is acid amides acidic group in aligning agent for liquid crystal, amido acid changes into imido transformation efficiency to be changed according to this firing temperature, but aligning agent for liquid crystal of the present invention there is no need 100% imidization.
About the thickness of the film after burning till, too thick, be disadvantageous from the viewpoint of the power consumption of liquid crystal display device, too thin, the reliability of liquid crystal display device can decline sometimes, is therefore preferably 10 ~ 200nm, is more preferably 50 ~ 100nm.
With known friction gear, as the material of friction cloth now, cotton, artificial silk, nylon etc. can be exemplified to the friction treatment of the coated surface be as above formed on substrate.
Substrate with the liquid crystal orientation film obtained by aforesaid method can manufacture liquid crystal cell by known method, forms liquid crystal display device.As the example making liquid crystal cell, generally adopt with the following method: will a pair substrate clamping preferably 1 ~ 30 μm, the more preferably spacer of 2 ~ 10 μm of liquid crystal orientation film be formed with, the requirement at any angle in 0 ~ 270 ° is become to arrange according to making frictional direction, surrounding sealing agent is fixed, and seals after injecting liquid crystal.As liquid crystal inclosure method, there is no particular limitation, can illustrate (ODF) method etc. of dripping of will carry out after injecting the vacuum method of liquid crystal, the liquid crystal that drips after obtained liquid crystal cell inner pressure relief sealing.
The liquid crystal display device obtained therefrom is applicable to TN liquid crystal display device, stn liquid crystal display element, TFT liquid crystal display device, OCB liquid crystal display device, also has all kinds display elements such as lateral electric-field type (IPS) liquid crystal display device, VA liquid crystal display device.
Embodiment
Below exemplify embodiment to be described in further detail the present invention, but do not form the explanation of limitation of the invention.
(synthesis example 1) 3,5-synthesis of diamino benzyl furans-2-carboxylicesters
1, the 3-dinitrobenzene benzylalcohol of 25.0g, the 2 furoyl chloride of 10.5mL and the tetrahydrofuran (THF) of 300mL is added in the there-necked flask of 500mL (milliliter).Dripped the pyridine of 9.0mL again, in stirred at ambient temperature 25 hours.After reaction terminates, add 50mL pure water, stir 1 hour.Add extraction into ethyl acetate organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Then, in organic layer, add anhydrous magnesium sulfate to dehydrate.After filtration, with rotatory evaporator except desolventizing.With tetrahydrofuran (THF)/hexane=1/3 (volume ratio, identical below), recrystallization is carried out to residue, obtain the Off-white solid (yield 93%) of 27.5g.This Off-white solid 1h-NMR measurement result is as follows.From this results verification, the solid of gained is target dinitro compound.In addition, 1h-NMR refers to the NMR (Nuclear Magnetic Resonance) spectrum of hydrogen atom in molecule.
1H NMR(400MHz，CDCl 3)：δ9.04(t,1H)，8.66－8.63(m，2H)，7.65(dd，1H)，7.32(dd，1H)，6.58(dd，1H)，5.53(s，2H)
Then, in the four-hole boiling flask of 500mL, add the dinitro compound of 23.8g, the platinum/carbon (mass ratio 1/10, identical below) of 2.4g and the methyl alcohol of 239g, stir 43 hours under a hydrogen atmosphere.After reaction terminates, carry out diatomite filtration, with rotatory evaporator except desolventizing.With Virahol, recrystallization is carried out to residue, obtain the orange solid (yield 85%) of 16.1g.
This shallow tan solid 1h-NMR measurement result is as follows.From results verification, the orange solid of gained is targeted diamine.
1H NMR(400MHz，CDCl 3)：δ7.58(dd，1H)，7.21(dd，1H)，6.51(dd，1H)，6.18(dt，2H)，6.00(t，1H)，5.16(s，2H)，3.62(br，4H)
The synthesis of (synthesis example 2) furans-2-ylmethyl 3,5-diaminobenzoic acid ester
The tetrahydrofuran (THF) of the 3,5 dinitrobenzoylchloride of 25.3g, the furfuralcohol of 10.0mL and 200mL is added in the four-hole boiling flask of 500mL.Dripped the pyridine of 9.7mL again, in stirred at ambient temperature 16 hours.After reaction terminates, add 50mL pure water, stir 1 hour.Add extraction into ethyl acetate organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Then, in organic layer, add anhydrous magnesium sulfate to dehydrate.After filtration, with rotatory evaporator except desolventizing.Residue silica gel column chromatography (solvent distillation is hexane: the mixed solvent of ethyl acetate=3:1) is refined, and obtains the dinitro compound (yield 95%) of 30.3g.Gained solid 1h-NMR measurement result is as follows.From this results verification, the solid of gained is target dinitro compound.
1H NMR(400MHz，CDCl 3)：δ9.23(t,1H)，9.17(d，2H)，7.49(dd，1H)，6.57(dd，1H)，6.43(dd，1H)，5.44(s，2H)
The dinitro compound of 30.3g, the platinum/carbon of 3.1g and the methyl alcohol of 400mL is added, under a hydrogen atmosphere in stirring at room temperature in the four-hole boiling flask of 500mL.After reaction terminates, carry out diatomite filtration, with rotatory evaporator except desolventizing.Carry out recrystallization with isopropanol/hexane=1/1 pair residue, obtain the shallow tan solid (yield 48%) of 11.6g.
This shallow tan solid 1h-NMR measurement result is as follows.From results verification, the shallow tan solid of gained is targeted diamine.
1H NMR(400MHz，DMSO－d 6)：δ7.71(dd,1H)，6.57(dd，1H)，6.48(dd，2H)，6.41(d，2H)，6.01(t，1H)，5.20(s，2H)，5.02(br，4H)
The synthesis of (synthesis example 3) N-(3,5-diamino-phenyl) furans-2-carboxylic acid amides
3, the 5-dinitranilines of 24.1g, the pyridine of 11.7mL and the tetrahydrofuran (THF) of 300mL is added in the there-necked flask of 500mL.Dripped the 2 furoyl chloride of 13.8mL again, in stirred at ambient temperature 18 hours.After reaction terminates, add 50mL pure water, stir 1 hour.Add extraction into ethyl acetate organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Then, in organic layer, add anhydrous magnesium sulfate to dehydrate.After filtration, with rotatory evaporator except desolventizing.Carry out recrystallization with tetrahydrofuran (THF)/hexane=1/3 pair residue, obtain the dinitro compound (yield 85%) of 31.1g.Gained solid 1h-NMR measurement result is as follows.From this results verification, the solid of gained is target dinitro compound.
1H NMR(400MHz，DMSO－d 6)：δ11.1(s，1H)，9.11(d，2H)，8.54(t，1H)，8.05(dd，1H)，7.46(dd，1H)，6.78(dd，1H)
The dinitro compound of 30.9g, the platinum/carbon of 4.2g, the Isosorbide-5-Nitrae-two of 300g is added in the four-hole boiling flask of 1L the tetrahydrofuran (THF) of alkane and 800g, under a hydrogen atmosphere in stirring at room temperature.After reaction terminates, carry out diatomite filtration, with rotatory evaporator except desolventizing.With Virahol, recrystallization is carried out to residue, obtain the shallow tan solid (yield 89%) of 21.4g.
This shallow tan solid 1h-NMR measurement result is as follows.From results verification, the shallow tan solid of gained is targeted diamine.
1H NMR(400MHz，DMSO－d 6)：δ9.51(s，1H)，7.87(dd，1H)，7.28(dd，1H)，6.65(dd，1H)，6.23(d，2H)，5.60(t，1H)，4.73(br，4H)
(synthesis example 4) 3,5-synthesis of diamino benzyl thiophene-2-carboxylic acid ester (DABTh)
3, the 5-dinitrobenzene benzylalcohols of 21.5g, the 2-thiophene chloride of 12.1mL and the tetrahydrofuran (THF) of 200mL is added in the there-necked flask of 500mL.Dripped the pyridine of 9.6mL again, in stirred at ambient temperature 48 hours.After reaction terminates, add 50mL pure water, stir 1 hour.Add extraction into ethyl acetate organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Then, in organic layer, add anhydrous magnesium sulfate to dehydrate.After filtration, with rotatory evaporator except desolventizing.With ethyl acetate and hexane, recrystallization is carried out to residue, obtain the dinitro compound (yield 82%) of 27.5g.Gained solid 1h-NMR measurement result is as follows.
1H NMR(400MHz,CDCl 3):δ9.03(t,1H),8.66-8.63(m,2H),7.90(dd,1H),7.66(dd,1H),7.17(dd,1H),5.52(s,2H)
In the four-hole boiling flask of 500mL, add the dinitro compound of 17.5g, the platinum/carbon of 4.3g and the tetrahydrofuran (THF) of 200g, stir 48 hours under a hydrogen atmosphere.After reaction terminates, carry out diatomite filtration, with rotatory evaporator except desolventizing.With tetrahydrofuran (THF) and Virahol, recrystallization is carried out to residue, obtain the shallow tan solid (yield 92%) of 12.9g.
This shallow tan solid 1h-NMR measurement result is as follows.From results verification, the shallow tan solid of gained is targeted diamine.
1H NMR(400MHz,CDCl 3):δ7.83(dd,1H),7.56(dd,1H),7.10(dd,1H),6.19-6.17(m,2H),6.00(t,1H),5.16(s,2H),3.61(br,4H)
(synthesis example 5) 3,5-synthesis of diamino benzyl-5-methyl furan-2 carboxylicesters (MeDABFr)
In the four-hole boiling flask of 500mL, add the 5-methyl-pyromucic acid of 8.5g and the methylene dichloride of 170mL, be cooled to 0 DEG C from room temperature.Then, add the oxalyl dichloro (Japanese: bis-salt オ キ ラ リ Le) of 5.9mL and the DMF of 0.5g, in stirred at ambient temperature 2 hours.After stirring, add 3, the 5-dinitrobenzene benzylalcohols of 13.4g and the pyridine of 6mL, in stirred at ambient temperature 16 hours.After reaction terminates, add 50mL pure water, stir 1 hour.Afterwards, add extraction into ethyl acetate organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.In organic layer, add anhydrous magnesium sulfate dehydrate, after diatomite filtration, with rotatory evaporator except desolventizing.Use Virahol cleaning residue, obtain the dinitro compound (yield 86%) of 17.1g.Gained solid 1h-NMR measurement result is as follows.
1H NMR(400MHz,CDCl 3):δ9.02(t,1H),8.65-8.62(m,2H),7.23-7.21(m,1H),6.20-6.18(m,1H),5.52-5.50(m,2H),2.43-2.41(m,3H)
In the four-hole boiling flask of 500mL, add the dinitro compound of 16.7g, the platinum/carbon of 1.7g and the tetrahydrofuran (THF) of 170g, stir 21 hours under a hydrogen atmosphere.After reaction terminates, carry out diatomite filtration, with rotatory evaporator except desolventizing.With Virahol, recrystallization is carried out to residue, obtain the shallow tan solid (yield 68%) of 9.1g.
This shallow tan solid 1h-NMR measurement result is as follows.From results verification, the shallow tan solid of gained is targeted diamine.
1H NMR(400MHz,CDCl 3):δ7.15(d,2H),7.10(d,1H),6.11-6.09(m,1H),5.97(t,1H),5.13(s,2H),3.57(br,4H),2.37(s,3H)
(synthesis example 6) 3,5-synthesis of diamino benzyl furans-3-carboxylicesters (3-DABFr)
In the four-hole boiling flask of 500mL, add the 3-furancarboxylic acid of 8.2g and the methylene dichloride of 240mL, be cooled to 0 DEG C from room temperature.Then, add the oxalyl dichloro of 6.4mL and the DMF of 0.5g, in stirred at ambient temperature 2 hours.After stirring, add 3, the 5-dinitrobenzene benzylalcohols of 15.0g and the pyridine of 9.7mL, in stirred at ambient temperature 47 hours.After reaction terminates, add 50mL pure water, stir 1 hour.Afterwards, add extraction into ethyl acetate organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.In organic layer, add anhydrous magnesium sulfate dehydrate, after filtration, with rotatory evaporator except desolventizing.By ethyl acetate, recrystallization is carried out to residue, obtain the dinitro compound (yield 78%) of 16.8g.Gained solid 1h-NMR measurement result is as follows.
1H NMR(400MHz,CDCl 3):δ9.03(t,1H),8.63-8.61(m,2H),8.12(dd,1H),7.41(dd,1H),6.79(dd,1H),5.48(d,2H)
In the four-hole boiling flask of 500mL, add the dinitro compound of 16.5g, the platinum/carbon of 1.7g and the tetrahydrofuran (THF) of 165g, stir 29 hours under a hydrogen atmosphere.After reaction terminates, carry out diatomite filtration, with rotatory evaporator except desolventizing.With tetrahydrofuran (THF) and Virahol, recrystallization is carried out to residue, obtain the shallow tan solid (yield 57%) of 7.4g.
This shallow tan solid 1h-NMR measurement result is as follows.From results verification, the shallow tan solid of gained is targeted diamine.
1H NMR(400MHz,CDCl 3):δ8.04(dd,1H),7.42(dd,1H),6.77(dd,1H),6.14(d,2H),5.98(t,1H),5.10(s,2H),3.57(br,4H)
The abbreviation of the compound that the synthesis etc. of polyamic acid and polyimide uses is as follows:
< tetracarboxylic dianhydride >
CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride
TDA:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride
< diamines >
2-DABFr:3,5-diamino benzyl furans-2-carboxylicesters
FrDAB: furans-2-ylmethyl 3,5-diaminobenzoic acid ester
DAAFr:N-(3,5-diamino-phenyl) furans-2-carboxylic acid amides
DABTh:3,5-diamino benzyl thiophene-2-carboxylic acid ester
MeDABFr:3,5-diamino benzyl-5-methyl furan-2 carboxylicesters
3-DABFr:3,5-diamino benzyl furans-3-carboxylicesters
Me4APhA:4-Amino-N-methyl phenylethylamine
P-PDA: p-phenylenediamine
DDM:4,4 '-diaminodiphenyl-methane
C14DAB:4-tetradecyl oxygen-1,3-diaminobenzene
C16DAB:4-hexadecyl oxygen-1,3-diaminobenzene
3-ABA:3-amino-benzylamine
< organic solvent >
NMP:N-N-methyl-2-2-pyrrolidone N-
γ-BL: gamma-butyrolactone
BC: ethylene glycol butyl ether
DPM: DPGME
DMF: dimethyl formamide
The mensuration > of < molecular weight
Molecular weight GPC (normal temperature gel permeation chromatography) device of the polyamic acid obtained by polyreaction or polyimide measures, and as the scaled value of polyoxyethylene glycol and polyethylene oxide, calculates number-average molecular weight and weight-average molecular weight.
GPC device: Showa Denko K. K (Shodex society) system (GPC-101)
Pillar: Showa Denko K. K's system (series connection of KD803 and KD803)
Column temperature: 50 DEG C
Elutriant: DMF (as additive, the lithiumbromide monohydrate (LiBrH of 30mmol/L 2o), the phosphoric acid anhydrous crystal (o-phosphoric acid) of 30mmol/L, the tetrahydrofuran (THF) (THF) of 10ml/L)
Sulfuric acid: 1.0ml/ divides
Calibration line making standard test specimen: (East ソ ー society of TOSOH Co., Ltd) TSK standard polyethylene oxide (molecular weight about 900 processed, 000,150,000,100,000,30,, and Polymer Laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyoxyethylene glycol (molecular weight about 12,000,4 of making 000), 000,1,000).
The mensuration > of < imide rate
The imide rate of the polyimide obtained by chemical imidization is calculated as follows: be dissolved in by this polyimide in d6-DMSO (dimethyl sulfoxide (DMSO)-d6), measures 1h-NMR, is obtained the ratio of non-imidization and residual acid amides acidic group, thus calculates imide rate by the ratio of the integrated value of proton peak.
The making > of < liquid crystal cell
Liquid crystal cell is made as described below by by embodiment and the formulated aligning agent for liquid crystal of comparative example.
Aligning agent for liquid crystal is spun on the glass substrate with transparency electrode, on the hot-plate of 70 DEG C after dry 70 seconds, the hot-plate of 210 DEG C carries out 10 minutes burn till, forms the film of thickness 100nm.With artificial silk cloth, this coated surface is rubbed under the condition of roller revolution 1000rpm, roller gait of march 50mm/ second, 0.3mm intrusion with the friction gear of roller footpath 120mm, obtain the substrate with liquid crystal orientation film.Prepare 2 pieces of substrates with liquid crystal orientation film, after the liquid crystal aligning face of a piece scatters the spacer of 6 μm, printing and sealing agent thereon, then make liquid crystal aligning face relatively and by another block baseplate-laminating under the orthogonal condition of frictional direction,, make sealant cures, make negative crystal born of the same parents.In negative crystal born of the same parents, inject liquid crystal MLC-2003 (Merck & Co., Inc. (メ ルク society) system) by decompression injection method, seal inlet, obtain Twisted Nematic liquid crystal structure cell.
Mensuration and the evaluating characteristics of the physical property of each liquid crystal cell made are as described below.
In addition, the result of the composition of each aligning agent for liquid crystal, the physical property measurement of each liquid crystal orientation film and evaluating characteristics etc. in embodiment 1 ~ 9 and comparative example 1 ~ 3 is shown in table 2, table 3.
< friction patience evaluates >
With the substrate of the method manufacture described in the making > of above-mentioned < liquid crystal cell with liquid crystal orientation film.Now, the intrusion of friction condition becomes 0.5mm.With confocal some laser capture microdissection sem observation gained liquid crystal orientation film surface, carry out following evaluation.
Zero: do not observe abrasive dust attachment or friction scar.
△: observe abrasive dust attachment or friction scar.
×: observe film and peel off or estimate friction scar.
< liquid crystal aligning evaluates >
For presenting the quality of liquid crystal aligning, make following liquid crystal cell.Aligning agent for liquid crystal is spun on the substrate with transparency electrode, on the hot-plate of 70 DEG C after dry 70 seconds, the hot-plate of 210 DEG C carries out 10 minutes burn till, forms the film of thickness 100nm.With artificial silk cloth, this coated surface is rubbed under the condition of roller revolution 1000rpm, roller gait of march 50mm/ second, 0.3mm intrusion with the friction gear of roller footpath 120mm, obtain the substrate with liquid crystal orientation film.Prepare 2 pieces of above-mentioned substrates with liquid crystal orientation film, after the liquid crystal aligning face of a piece scatters the spacer of 6 μm, printing and sealing agent thereon, then make liquid crystal aligning face relatively and frictional direction be the condition of 180 ° under by another block baseplate-laminating, make sealant cures, make negative crystal born of the same parents.In negative crystal born of the same parents, inject liquid crystal MLC-2003 (Merck & Co., Inc.'s system) by decompression injection method, seal inlet, obtain antiparallel type liquid crystal cell.The initial stage orientation of this liquid crystal cell of visual observations.Evaluate as follows.The results are shown in aftermentioned table 2.
Zero: orientation well.
×: observe more light leak or orientation bad position.
< tilt angle measures >
Twisted Nematic liquid crystal structure cell method described in making > with above-mentioned < liquid crystal cell manufactured after 2 hours, carries out the mensuration of tilt angle and the mensuration of voltage retention in 105 DEG C of heating.Tilt angle Crystal Rotation method measures.
The mensuration > of < voltage retention
Carry out with being determined as follows of voltage retention of the Twisted Nematic liquid crystal structure cell of the method manufacture described in the making > of above-mentioned < liquid crystal cell: at the temperature of 90 DEG C, between 60 μ s, apply 4V voltage, measure the voltage after 16.67ms, calculate voltage and can keep how many, using this as voltage retention.In addition, the mensuration of voltage retention uses Dongyang technology Co., Ltd. (East Yang テ Network ニ カ society) the voltage retention determinator of VHR-1 processed.
< puts aside the mensuration > of electric charge (RDC)
To the Twisted Nematic liquid crystal structure cell that the method described in the making > with above-mentioned < liquid crystal cell manufactures, volts DS is applied until 1.0V with the interval of 0V ~ 0.1V at the temperature of 23 DEG C, measure the flicker amplitude level under each voltage, make calibration line.After 5 minutes ground connection, apply 3.0V voltage of alternating current, 5.0V volts DS 1 hour, only volts DS has been just measure flicker amplitude level immediately after 0V afterwards, by estimating RDC (estimating and measuring method of this RDC is with reference to flicker reference entry) according to the calibration line made in advance.
Embodiment 1
With the CBDA of 5.00g (0.025mol) as tetracarboxylic dianhydride's composition, with the 2-DABFr of 6.03g (0.026mol) as diamine component, in the NMP of 44.14g, react 16 hours under room temperature, the concentration obtaining polyamic acid (PAA-1) is the solution of 20 quality %.Dilute polyamic acid (PAA-1) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, obtain the aligning agent for liquid crystal that polyamic acid (PAA-1) is 4.6 quality %.The evaluation of friction patience, tilt angle, voltage retention (VHR) and RDC is carried out with this aligning agent for liquid crystal.Result is shown in table 2.
Embodiment 2
The NMP adding 93.33g in polyamic acid (PAA-1) solution (PAA-1 concentration is 20 quality %) of the 40g obtained by the method identical with embodiment 1 dilutes, add the diacetyl oxide of 5.77g and the pyridine of 2.39g again, react 3 hours with imidization in 40 DEG C.After about this reaction soln cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solids of precipitation.Again by this solids of methanol cleaning 2 times, afterwards in 100 DEG C of drying under reduced pressure, obtain the white powder of polyimide (SPI-1).The number-average molecular weight of this polyimide is 13204, and weight-average molecular weight is 30700.In addition, imide rate is 87%.
In the gained polyimide (SPI-1) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the DPM of the γ-BL of 8.0g, BC and 6.00g of 6.00g again, stir 20 hours in 50 DEG C, obtain the aligning agent for liquid crystal that polyimide (SPI-1) is 5 quality %.The evaluation identical with embodiment 1 is carried out with this aligning agent for liquid crystal.Result is shown in table 2.
Embodiment 3
With the CBDA of 5.52g (0.028mol) as tetracarboxylic dianhydride's composition, with the C14DAB of 3-ABA and 2.76g (0.009mol) of 2-DABFr, 1.40g (0.011mol) of 2.00g (0.009mol) as diamine component, in the NMP of 46.7g, react 16 hours under room temperature, the concentration obtaining polyamic acid (PAA-2) is the solution of 20 quality %.Dilute polyamic acid (PAA-2) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, obtain the aligning agent for liquid crystal that polyamic acid (PAA-2) is 4.6 quality %.The evaluation identical with embodiment 1 is carried out with this aligning agent for liquid crystal.Result is shown in table 2.
Embodiment 4
The NMP adding 93.3g in polyamic acid (PAA-2) solution (PAA-2 concentration is 20 quality %) of the 40.0g obtained by the method identical with embodiment 3 dilutes, add the diacetyl oxide of 6.02g and the pyridine of 2.49g again, react 3 hours with imidization in 60 DEG C.After about this reaction soln cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solids of precipitation.Again by this solids of methanol cleaning 2 times, afterwards in 100 DEG C of drying under reduced pressure, obtain the white dark brown powder of polyimide (SPI-2).The number-average molecular weight of this polyimide is 15850, and weight-average molecular weight is 42234.In addition, imide rate is 92%.
In the gained polyimide (SPI-2) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the DPM of the γ-BL of 8.00g, BC and 6.00g of 6.00g again, stir 20 hours in 50 DEG C, obtain the aligning agent for liquid crystal that polyimide (SPI-2) is 5 quality %.The evaluation identical with embodiment 1 is carried out with this aligning agent for liquid crystal.Result is shown in table 2.
Embodiment 5
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of 3-ABA and 2.79g (0.009mol) of FrDAB, 1.42g (0.012mol) of 2.02g (0.009mol) as diamine component, in the NMP of 46.7g, react 16 hours under room temperature, the concentration obtaining polyamic acid (PAA-3) is the solution of 20 quality %.
Dilute this polyamic acid (PAA-3) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, the polyamic acid (PAA-3) obtained as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Its coating fluid is used to carry out the evaluation identical with embodiment 1.Result is shown in table 2.
Embodiment 6
The NMP adding 93.3g in polyamic acid (PAA-3) solution (PAA-3 concentration is 20 quality %) of the 40.0g obtained by the method identical with embodiment 5 dilutes, add the diacetyl oxide of 6.06g and the pyridine of 2.53g again, react 3 hours with imidization in 60 DEG C.After about this reaction soln cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solids of precipitation.Again by this solids of methanol cleaning 2 times, afterwards in 100 DEG C of drying under reduced pressure, obtain the white dark brown powder of polyimide (SPI-3).The number-average molecular weight of this polyimide is 17920, and weight-average molecular weight is 41290.In addition, imide rate is 89%.
In the gained polyimide (SPI-3) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the DPM of the γ-BL of 8.00g, BC and 6.00g of 6.00g again, stir 20 hours in 50 DEG C, obtain the aligning agent for liquid crystal that polyimide (SPI-3) is 5 quality %.The evaluation identical with embodiment 1 is carried out with this aligning agent for liquid crystal.Result is shown in table 2.
Embodiment 7
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of 3-ABA and 2.79g (0.009mol) of DAAFr, 1.42g (0.012mol) of 1.89g (0.009mol) as diamine component, in the NMP of 46.7g, react 16 hours under room temperature, the concentration obtaining polyamic acid (PAA-4) is the solution of 20 quality %.
Dilute polyamic acid (PAA-4) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, the polyamic acid (PAA-4) obtained as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Its coating fluid is used to carry out the evaluation identical with embodiment 1.Result is shown in table 2.
Embodiment 8
The NMP adding 93.3g in polyamic acid (PAA-4) solution (PAA-4 concentration is 20 quality %) of the 40.0g obtained by the method identical with embodiment 7 dilutes, add the diacetyl oxide of 6.06g and the pyridine of 2.53g again, react 3 hours with imidization in 60 DEG C.After this reaction soln cool to room temperature degree, drop in the methyl alcohol of 500mL, reclaim the solids of precipitation.Again by this solids of methanol cleaning 2 times, afterwards in 100 DEG C of drying under reduced pressure, obtain the white dark brown powder of polyimide (SPI-4).The number-average molecular weight of this polyimide is 15367, and weight-average molecular weight is 39880.In addition, imide rate is 90%.
In the gained polyimide (SPI-4) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the DPM of the γ-BL of 8.00g, BC and 6.00g of 6.00g again, stir 20 hours in 50 DEG C, obtain the aligning agent for liquid crystal that polyimide (SPI-4) is 5 quality %.The evaluation identical with embodiment 1 is carried out with this aligning agent for liquid crystal.Result is shown in table 2.
Embodiment 9
With the TDA of 12.0g (0.040mol) as tetracarboxylic dianhydride's composition, with the C16DAB1 of 2-DABFr and 1.39g (0.004mol) of p-PDA, 2.79g (0.012mol) of 2.59g (0.024mol) as diamine component, in the NMP of 75.7g, in 50 DEG C of reactions 24 hours, the concentration obtaining polyamic acid was the solution of 20 quality %.
The NMP adding 187g in this polyamic acid solution of 90.0g dilutes, then adds the diacetyl oxide of 39.6g and the pyridine of 18.4g, reacts 3 hours with imidization in 40 DEG C.
After about this reaction soln cool to room temperature, drop in the methyl alcohol of 1.17L, reclaim the solids of precipitation.Again by this solids of methanol cleaning 2 times, afterwards in 100 DEG C of drying under reduced pressure, obtain the white powder of polyimide (SPI-5).The number-average molecular weight of this polyimide is 15322, and weight-average molecular weight is 28239.In addition, imide rate is 81%.
In the polyimide (SPI-5) of 5.00g, add the γ-BL of 62.5g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the γ-BL of 20.8g again, stir 20 hours in 50 DEG C, make the solution that polyimide (SPI-5) is 5.7 quality %.
On the other hand, make the DDM of PMDA and 19.8g (0.10mol) of CBDA, 9.60g (0.044mol) of 9.80g (0.050mol) in room temperature reaction 5 hours in the mixed solvent of the γ-BL of NMP and 111g of 111g, the concentration making polyamic acid (PAA-5) is the solution of 15 quality %.The number-average molecular weight of this polyamic acid is 10925, and weight-average molecular weight is 27314.
In the solution of this polyamic acid (PAA-5) of 200g, add the γ-BL of 225g and the BC of 75.0g, in stirred at ambient temperature 2 hours, the concentration obtaining polyamic acid (PAA-5) was the solution of 6 quality %.By 6 quality % solution of the 6 quality % solution of this polyamic acid (PAA-5) of 200g and the polyimide obtained above (SPI-5) of 50.0g in stirred at ambient temperature after 20 hours, solids component (total mass concentration of PAA-5 と SPI-5) reaches 5.9 quality %, obtains aligning agent for liquid crystal of the present invention (BL-1).The evaluation identical with embodiment 1 is carried out with this aligning agent for liquid crystal.Result is shown in table 2.
Embodiment 10
With the CBDA of 5.78g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of 3-ABA and 2.89g (0.009mol) of DABTh, 1.47g (0.012mol) of 2.24g (0.009mol) as diamine component, in the NMP of 44.96g, react 16 hours under room temperature, obtain the polyamic acid solution (PAA-6) of 20 quality %.
Dilute polyamic acid (PAA-6) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, the solids component obtained as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Its coating fluid is used to carry out the evaluation identical with embodiment 1.Result is shown in table 2.
Embodiment 11
The NMP adding 93.33g in polyamic acid (PAA-6) solution (PAA-7 concentration is 20 quality %) of the 40g obtained by the method identical with embodiment 10 dilutes, add the diacetyl oxide of 5.61g and the pyridine of 2.32g again, react 3 hours with imidization in 60 DEG C.After about this reaction soln cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solids of precipitation.Again by this solids of methanol cleaning 2 times, afterwards in 100 DEG C of drying under reduced pressure, obtain the white dark brown powder of polyimide (SPI-6).The number-average molecular weight of this polyimide is 13163, and weight-average molecular weight is 30211.In addition, imide rate is 85%.
In the gained polyimide (SPI-6) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the DPM of the γ-BL of 8.0g, BC and 6.00g of 6.00g again, stir 20 hours in 50 DEG C, obtaining polyimide (SPI-6) is that the solution of 5 quality % is as aligning agent for liquid crystal of the present invention.The evaluation identical with embodiment 1 is carried out with its coating fluid.Result is shown in table 2.
Embodiment 12
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of 3-ABA and 2.79g (0.009mol) of MeDABFr, 1.42g (0.012mol) of 2.14g (0.009mol) as diamine component, in the NMP of 46.7g, react 16 hours under room temperature, the concentration obtaining polyamic acid (PAA-7) is the solution of 20 quality %.
Dilute polyamic acid (PAA-7) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, the polyamic acid (PAA-7) obtained as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Its coating fluid is used to carry out the evaluation identical with embodiment 1.Result is shown in table 2.
Embodiment 13
The NMP adding 93.3g in polyamic acid (PAA-7) solution (PAA-7 concentration is 20 quality %) of the 40.0g obtained by the method identical with embodiment 12 dilutes, add the diacetyl oxide of 6.06g and the pyridine of 2.53g again, react 3 hours with imidization in 60 DEG C.After about this reaction soln cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solids of precipitation.Again by this solids of methanol cleaning 2 times, afterwards in 100 DEG C of drying under reduced pressure, obtain the white dark brown powder of polyimide (SPI-7).The number-average molecular weight of this polyimide is 15787, and weight-average molecular weight is 36433.In addition, imide rate is 87%.
In the gained polyimide (SPI-7) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the DPM of the γ-BL of 8.00g, BC and 6.00g of 6.00g again, stir 20 hours in 50 DEG C, obtain the aligning agent for liquid crystal that polyimide (SPI-7) is 5 quality %.The evaluation identical with embodiment 1 is carried out with this aligning agent for liquid crystal.Result is shown in table 2.
Embodiment 14
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of 3-ABA and 2.79g (0.009mol) of 3-DABFr, 1.42g (0.012mol) of 2.02g (0.009mol) as diamine component, in the NMP of 46.7g, react 16 hours under room temperature, the concentration obtaining polyamic acid (PAA-8) is the solution of 20 quality %.
Dilute polyamic acid (PAA-8) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, the polyamic acid (PAA-8) obtained as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Its coating fluid is used to carry out the evaluation identical with embodiment 1.Result is shown in table 2.
Embodiment 15
The NMP adding 93.3g in polyamic acid (PAA-8) solution (PAA-8 concentration is 20 quality %) of the 40.0g obtained by the method identical with embodiment 14 dilutes, add the diacetyl oxide of 6.06g and the pyridine of 2.53g again, react 3 hours with imidization in 60 DEG C.After about this reaction soln cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solids of precipitation.Again by this solids of methanol cleaning 2 times, afterwards in 100 DEG C of drying under reduced pressure, obtain the white dark brown powder of polyimide (SPI-8).The number-average molecular weight of this polyimide is 16142, and weight-average molecular weight is 38574.In addition, imide rate is 89%.
In the gained polyimide (SPI-8) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the DPM of the γ-BL of 8.00g, BC and 6.00g of 6.00g again, stir 20 hours in 50 DEG C, obtain the aligning agent for liquid crystal that polyimide (SPI-8) is 5 quality %.The evaluation identical with embodiment 1 is carried out with this aligning agent for liquid crystal.Result is shown in table 2.
Embodiment 16
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the Me4APhA of 2-DABFr and 3.05g (0.021mol) of 2.02g (0.009mol) as diamine component, in the NMP of 46.7g, react 16 hours under room temperature, the concentration obtaining polyamic acid (PAA-9) is the solution of 20 quality %.The number-average molecular weight of this polyamic acid is 21329, and weight-average molecular weight is 45294.
Dilute polyamic acid (PAA-9) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, the polyamic acid (PAA-9) obtained as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Its coating fluid is used to carry out the evaluation identical with embodiment 1.Result is shown in table 2.
Comparative example 1
With the CBDA of 12.5g (0.064mol) as tetracarboxylic dianhydride's composition, with the C14DAB of 3-ABA and 6.25g (0.020mol) of 5.56g (0.046mol) as diamine component, in the NMP of 97.20g, react 16 hours under room temperature, the concentration obtaining polyamic acid (PAA-10) is the solution of 20 quality %.
Dilute polyamic acid (PAA-10) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, obtain the solution that polyamic acid (PAA-10) is 4.6 quality %, this solution is the aligning agent for liquid crystal being used as comparison other.Use its coating fluid and embodiment 1 similarly obtained liquid crystal cell, and carry out the mensuration of physical property and the evaluation of characteristic
Comparative example 2
The NMP adding 116.67g in polyamic acid (PAA-10) solution (PAA-10 concentration is 20 quality %) of the 50g obtained by the method identical with comparative example 1 dilutes, add the diacetyl oxide of 7.39g and the pyridine of 3.15g again, react 3 hours with imidization in 70 DEG C, but in reaction, gelation occurs.
The NMP again adding 116.67g in polyamic acid (PAA-10) solution (PAA-10 concentration is 20 quality %) of the 50g obtained by the method identical with comparative example 1 dilutes, adding the diacetyl oxide of 7.39g and the pyridine of 3.15g again, is carry out imidization under the condition of 50 DEG C in temperature of reaction.
After about this reaction soln cool to room temperature, drop in the methyl alcohol of 250mL, reclaim the solids of precipitation.Again by this solids of methanol cleaning 2 times, afterwards in 100 DEG C of drying under reduced pressure, obtain the white powder of polyimide (SPI-9).The number-average molecular weight of this polyimide is 16338, and weight-average molecular weight is 39865.In addition, imide rate is 80%.
In the polyimide (SPI-9) of 1g, add the γ-BL of 9g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the DPM of the γ-BL of 4.0g, BC and 3.0g of 3.00g again, stir 20 hours in 50 DEG C, obtain the solution that polyimide (SPI-9) is 5 quality %, obtain the aligning agent for liquid crystal as comparison other.Make liquid crystal cell in the same manner by this aligning agent for liquid crystal and embodiment 1, and carry out physical property measurement, evaluating characteristics.
Comparative example 3
With the CBDA of 5.70g (0.029mol) as tetracarboxylic dianhydride's composition, with the Me4APhA of 4.51g (0.030mol) as diamine component, in the NMP of 46.7g, react 16 hours under room temperature, the concentration obtaining polyamic acid (PAA-11) is the solution of 20 quality %.The number-average molecular weight of this polyamic acid is 19630, and weight-average molecular weight is 48201.
Dilute polyamic acid (PAA-11) solution of 10.0g with the BC of NMP and 10.0g of 23.3g, obtain the solution that polyamic acid (PAA-11) is 4.6 quality %, obtain the aligning agent for liquid crystal as comparison other.Make liquid crystal cell in the same manner by this aligning agent for liquid crystal and embodiment 1, and carry out physical property measurement, evaluating characteristics.
[table 1]
[table 2]
Industrial utilizes possibility
By aligning agent for liquid crystal of the present invention, even if when can obtain rubbing, not easily film is peeled off or is cut, voltage retention is high and apply volts DS to liquid crystal cell and also not easily cause the liquid crystal orientation film of the savings of initial stage electric charge.Therefore, the liquid crystal display device made with aligning agent for liquid crystal of the present invention can obtain the high liquid crystal display of reliability, is applicable to various types of display elements such as TN liquid crystal display device, stn liquid crystal display element, TFT liquid crystal display device, VA liquid crystal display device, IPS liquid crystal display device, OCB liquid crystal display device.
In addition, the announcement of full content as specification sheets of the present invention of the specification sheets of No. 2008-260486, the Japanese patent application that on October 7th, 2008 proposes, right and summary is quoted here.

Claims (3)

1. the diamines that represents of following formula [2]:
In formula, any hydrogen atom of furan nucleus is replaced by the alkyl of carbon number 1 ~ 5 or is not replaced.
2. diamines as claimed in claim 1, it is characterized in that, any hydrogen atom of furan nucleus is by methyl substituted or do not replace.
3. polyamic acid or the polyimide that obtained by this polyamic acid imidization, described polyamic acid reacts by making the diamine component containing the diamines described in claim 1 or 2 and tetracarboxylic dianhydride's composition and obtains.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030194621A1 (en) * 1999-01-25 2003-10-16 Riken Printed wiring board and semiconductor device and processes to prepare the same
CN1501921A (en) * 2001-04-13 2004-06-02 钟渊化学工业株式会社 Diamine, acid dianhydride, polyimide composition having reactive group obtained therefrom, and processes for producing these
CN1572815A (en) * 2003-06-18 2005-02-02 三菱瓦斯化学株式会社 Novel acid anhydride and polyimide using the same
CN1605587A (en) * 2003-10-08 2005-04-13 中国科学院化学研究所 Fluoro-aromatic organic tetracarboxylic dianhydride and its preparation method and use

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4258690B2 (en) * 1999-05-26 2009-04-30 独立行政法人理化学研究所 Photosensitive resin composition
JP3942063B2 (en) 1999-06-28 2007-07-11 株式会社カネカ Novel polyimide composition and novel acid dianhydride used in the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030194621A1 (en) * 1999-01-25 2003-10-16 Riken Printed wiring board and semiconductor device and processes to prepare the same
CN1501921A (en) * 2001-04-13 2004-06-02 钟渊化学工业株式会社 Diamine, acid dianhydride, polyimide composition having reactive group obtained therefrom, and processes for producing these
CN1572815A (en) * 2003-06-18 2005-02-02 三菱瓦斯化学株式会社 Novel acid anhydride and polyimide using the same
CN1605587A (en) * 2003-10-08 2005-04-13 中国科学院化学研究所 Fluoro-aromatic organic tetracarboxylic dianhydride and its preparation method and use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Photo-oxidation Induced Polycondensation Resin II;Yusuke Tajima等;《Journal of Photopolymer Science and Technology》;19991231;第12卷(第1期);第125-128页 *

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