CN104230973A - Siloxane dianhydride, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents
Siloxane dianhydride, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDFInfo
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- CN104230973A CN104230973A CN201410242001.7A CN201410242001A CN104230973A CN 104230973 A CN104230973 A CN 104230973A CN 201410242001 A CN201410242001 A CN 201410242001A CN 104230973 A CN104230973 A CN 104230973A
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- Prior art keywords
- acid anhydride
- liquid crystal
- diacid acid
- siloxane diacid
- siloxane
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 82
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 65
- -1 Siloxane dianhydride Chemical class 0.000 title abstract description 20
- 229920000642 polymer Polymers 0.000 title abstract description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 113
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 84
- 239000013078 crystal Substances 0.000 claims description 59
- 239000000126 substance Substances 0.000 claims description 47
- 239000004642 Polyimide Substances 0.000 claims description 36
- 229920001721 polyimide Polymers 0.000 claims description 36
- 150000008064 anhydrides Chemical class 0.000 claims description 35
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 229920005575 poly(amic acid) Polymers 0.000 claims description 23
- 150000004985 diamines Chemical class 0.000 claims description 20
- 239000000376 reactant Substances 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000000962 organic group Chemical group 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 51
- 239000000243 solution Substances 0.000 description 37
- 239000007787 solid Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000002904 solvent Substances 0.000 description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 7
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- MHRLWUPLSHYLOK-UHFFFAOYSA-N thiomorpholine-3,5-dicarboxylic acid Chemical compound OC(=O)C1CSCC(C(O)=O)N1 MHRLWUPLSHYLOK-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 4
- WVOLTBSCXRRQFR-DLBZAZTESA-M cannabidiolate Chemical compound OC1=C(C([O-])=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-M 0.000 description 4
- 238000006210 cyclodehydration reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 0 CC(*C(C1C(C2)C=CC2C1)=O)OC Chemical compound CC(*C(C1C(C2)C=CC2C1)=O)OC 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- QVEIRZNRYOJFCL-UHFFFAOYSA-N 6053-46-9 Chemical compound O=C1OC(=O)C2CC1C1C2CC(=O)OC1=O QVEIRZNRYOJFCL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- GQQPGLNCIGVYAC-UHFFFAOYSA-N 4,10-dioxatricyclo[6.3.1.02,7]dodeca-1,7-diene-3,5,9,11-tetrone Chemical compound C1C2=C(C(=O)OC(=O)C3)C3=C1C(=O)OC2=O GQQPGLNCIGVYAC-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- TZGHZDGBVHWPFG-UHFFFAOYSA-N CCCC1CCC(CC1)C2CCC(CC2)C3=C(C=C(C(=C3N)C)C(=O)O)N Chemical compound CCCC1CCC(CC1)C2CCC(CC2)C3=C(C=C(C(=C3N)C)C(=O)O)N TZGHZDGBVHWPFG-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical group C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides siloxane dianhydride, a series of polymers prepared from the siloxane dianhydride, a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element comprising the liquid crystal alignment film. The solubility of siloxane dianhydride, polymer and liquid crystal alignment agent is good, the processing temperature required by the liquid crystal alignment agent is low, the vertical alignment and the adhesiveness of the liquid crystal alignment film are good, and the product reliability of the liquid crystal display element is high.
Description
Technical field
The present invention relates to a kind of dicarboxylic anhydride, polymkeric substance, crystal aligning agent, liquid crystal orienting film and liquid crystal display device, and particularly relate to a kind of siloxane diacid acid anhydride, the polymkeric substance that uses this siloxane diacid acid anhydride to prepare, crystal aligning agent, liquid crystal orienting film and comprise the liquid crystal display device of foregoing liquid crystal alignment film.
Prior art
Liquid-crystal display, because having frivolous, the characteristic such as power saving and high image quality, gradually becomes the market mainstream and is widely used on various electronic product.In typical liquid crystal orienting film processing procedure, often because the solubleness of crystal aligning agent is not good, and then when coating process or apparatus for coating leave unused, crystal aligning agent brings out the phenomenon that solute is separated out or levelling property declines because of the aqueous vapor touched in air, not only can make the deterioration in characteristics of liquid-crystal display, also virtually wasting material and increasing environmental pressure.
On the other hand, how crystal aligning agent is general is obtained by the polymer blending respectively with high surface energy and low surface energy, by follow-up high temperature process processing procedure, make it effectively reach to be separated, and then contact with liquid crystal molecule on upper strata in the polymer position of film forming low surface energy in season, make the regiospecific that liquid crystal molecule is kept stable, the polymer (namely having more carboxyl person) with seasonal high surface energy moves towards the glass substrate of lower floor, and high molecular adherence characteristic is promoted.But once processing temperature is not high enough, then after crystal aligning agent film forming, not only tack is not good, and regiospecific also will be affected.Just processing temperature is higher, and the quantity discharged that relatively represent carbonic acid gas will be higher, and the loss of electric energy and heat energy also the more, also therefore becomes the obstruction that liquid-crystal display marches toward pollution-free industry.
Summary of the invention
Therefore, an embodiment of an aspect of of the present present invention is providing a kind of siloxane diacid acid anhydride, and solubleness is excellent, is conducive to the preparation of polymkeric substance, crystal aligning agent and liquid crystal orienting film.
Secondly, another embodiment of an aspect of of the present present invention is providing a kind of polymkeric substance, and it is obtained through polyreaction by aforementioned silicone dicarboxylic anhydride and diamines.Polymkeric substance not completely cyclisation time solubleness excellent, complete cyclisation and after baking then tack and mechanical properties good, be conducive to the preparation of crystal aligning agent and liquid crystal orienting film.
Moreover the another embodiment of an aspect of of the present present invention is providing a kind of crystal aligning agent, and it comprises aforementioned polymer.The solubleness of crystal aligning agent is excellent, be conducive to coating, and required processing temperature is low, is conducive to save energy and alleviates environmental pressure.
Then, an embodiment again of an aspect of of the present present invention is providing a kind of liquid crystal orienting film, and it formed by foregoing liquid crystal orientation agent.Liquid crystal orienting film has excellent vertical orientation and tack, can the reliability of improving product.
Finally, a more embodiment of an aspect of of the present present invention is providing a kind of liquid crystal display device, and it comprises foregoing liquid crystal alignment film, therefore product reliability is good.
According to an embodiment of an aspect of of the present present invention, propose a kind of siloxane diacid acid anhydride, have as shown in the formula the structure shown in (I):
Wherein G
1for:
R
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independent is separately monovalent organic group, and n is the integer of 0 to 30, and when n is 0, R
1, R
2, R
5and R
6at least both are phenyl or at least one is-CH
2cH
2cF
3.
According to an embodiment of an embodiment of the present invention, structure is such as formula the R of the siloxane diacid acid anhydride shown in (I)
1to R
6except at least both be phenyl or at least one are-CH
2cH
2cF
3outward, all the other can be independently the alkyl of carbon number 1 to 5 separately.
According to another embodiment of an aspect of of the present present invention, a kind of polymkeric substance is proposed, polymkeric substance is obtained through polyreaction by reactant and diamines, polymkeric substance comprises polyamic acid, polyimide or polyamic acid-polyimide copolymer, and reactant comprises siloxane diacid acid anhydride, and siloxane diacid acid anhydride has the structure as shown in above-mentioned formula (I), wherein R
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independent is separately monovalent organic group, and n is the integer of 0 to 30, and when n is 0, R
1, R
2, R
5and R
6at least both are phenyl or at least one is-CH
2cH
2cF
3.
According to an embodiment of another embodiment of the present invention, the R of the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I)
1to R
6except at least both be phenyl or at least one are-CH
2cH
2cF
3outward, all the other can be independently the alkyl of carbon number 1 to 5 separately.
According to another embodiment of another embodiment of the present invention, the n of the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I) can be 1, and R
3and R
4can be phenyl, and R
1, R
2, R
5and R
6can be independently the alkyl of carbon number 1 separately.
According to the another embodiment of another embodiment of the present invention, the n of the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I) can be 4, and R
3can be-CH
2cH
2cF
3, and R
1, R
2, R
4, R
5and R
6can be independently the alkyl of carbon number 1 separately.
According to an embodiment again of another embodiment of the present invention, reactant can more comprise other dicarboxylic anhydrides, and the content of siloxane diacid acid anhydride can be 10 molar percentage to 99 molar percentages of the total amount of siloxane diacid acid anhydride and other dicarboxylic anhydrides.
According to the another embodiment of an aspect of of the present present invention, a kind of crystal aligning agent is proposed, comprise polymkeric substance, and polymkeric substance is obtained through polyreaction by reactant and diamines, polymkeric substance comprises polyamic acid, polyimide or polyamic acid-polyimide copolymer, and reactant comprises siloxane diacid acid anhydride, siloxane diacid acid anhydride has the structure as shown in above-mentioned formula (I) again, wherein R
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independent is separately monovalent organic group, and n is the integer of 0 to 30, and when n is 0, R
1, R
2, R
5and R
6at least both are phenyl or at least one is-CH
2cH
2cF
3.
According to an embodiment of the another embodiment of the present invention, the R of the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I)
1to R
6except at least both be phenyl or at least one are-CH
2cH
2cF
3outward, all the other can be independently the alkyl of carbon number 1 to 5 separately.
According to another embodiment of the another embodiment of the present invention, the n of the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I) can be 1, and R
3and R
4can be phenyl, and R
1, R
2, R
5and R
6can be independently the alkyl of carbon number 1 separately.
According to the another embodiment of the another embodiment of the present invention, the n of the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I) can be 4, and R
3can be-CH
2cH
2cF
3, and R
1, R
2, R
4, R
5and R
6can be independently the alkyl of carbon number 1 separately.
According to an embodiment again of the another embodiment of the present invention, reactant can more comprise other dicarboxylic anhydrides, and the content of siloxane diacid acid anhydride can be 10 molar percentage to 99 molar percentages of the total amount of siloxane diacid acid anhydride and other dicarboxylic anhydrides, 30 molar percentage to 99 molar percentages or 70 molar percentage to 99 molar percentages.
According to an embodiment again of an aspect of of the present present invention, proposing a kind of liquid crystal orienting film, is formed by foregoing liquid crystal orientation agent.
According to a more embodiment of an aspect of of the present present invention, propose a kind of liquid crystal display device, comprise foregoing liquid crystal alignment film.
Brief description of drawingsfig
Fig. 1 illustrates a kind of siloxane diacid acid anhydride according to one embodiment of the invention
1h NMR spectrogram.
Fig. 2 illustrates a kind of siloxane diacid acid anhydride according to another embodiment of the present invention
1h NMR spectrogram.
Embodiment
The invention provides a kind of siloxane diacid acid anhydride and a series of polymkeric substance, crystal aligning agent, the liquid crystal orienting film that obtain with siloxane diacid acid anhydride and comprise the liquid crystal display device of liquid crystal orienting film.
siloxane diacid acid anhydride
Siloxane diacid acid anhydride provided by the present invention, has as shown in the formula the structure shown in (I):
Wherein G
1for:
R
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independent is separately monovalent organic group, and is independently preferably the alkyl of carbon number 1 to 5 separately.On the other hand, n is the integer of 0 to 30, and when n is 0, R
1, R
2, R
5and R
6at least both are phenyl or at least one is-CH
2cH
2cF
3.In addition, n is preferably the integer of 1 to 15, is more preferably the integer of 1 to 4.
The siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I) is prepared by typical hydrosilation reaction (Hydrosilylation).More specifically, acid anhydrides precursor to be dissolved in solvent and under the catalysis of transition metal, to carry out hydrosilation reaction with polysiloxane precursor thing and obtain, and after reaction can more further desolvation to promote purity.Wherein, temperature of reaction is generally 40 DEG C to 110 DEG C, is preferably 90 DEG C to 110 DEG C, and the reaction times is generally 2 little of 30 hours, is preferably 8 little of 12 hours.Solvent is such as the common solvent of typical hydrosilation reaction, and is preferably ether, tetrahydrofuran (THF) (tetrahydrofuran, THF) or ethyl acetate, is more preferably toluene.Catalyzer is such as that well-known Speier catalyst, Karstedt catalyst are (as commercially available prod PC072, PC075 etc., United Chemical Tech., Inc.), Ashby catalyst is (as commercially available prod PC085 etc., United Chemical Tech., Inc.), Lamoreaux catalyst etc. is containing the catalyst of transition metal platinum.
In order to prepare the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I) the optional following table freely of polysiloxane precursor thing shown in compound, and the compound shown in the optional following table freely two of acid anhydrides precursor.But polysiloxane precursor thing and acid anhydrides precursor are not limited with disclosed compound, as long as polysiloxane precursor thing has at least two phenyl or at least one-CH
2cH
2cF
3group, and acid anhydrides precursor comprises norbornylene structure or tetrahydrochysene acid phthalic anhydride structure.
Table one
Note :-Ph represents phenyl (phenyl group)
Table two
polymkeric substance
Polymkeric substance provided by the present invention is obtained through polyreaction by reactant and diamines.More specifically, be dissolved in solvent by reactant, then add diamines and obtain to carry out polyreaction, in process, still visual demand is with the solids content of same solvent adjustment polymkeric substance.Wherein, temperature of reaction is generally 20 DEG C to 180 DEG C, is preferably 60 DEG C to 110 DEG C, and the reaction times is generally 2 little of 24 hours, is preferably 4 little of 12 hours, is more preferably 8 hours, solids content is generally 10wt% to 50wt%, is preferably 10wt% to 30wt%, is more preferably 15wt%.
Reactant comprises the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I), and the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I) is preferably n is 1, R
3and R
4for phenyl, and R
1, R
2, R
5and R
6respective is independently the alkyl of carbon number 1, or n is 4, R
3for-CH
2cH
2cF
3, and R
1, R
2, R
4, R
5and R
6respective is independently the alkyl of carbon number 1.And solvent is such as N-Methyl pyrrolidone (N-methylpyrrolidinone, NMP), N, dinethylformamide (dimethylformamide, DMF), N, N-N,N-DIMETHYLACETAMIDE (dimethylacetamide, DMAc), dimethyl sulfoxide (DMSO) (dimethyl sulfoxide, DMSO), N-methyl caprolactam, Virahol (isopropyl alcohol, IPA) etc.
In addition, reactant can be anhydride compounds, also can be the mixture being mixed with two or more anhydride compounds, such as, be to be mixed with other dicarboxylic anhydrides by the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I).And diamines can be diamine compound, it also can be the mixture being mixed with two or more diamine compounds.As for polymkeric substance then depending on the polymerization in polymerization process and dehydration closed-loop degree and polyamic acid, polyimide or polyamic acid-polyimide copolymer can be comprised.In other words, aforesaid polyreaction, except comprising being polymerized of dicarboxylic anhydride and diamines, also can comprise follow-up dehydration closed-loop reaction.
More specifically, reactant preferably comprises the siloxane diacid acid anhydride of structure as shown in above-mentioned formula (I) and the mixture of other dicarboxylic anhydrides, and the former content is 10 molar percentage to 99 molar percentages of the total amount of both front and back, preferably 30 molar percentage to 99 molar percentages, are more preferably 70 molar percentage to 99 molar percentages.And diamines is preferably mixed with the mixture of two or more diamine compounds.
Other dicarboxylic anhydrides are such as 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride (1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, CBDA), pyromellitic acid anhydride (pyromellitic dianhydride, PMDA), 3, 3', 4, 4'-bibenzene tetracarboxylic dianhydride (3, 3', 4, 4'-biphenyl tetracarboxylic dianhydride, BPDA), 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic acid dianhydride (3, 4-dicarboxy-1, 2, 3, 4-tetrahydro-1-naphthalene succinicanhydride, TDA), Rikacid BT-100 (1, 2, 3, 4-ethylene-dimalonic acid dianhydride) (1, 2, 3, 4-butanetetracarboxylic dianhydride), Rikacid TMEG-100 (ethylene glycol bis dehydration trimellitate) (ethylene glycol bis-anhydro trimellitate) or 5, 9-first bridge-1H-pyrans also [3, 4-d] oxa-
-1, 3, 6, 8 (4H)-tetraketones, tetrahydrochysene (5, 9-methano-1H-pyrano [3, 4-d] oxepin-1, 3, 6, 8 (4H)-tetrone, tetrahydro) (TCA-AH, chemical substance accession number CAS:6053-46-9) etc., and diamine compound is such as 5 (6)-amino-1, 3, 3-trimethylammonium-1-(4-aminophenyl)-indane (5 (6)-amino-1, 3, 3-trimethyl-1-(4-aminophenyl)-indan) (TMDA, chemical substance accession number CAS:54628-89-6) or two (the hexanaphthene)-4-base-3 of 4'-propyl group, 5-diamino-2-methyl benzoic acid ester (4'-propylbi (cyclohexan)-4-yl-3, 5-diamino-2-methylbenzoate) (3CC, Daxin Materials Co., Ltd) etc., but took off not and be limited, other dicarboxylic anhydrides and diamine compound also can be any known conventional dicarboxylic anhydride and diamine compound.
crystal aligning agent
Crystal aligning agent provided by the present invention comprises aforementioned polymkeric substance provided by the present invention.Preferably, crystal aligning agent comprises aforementioned polymkeric substance provided by the present invention and other polymkeric substance, and other polymkeric substance so-called are obtained through polyreaction by other dicarboxylic anhydrides aforesaid and aforesaid diamines.More specifically, crystal aligning agent is that polymkeric substance provided by the present invention and other mixed with polymers is even, and demand of looking is with the solids content of solvent adjustment crystal aligning agent.Wherein, temperature during mixing is generally 20 DEG C to 60 DEG C, and be preferably 25 DEG C to 40 DEG C, the solids content of crystal aligning agent is generally 3.0wt% to 8.0wt%, is preferably 3.5wt% to 6.5wt%, is more preferably 6.5wt%.Solvent is such as the mixture of NMP and diethylene glycol monobutyl ether (butyl carbitol, BC), and both weight ratios are preferably 1:1.The solvent that is suitable for before do not take off and be limited, also can be any known can in order to adjust the common solvent of the solids content of crystal aligning agent.
liquid crystal orienting film
Liquid crystal orienting film provided by the present invention formed by aforementioned crystal aligning agent provided by the present invention.First, crystal aligning agent is coated on glass substrate, and coating method can be roller coating, rotary coating or printing etc. commonly use coating method.Then carry out heated baking, form liquid crystal orienting film to make the crystal aligning agent coated on glass substrate.Wherein, heated baking temperature is generally 180 DEG C to 250 DEG C, is preferably 200 DEG C to 230 DEG C, is more preferably 230 DEG C; The heated baking time is generally 20 minutes to 120 minutes, is preferably 30 minutes to 60 minutes, is more preferably 30 minutes; And the thickness of the liquid crystal orienting film formed is generally 0.05 micron to 0.20 micron, is preferably 0.06 micron to 0.15 micron, is more preferably 0.12 micron.
liquid crystal display device
Liquid crystal display device provided by the present invention comprises aforementioned liquid crystal orienting film provided by the present invention.The method for making of liquid crystal display device for example, is first get the glass substrate that two pieces are formed with aforementioned liquid crystal orienting film provided by the present invention, then on wherein one piece of glass substrate, is coated with frame glue, and sprays separation material on another block glass substrate.Afterwards two pieces of glass substrates are combined in mode that is vertical or that be parallel to each other mutually with brush film direction each other.Finally, in the gap of two pieces of glass substrates, inject liquid crystal molecule, then sealing injection hole can complete.
Be described further to siloxane diacid acid anhydride provided by the present invention and a series of polymkeric substance, crystal aligning agent, liquid crystal orienting film and liquid crystal display device of comprising liquid crystal orienting film obtained with siloxane diacid acid anhydride below.
embodiment: siloxane diacid acid anhydride (I-1)
Siloxane diacid acid anhydride (I-1) obtains by following reaction formula.
First, the acid anhydrides precursor (2-1) of 328.32 grams is mixed in the toluene of 330.47 grams, and adds PC085 catalyst (United Chemical Tech., the Inc.) uniform stirring of 1.0 grams.Then be warming up to 110 DEG C and maintain 8 hours, be cooled to 90 DEG C subsequently and add the polysiloxane precursor thing (1-2) of 349.25 grams, then holding temperature keeps 12 hours at 90 DEG C.Finally, drain toluene and can obtain siloxane diacid acid anhydride (I-1), productive rate is 93%.
Fig. 1 is siloxane diacid acid anhydride (I-1)
1by this collection of illustrative plates, H nucleus magnetic resonance (nuclear magnetic resonance, NMR) spectrogram, can confirm that aforementioned preparation method really can obtain siloxane diacid acid anhydride (I-1).Separately, siloxane diacid acid anhydride (I-1) is at room temperature transparent solid, and can to record its fusing point be 40 DEG C to 55 DEG C by Differential Scanning Calorimeter analyser (differential scanning calorimeter, DSC).
embodiment: siloxane diacid acid anhydride (I-2)
Siloxane diacid acid anhydride (I-2) obtains by following reaction formula.
First, the acid anhydrides precursor (2-1) of 328.32 grams is mixed in the toluene of 50.07 grams, and adds the PC085 catalyst uniform stirring of 0.01 gram.Then be warming up to 110 DEG C and maintain 8 hours, be cooled to 90 DEG C subsequently and add the polysiloxane precursor thing (1-7) of 70.68 grams, then holding temperature keeps 12 hours at 90 DEG C.Finally, drain toluene and can obtain siloxane diacid acid anhydride (I-2), productive rate is 97%.
Fig. 2 is siloxane diacid acid anhydride (I-2)
1by this collection of illustrative plates, H NMR spectrogram, can confirm that aforementioned preparation method really can obtain siloxane diacid acid anhydride (I-2).Separately, siloxane diacid acid anhydride (I-2) is at room temperature transparent liquid.
Siloxane diacid acid anhydride (I-1) and siloxane diacid acid anhydride (I-2) are compared to other dicarboxylic anhydrides to the solubleness of different solvents as shown in Table 3.The test mode of solubleness is under room temperature environment (about 25 DEG C), and the dicarboxylic anhydride getting 0.5 gram is inserted in the solvent of 30 grams and stirred 30 minutes, observes the dissolving situation of dicarboxylic anhydride in all kinds of SOLVENTS.Be that clear state person's (solvable) is denoted as "+" by dissolving situation, be denoted as " ± " in suspended state person (solvable), be denoted as "-" in precipitated form person (soluble).Other dicarboxylic anhydrides in order to carry out testing are CBDA, PMDA, BPDA, TDA, Rikacid BT-100 and Rikacid TMEG-100.Solvent is Equamide M100 (ProductName, Idemitsu Kosan Co., Ltd, Japan), meta-cresol (m-cresol), THF, NMP, DMSO, DMF, DMAc, acetone (Acetone) and 1-Methoxy-2-propyl acetate (Propylene glycol monomethyl ether acetate, PGMEA).
Table three
| Dicarboxylic anhydride | S1 | S2 | S3 | S4 | S5 | S6 | S7 | S8 | S9 |
| (I-1) | + | + | + | + | + | + | + | + | + |
| (I-2) | + | + | + | + | + | + | + | + | + |
| CBDA | + | － | － | + | + | + | + | － | － |
| PMDA | + | － | + | + | + | + | + | + | + |
| BPDA | ± | － | － | + | ± | + | + | － | － |
| TDA | + | ± | + | + | + | + | + | + | ± |
| Rikacid?BT-100 | + | ± | － | + | + | + | + | + | － |
| Rikacid?TMEG-100 | + | + | + | + | + | + | + | + | － |
Note: S1 ~ S9 sequentially represents Equamide M100, m-cresol, THF, NMP, DMSO, DMF, DMAc, Acetone, PGMEA.
As shown in Table 3, siloxane diacid acid anhydride (I-1) and siloxane diacid acid anhydride (I-2) can show more excellent dissolubility property compared to other dicarboxylic anhydrides, therefore are conducive to the preparation of the polymkeric substance such as polyamic acid or polyimide and crystal aligning agent and liquid crystal orienting film.
embodiment: polymkeric substance (PAA)
For in order to carry out reacting to obtain for the dicarboxylic anhydride of polymkeric substance with diamines, the employing of siloxane diacid acid anhydride (I-1) or siloxane diacid acid anhydride (I-2) all can make the polymkeric substance (as polyamic acid) of the not cyclisation completely of reaction gained have excellent solubleness.
For siloxane diacid acid anhydride (I-1), first, the siloxane diacid acid anhydride (I-1) of 0.1 mole is dissolved in the NMP of 150 milliliters, add the TMDA of 0.1 mole afterwards to carry out polyreaction, with NMP, solids content is adjusted to 15wt% simultaneously, react after 8 hours, the polyamic acid solution (PAA-1) that solids content is 15wt% can be obtained.
The siloxane diacid acid anhydride (I-1) of 0.05 mole is dissolved in the NMP of 150 milliliters with the Rikacid BT-100 of 0.05 mole, add the TMDA of 0.1 mole afterwards to carry out polyreaction, with NMP, solids content is adjusted to 15wt% simultaneously, react after 8 hours, the polyamic acid solution (PAA-2) that solids content is 15wt% can be obtained.
Compare for convenience, the TMDA of 0.1 mole is dissolved in the NMP of 150 milliliters, add the Rikacid BT-100 of 0.1 mole afterwards to carry out polyreaction, with NMP, solids content is adjusted to 15wt% simultaneously, react after 8 hours, the polyamic acid solution (C-PAA) that solids content is 15wt% can be obtained, accordingly compared with polyamic acid solution (PAA-1) and polyamic acid solution (PAA-2).
The polyamic acid solution (PAA-1) of same solid content, polyamic acid solution (PAA-2) and polyamic acid solution (C-PAA) are to the solubleness of different solvents as shown in Table 4.The test mode of solubleness is under room temperature environment (about 25 DEG C), and the polyamic acid solution getting 2 grams is inserted in the solvent of 20 grams and stirred 30 minutes, observes the dissolving situation of polyamic acid solution in all kinds of SOLVENTS that solids content is all 15wt%.Be that clear state person's (solvable) is denoted as "+" by dissolving situation, be denoted as " ± " in suspended state person (solvable), be denoted as "-" in precipitated form person (soluble).
Table four
| Polyamic acid solution | S1 | S2 | S3 | S4 | S5 | S6 | S7 | S8 | S9 | S10 |
| (PAA-1) | + | + | + | + | + | + | + | + | + | + |
| (PAA-2) | + | + | + | + | + | + | + | + | ± | ± |
| (C-PAA) | + | － | + | + | + | + | + | － | － | － |
Note: S1 ~ S10 sequentially represents Equamide M100, m-cresol, THF, NMP, DMSO, DMF, DMAc, Acetone, PGMEA, IPA.
As shown in Table 4, carry out in the dicarboxylic anhydride of polyreaction with diamines, the content of siloxane diacid acid anhydride (I-1) the more, then the polyamic acid be obtained by reacting for various solvent solubleness also better, therefore be conducive to the preparation of crystal aligning agent and liquid crystal orienting film.
embodiment: polymkeric substance (PI)
For in order to carry out reacting to obtain for the dicarboxylic anhydride of polymkeric substance with diamines, the employing of siloxane diacid acid anhydride (I-1) or siloxane diacid acid anhydride (I-2) all can make the polymkeric substance (as polyimide) of the complete cyclisation of reaction gained after overbaking, show excellent tack and mechanical properties.
For siloxane diacid acid anhydride (I-1), first, the siloxane diacid acid anhydride (I-1) of 0.1 mole is dissolved in the NMP of 150 milliliters, add the TMDA of 0.1 mole afterwards to carry out polyreaction, with NMP, solids content is adjusted to 15wt% simultaneously, react and utilize toluene cyclodehydration after 8 hours, the polyimide solution (PI-1) that solids content is 15wt% can be obtained.
Compare for convenience, the hexam ethylcyclotrisiloxane dicarboxylic anhydride of 0.1 mole is dissolved in the NMP of 150 milliliters, add the TMDA of 0.1 mole afterwards to carry out polyreaction, with NMP, solids content is adjusted to 15wt% simultaneously, react and utilize toluene cyclodehydration after 8 hours, the polyimide solution (C-PI) that solids content is 15wt% can be obtained, accordingly compared with polyimide solution (PI-1).Wherein, the preparation method of hexam ethylcyclotrisiloxane dicarboxylic anhydride can see the high-effect polymer periodical (High Performance Polymers, June2008, vol.20, no.3, pp281-295) of in June, 2008 publication.
First mode is relatively polyimide solution (PI-1) and polyimide solution (C-PI) are dissolved in solvent respectively, and utilizes solvent that solids content is adjusted to 6.5wt%.Solvent herein utilizes NMP and BC to form with the allotment of the ratio of weight ratio 1:1.Afterwards, the polyimide solution (PI-1) of solids content through being adjusted to 6.5wt% is coated on indium tin oxide (indium tin oxide with method of spin coating respectively with polyimide solution (C-PI), ITO) on substrate, and utilize baking oven with 230 DEG C of bakings 30 minutes, to form a Kapton.
Then, with the platform movement speed of the rotating speed of 1000 revs/min, 60 mm/second, orientation brush is carried out to Kapton and rub 10 times, the surface after then being rubbed by polarizing microscope visual observation brush.Through microscopic examination, the Kapton that polyimide solution (PI-1) is formed is after the brush going through aforementioned several rubs, and the amounts of particles of its margin residual is obviously less than the Kapton that polyimide solution (C-PI) is formed.
In addition, the pencil method of testing (ASTM D3363) developed with American Standard Test association is tested the hardness of Kapton.The pencil hardness that result shows the Kapton formed by polyimide solution (PI-1) is 1B, and the pencil hardness of the Kapton formed by polyimide solution (C-PI) is 4B.More than can it serves to show, for in order to carry out reacting to obtain for the dicarboxylic anhydride of polymkeric substance with diamines, siloxane diacid acid anhydride provided by the present invention really can make the polymkeric substance of the complete cyclisation of reaction gained showing excellent tack and mechanical properties after overbaking, is conducive to the preparation of crystal aligning agent and liquid crystal orienting film accordingly.
embodiment: crystal aligning agent (AA), liquid crystal orienting film and liquid crystal display device
According to the consumption of the dicarboxylic anhydride shown in table five and diamines, first dicarboxylic anhydride is dissolved in the NMP of 150 milliliters, add diamines afterwards to carry out polyreaction, and with NMP, solids content is adjusted to 15wt% simultaneously, react and utilize toluene cyclodehydration after 8 hours, can obtain the polyimide solution that eight kinds of solids contents are all 15wt%, namely polyimide solution (PI-M1) is to polyimide solution (PI-M8).
Table five
On the other hand, the TMDA getting 0.1 mole is dissolved in the NMP of 130 milliliters, adds the CBDA of 0.1 mole afterwards to carry out polyreaction, with NMP, solids content is adjusted to 15wt% simultaneously, react 8 hours, the polyamic acid solution (M-PAA) that solids content is 15wt% can be obtained.
Then by aforementioned eight kinds of polyimide solutions, namely polyimide solution (PI-M1) mixes with the ratio of weight ratio 1:1 with polyamic acid solution (M-PAA) respectively to polyimide solution (PI-M8), and with solvent, solids content is adjusted to 6.5wt%.Solvent herein utilizes NMP and BC to form with the allotment of the ratio of weight ratio 1:1.So, can obtain eight kinds of crystal aligning agents, namely crystal aligning agent (AA-1) is to crystal aligning agent (AA-8).Wherein, based on the employing of siloxane diacid acid anhydride (I-1) or siloxane diacid acid anhydride (I-2), therefore crystal aligning agent (AA-1) to crystal aligning agent (AA-8) all shows excellent solubleness and is easy to coating.
Compare for convenience, according to the consumption of the dicarboxylic anhydride shown in table six and diamines, first dicarboxylic anhydride is dissolved in the NMP of 150 milliliters, add diamines afterwards to carry out polyreaction, and with NMP, solids content is adjusted to 15wt% simultaneously, react and utilize toluene cyclodehydration after 8 hours, can obtain the polyimide solution that three kinds of solids contents are all 15wt%, namely polyimide solution (C-PI-M1) is to polyimide solution (C-PI-M3).
Table six
Then by aforementioned three kinds of polyimide solutions, namely polyimide solution (C-PI-M1) mixes with the ratio of weight ratio 1:1 with polyamic acid solution (M-PAA) respectively to polyimide solution (C-PI-M3), and with solvent, solids content is adjusted to 6.5wt%.Solvent herein utilizes NMP and BC to form with the allotment of the ratio of weight ratio 1:1.So, three kinds of crystal aligning agents confession comparing can be obtained, i.e. crystal aligning agent (C-AA-1), crystal aligning agent (C-AA-2) and crystal aligning agent (C-AA-3), accordingly compared with crystal aligning agent (AA-1) to crystal aligning agent (AA-8).
First mode is relatively that aforementioned each crystal aligning agent is made liquid crystal orienting film, is separately assembled into liquid crystal display device in conjunction with the component such as liquid crystal molecule and electrode again.More specifically, liquid crystal orienting film is first by aforementioned each crystal aligning agent with method of spin coating coating on the glass substrate, forms thickness by this and is
the film of (about 0.12 micron), then utilizes baking oven with 230 DEG C of bakings 30 minutes (being generally referred to as " Gu roasting "), can obtain liquid crystal orienting film.As for liquid crystal display device, be then first get the glass substrate that two pieces are formed with foregoing liquid crystal alignment film, one coating frame glue, another one sprays upper separation material.After completing, two pieces of glass substrates is combined and in the gap of two pieces of glass substrates, inject liquid crystal molecule (MJ012008, Merck), then sealing injection hole.
The detected result of liquid crystal orienting film in poach hundred lattice that table seven is formed at different admittedly roasting temperature for each crystal aligning agent, and include the detected result of liquid crystal display device in tilt angle of liquid crystal orienting film.Wherein, it is that each liquid crystal orienting film is after poach that poach hundred lattice detect, the detection method (ASTM M3359) adopting American Standard Test association to develop detects, and the ASTM grade (as shown in Table 8) that detected result divides according to it gives record.Detecting as tilt angle is then measured by crystallization rotational method by the liquid crystal display device injecting liquid crystal molecule.
Table seven
Table eight
As shown in Table 7, crystal aligning agent (C-AA-1) is to crystal aligning agent (C-AA-3) liquid crystal orienting film that machining is formed at lower admittedly roasting temperature, and its vertical orientation and tack show neither good.By contrast, crystal aligning agent (AA-1) all has excellent vertical orientation and tack to crystal aligning agent (AA-8) liquid crystal orienting film that machining is formed at various admittedly roasting temperature.In other words, crystal aligning agent (AA-1) is to crystal aligning agent (AA-8), processing temperature can be made effectively to reduce, be conducive to save energy and alleviate environmental pressure, its liquid crystal orienting film formed then possesses excellent regiospecific and tack, can promote the reliability of liquid crystal display device jointly.
From the invention described above embodiment and embodiment, siloxane diacid acid anhydride provided by the present invention, solubleness is excellent, and the polymkeric substance that itself and diamines obtain through polyreaction, not completely cyclisation time (as polyamic acid) inherit the excellent characteristic of solubleness, in complete cyclisation (as polyimide) and through baking after then can represent excellent tack and mechanical properties, be all conducive to the preparation of crystal aligning agent, liquid crystal orienting film etc.Secondly, the crystal aligning agent including aforementioned polymer is easy to coating because solubleness is good, and required processing temperature is low, is conducive to save energy and alleviates environmental pressure.Moreover the liquid crystal orienting film formed through aforementioned crystal aligning agent has excellent vertical orientation and tack, the product reliability of liquid crystal display device can be promoted.Jointly, the liquid-crystal display including foregoing liquid crystal alignment film has preferably product reliability.
Although the present invention discloses as above with embodiment; so itself and be not used to limit the present invention, anyly have the knack of this those skilled in the art, without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations, therefore protection scope of the present invention is when being as the criterion depending on the accompanying claim person of defining.
Claims (16)
1. a siloxane diacid acid anhydride, has as shown in the formula the structure shown in (I):
Wherein G
1for:
R
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independent is separately monovalent organic group, and n is the integer of 0 to 30, and when n is 0, R
1, R
2, R
5and R
6at least both are phenyl or at least one is-CH
2cH
2cF
3.
2. siloxane diacid acid anhydride, wherein R as claimed in claim 1
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independently the alkyl of carbon number 1 to 5 separately.
3. a polymkeric substance, obtained through polyreaction by reactant and diamines, this polymkeric substance comprises polyamic acid, polyimide or polyamic acid-polyimide copolymer, and this reactant comprises siloxane diacid acid anhydride, and this siloxane diacid acid anhydride has as shown in the formula the structure shown in (I):
Wherein G
1for:
R
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independent is separately monovalent organic group, and n is the integer of 0 to 30, and when n is 0, R
1, R
2, R
5and R
6at least both are phenyl or at least one is-CH
2cH
2cF
3.
4. polymkeric substance as claimed in claim 3, wherein structure is such as formula the R of this siloxane diacid acid anhydride shown in (I)
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independently the alkyl of carbon number 1 to 5 separately.
5. polymkeric substance as claimed in claim 3, wherein structure is 1, R such as formula the n of this siloxane diacid acid anhydride shown in (I)
3and R
4for phenyl, and R
1, R
2, R
5and R
6respective is independently the alkyl of carbon number 1.
6. polymkeric substance as claimed in claim 3, wherein structure is 4, R such as formula the n of this siloxane diacid acid anhydride shown in (I)
3for-CH
2cH
2cF
3, and R
1, R
2, R
4, R
5and R
6respective is independently the alkyl of carbon number 1.
7. polymkeric substance as claimed in claim 3, wherein this reactant more comprises other dicarboxylic anhydrides, and the content of this siloxane diacid acid anhydride is 10 molar percentage to 99 molar percentages of the total amount of this siloxane diacid acid anhydride and these other dicarboxylic anhydrides.
8. a crystal aligning agent, comprise polymkeric substance, this polymkeric substance is obtained through polyreaction by reactant and diamines, this polymkeric substance comprises polyamic acid, polyimide or polyamic acid-polyimide copolymer, this reactant comprises siloxane diacid acid anhydride, and this siloxane diacid acid anhydride has as shown in the formula the structure shown in (I):
Wherein G
1for:
R
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independent is separately monovalent organic group, and n is the integer of 0 to 30, and when n is 0, R
1, R
2, R
5and R
6at least both are phenyl or at least one is-CH
2cH
2cF
3.
9. crystal aligning agent as claimed in claim 8, wherein structure is such as formula the R of this siloxane diacid acid anhydride shown in (I)
1to R
6at least both are phenyl or at least one is-CH
2cH
2cF
3, all the other are independently the alkyl of carbon number 1 to 5 separately.
10. crystal aligning agent as claimed in claim 8, wherein structure is 1, R such as formula the n of this siloxane diacid acid anhydride shown in (I)
3and R
4for phenyl, and R
1, R
2, R
5and R
6respective is independently the alkyl of carbon number 1.
11. crystal aligning agents as claimed in claim 8, wherein structure is 4, R such as formula the n of this siloxane diacid acid anhydride shown in (I)
3for-CH
2cH
2cF
3, and R
1, R
2, R
4, R
5and R
6respective is independently the alkyl of carbon number 1.
12. crystal aligning agents as claimed in claim 8, wherein this reactant more comprises other dicarboxylic anhydrides, and the content of this siloxane diacid acid anhydride is 10 molar percentage to 99 molar percentages of the total amount of this siloxane diacid acid anhydride and these other dicarboxylic anhydrides.
13. crystal aligning agents as claimed in claim 8, wherein this reactant more comprises other dicarboxylic anhydrides, and the content of this siloxane diacid acid anhydride is 30 molar percentage to 99 molar percentages of the total amount of this siloxane diacid acid anhydride and these other dicarboxylic anhydrides.
14. crystal aligning agents as claimed in claim 8, wherein this reactant more comprises other dicarboxylic anhydrides, and the content of this siloxane diacid acid anhydride is 70 molar percentage to 99 molar percentages of the total amount of this siloxane diacid acid anhydride and these other dicarboxylic anhydrides.
15. 1 kinds of liquid crystal orienting films, by as claim 8 to any one of claim 14 crystal aligning agent formed.
16. 1 kinds of liquid crystal display device, comprise the liquid crystal orienting film as claim 15.
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| CN114181393A (en) * | 2022-01-27 | 2022-03-15 | 中国科学院过程工程研究所 | Semi-alicyclic polyimide material, semi-alicyclic polyimide film, and preparation method and application thereof |
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| TWI508970B (en) * | 2014-03-07 | 2015-11-21 | Daxin Materials Corp | Siloxane-containing trianhydride, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
| CN104961894B (en) * | 2015-07-13 | 2017-09-01 | 深圳市华星光电技术有限公司 | The preparation method of polymer and alignment films as aligning film material |
| GB201717174D0 (en) | 2017-10-19 | 2017-12-06 | Univ Leeds Innovations Ltd | Aligned nematic elastomer |
| JP7388296B2 (en) * | 2020-06-11 | 2023-11-29 | 信越化学工業株式会社 | Silicon-containing tetracarboxylic dianhydride, its production method and polyimide resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732262A (en) * | 2011-04-14 | 2012-10-17 | 达兴材料股份有限公司 | Liquid crystal aligning agent |
| WO2012173460A2 (en) * | 2011-06-17 | 2012-12-20 | 주식회사 엘지화학 | Curable composition |
| CN103074028A (en) * | 2011-10-25 | 2013-05-01 | 上海本诺电子材料有限公司 | Organosilicon polyimide insulation adhesive for LED |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3550762B2 (en) * | 1994-10-28 | 2004-08-04 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| JPH08254704A (en) * | 1995-03-15 | 1996-10-01 | Hoechst Ind Kk | Liquid crystal oriented film and liquid crystal display element |
| US20060147719A1 (en) * | 2002-11-22 | 2006-07-06 | Slawomir Rubinsztajn | Curable composition, underfill, and method |
| JP5018998B2 (en) * | 2009-02-18 | 2012-09-05 | 日立化成工業株式会社 | Novel liquid tetracarboxylic dianhydride and process for producing the same |
| TWI516527B (en) * | 2009-12-10 | 2016-01-11 | 信越化學工業股份有限公司 | Photo-curable resin composition, pattern forming method and substrate protecting film, and film-shaped adhesive and adhesive sheet using said composition |
| JP5417623B2 (en) * | 2009-12-10 | 2014-02-19 | 信越化学工業株式会社 | Polyimide-based photocurable resin composition, pattern forming method, and film for protecting substrate |
| JP5352527B2 (en) * | 2010-05-07 | 2013-11-27 | 信越化学工業株式会社 | Novel polyimide and method for producing the same |
| JP5447205B2 (en) * | 2010-06-15 | 2014-03-19 | 信越化学工業株式会社 | Thin wafer manufacturing method |
| CN102286259B (en) * | 2011-06-24 | 2014-04-02 | 上海本诺电子材料有限公司 | Epoxy functionalized organosilicon conductive adhesive for light emitting diode (LED) |
-
2013
- 2013-06-13 TW TW102120945A patent/TWI468415B/en active
-
2014
- 2014-06-03 CN CN201410242001.7A patent/CN104230973B/en active Active
- 2014-06-13 JP JP2014122358A patent/JP5873529B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732262A (en) * | 2011-04-14 | 2012-10-17 | 达兴材料股份有限公司 | Liquid crystal aligning agent |
| WO2012173460A2 (en) * | 2011-06-17 | 2012-12-20 | 주식회사 엘지화학 | Curable composition |
| CN103074028A (en) * | 2011-10-25 | 2013-05-01 | 上海本诺电子材料有限公司 | Organosilicon polyimide insulation adhesive for LED |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107304363A (en) * | 2016-04-18 | 2017-10-31 | 达兴材料股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device using same |
| CN107304363B (en) * | 2016-04-18 | 2021-07-02 | 达兴材料股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device using same |
| CN114181393A (en) * | 2022-01-27 | 2022-03-15 | 中国科学院过程工程研究所 | Semi-alicyclic polyimide material, semi-alicyclic polyimide film, and preparation method and application thereof |
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| TW201446779A (en) | 2014-12-16 |
| JP5873529B2 (en) | 2016-03-01 |
| CN104230973B (en) | 2017-05-24 |
| JP2015000983A (en) | 2015-01-05 |
| TWI468415B (en) | 2015-01-11 |
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