CN113480732A - Polyimide and colorless transparent polyimide film - Google Patents
Polyimide and colorless transparent polyimide film Download PDFInfo
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- CN113480732A CN113480732A CN202110664540.XA CN202110664540A CN113480732A CN 113480732 A CN113480732 A CN 113480732A CN 202110664540 A CN202110664540 A CN 202110664540A CN 113480732 A CN113480732 A CN 113480732A
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- polyimide
- polyimide film
- film
- dianhydride
- aromatic
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 175
- 239000004642 Polyimide Substances 0.000 title claims abstract description 93
- 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 claims abstract description 33
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 18
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 5
- 229920005575 poly(amic acid) Polymers 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 claims description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 238000002834 transmittance Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 5
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 5
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- 239000011521 glass Substances 0.000 description 41
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 32
- 239000000758 substrate Substances 0.000 description 32
- 238000001035 drying Methods 0.000 description 27
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000002244 precipitate Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- OVASAEXSPYGGES-UHFFFAOYSA-N C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 Chemical compound C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 OVASAEXSPYGGES-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012546 transfer Methods 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides polyimide and a colorless transparent polyimide film, wherein the polyimide is prepared by performing polycondensation on alicyclic dianhydride, aromatic diacid chloride and aromatic diamine; the polyimide film is prepared by film formation of the polyimide. The polyimide film prepared by the invention has very low yellow index and excellent heat-resistant dimensional stability.
Description
Technical Field
The invention relates to the technical field of flexible display materials, in particular to polyimide and a colorless transparent polyimide film.
Background
In recent years, polyimide has been widely used in the market because of its excellent heat resistance and flexible flexibility. In particular, for the purpose of weight reduction and flexibility of devices, there is a strong demand for replacing glass substrates used in image display devices such as liquid crystal displays and OLED displays with plastic substrates, and studies have been actively conducted on polyimides which are most suitable as one of the plastic materials.
However, conventional polyimides are generally wholly aromatic and are generally prepared by a polycondensation reaction of a diamine and a dianhydride to prepare a prepolymer, followed by imidization. Since the electron donating property of the diamine residue and the electron withdrawing property of the dianhydride residue cause the movement of charges in the molecule to form an electron transfer complex (CTC), the light transmittance is low and the polyimide film shows a characteristic yellow or brownish yellow color, greatly limiting its application in an image display device.
Although scholars at home and abroad inhibit the formation of CTC by introducing fluorine-containing groups, alicyclic structures, non-coplanar structures, meta-substituted structures, sulfone groups and the like into the polyimide main chain, so that the light transmittance of the polyimide film is improved, and the yellow index of the film is reduced. However, the above means have a limited effect and may cause a decrease in the heat resistance of the film.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides polyimide and a colorless transparent polyimide film, wherein the polyimide film has a very low yellow index and excellent heat-resistant dimensional stability.
The polyimide is prepared by carrying out polycondensation on alicyclic dianhydride, aromatic diacid chloride and aromatic diamine;
wherein the structural formula of the alicyclic dianhydride is shown as follows:
preferably, the aromatic dianhydride is at least one of 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride, 4, 4' -oxydiphthalic anhydride, 3', 4, 4' -benzophenone tetracarboxylic dianhydride, and 3, 3', 4, 4' -biphenyl tetracarboxylic dianhydride.
Preferably, the aromatic diacid chloride is at least one of terephthaloyl chloride or isophthaloyl chloride.
Preferably, the aromatic diamine is at least one of 2, 2' -bis (trifluoromethyl) diaminobiphenyl, 4' -diaminodiphenyl ether, or 4, 4' -diaminooctafluorobiphenyl.
Preferably, the alicyclic dianhydride is used in an amount of 30 to 60 mol% based on the aromatic diamine, and the aromatic diacid chloride is used in an amount of 10 to 40 mol% based on the aromatic diamine.
Preferably, the polyimide is prepared by the following method:
carrying out polymerization reaction on alicyclic dianhydride, aromatic diacid chloride and aromatic diamine in an organic solvent to obtain polyamic acid;
and carrying out imidization reaction on the polyamic acid to obtain the polyimide.
Preferably, the organic solvent is at least one of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, or xylene.
The invention also provides a colorless transparent polyimide film, which is prepared by forming the polyimide film.
Preferably, the polyimide film has a linear thermal expansion coefficient of 25ppm/K or less, a transmittance of light having a wavelength of 400nm of 85% or more, and a yellowness index of 3 or less.
Preferably, the present invention proposes an image display device comprising the above polyimide or polyimide film.
The invention provides a polyimide and a colorless transparent polyimide film, wherein the polyimide is prepared by compounding alicyclic dianhydride, aromatic dianhydride and aromatic diacid chloride with a specific structural formula, so that the transparency of the prepared polyimide and the polyimide film is improved, and the linear thermal expansion coefficient of the prepared polyimide and the polyimide film is effectively reduced, therefore, the polyimide and the polyimide film can be widely applied to various optical elements.
Detailed Description
The polyimide and the polyimide film provided by the invention are prepared by carrying out polycondensation on alicyclic dianhydride, aromatic diacid chloride and aromatic diamine;
wherein the structural formula of the alicyclic dianhydride is shown as follows:
in the invention, the alicyclic dianhydride is selected from the dianhydrides shown in the structural formula, so that the aliphatic skeleton structure can be used for inhibiting charge transfer, and the structure of bridged cyclic hydrocarbon of macromolecules can be used for preventing the macromolecular chains from being closely stacked. Therefore, the specific selection of the alicyclic dianhydride simultaneously introduces the structures of amido bond, imide bond and bridged hydrocarbon into the polymer chains of the polyimide and the polyimide film, so that the light transmittance of the corresponding polyimide and the polyimide film is improved, the yellow index is reduced, and the thermal expansion property of the polyimide and the polyimide film is obviously improved.
In the present invention, the aromatic dianhydride may be selected from at least one of 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride, 4, 4' -oxydiphthalic anhydride, 3', 4, 4' -benzophenone tetracarboxylic dianhydride, and 3, 3', 4, 4' -biphenyl tetracarboxylic dianhydride.
On one hand, the introduction of the aromatic dianhydride can be compounded with the alicyclic dianhydride, so that the polyimide and the polyimide film have a composite structure with aromatic rigidity and alicyclic flexibility in a high molecular chain, and the mechanical properties of the corresponding polyimide and the polyimide film are ensured. On the other hand, when 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride aromatic dianhydride is used as the dianhydride monomer in consideration of the charge transfer effect of the fluorine substituent, it is apparent that the optical transparency of the resulting polyimide and polyimide film can be further improved.
Also in the present invention, the aromatic diamine may be selected from at least one of 2, 2' -bis (trifluoromethyl) diaminobiphenyl, 4' -diaminodiphenyl ether, or 4, 4' -diaminooctafluorobiphenyl. Similarly, when 2, 2' -bis (trifluoromethyl) diaminobiphenyl is used as the diamine monomer, the resulting polyimide and polyimide film can be provided with excellent optical transparency due to the charge transfer effect of the fluorine substituent.
In the present invention, the aromatic diacid chloride may be at least one of terephthaloyl chloride or isophthaloyl chloride. The introduction of aromatic diacid chloride reacts with aromatic diamine, so that an amide bond structure can be introduced into the polyimide and the polymer chain of the polyimide film, the hydrogen bond acting force between the polymer chains is enhanced by the amide bond structure, the yellow index of the polyimide and the polyimide film is reduced, and the reduction of linear thermal expansion coefficient is also obviously improved.
In the present invention, in order to further improve the performance of the polyimide and the polyimide film obtained, the amount of the alicyclic dianhydride is limited to 30 to 60 mol% based on the aromatic diamine, and the amount of the aromatic diacid chloride is limited to 10 to 40 mol% based on the aromatic diamine.
The limited raw material proportion can effectively control the reaction degree and the molecular chain structure of the polyimide and the polyimide film, not only further improves the optical transparency of the polyimide and the polyimide film, but also further reduces the linear thermal expansion coefficient of the polyimide and the polyimide film.
In the present invention, the polyimide is polymerized by a known method to obtain a polyamic acid as a polyimide precursor, and the polyamic acid is imidized by a thermal imidization method or a chemical imidization method to obtain the polyimide.
The polyamic acid is obtained by adding a monomer into an organic solvent and carrying out copolymerization reaction at room temperature. The organic solvent may be selected from any solvent that can dissolve the polyamic acid, such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, or xylene.
In the present invention, imidization of the polyamic acid to obtain the polyimide is preferably carried out by a chemical imidization method. Specifically, a dehydrating agent and an imidizing agent are added into a polyamic acid solution to complete imidization reaction after full reaction. The dehydrating agent can be selected from anhydride reagents which are beneficial to the reaction, such as acetic anhydride, propionic anhydride, maleic anhydride or phthalic anhydride and the like. The imidizing agent can be selected from tertiary amine reagents such as pyridine, isoquinoline or triethylamine.
In the present invention, the polyimide film is obtained by forming the polyimide film. Polyimide may be formed by coating a polyimide solution on a support and drying the polyimide solution, or may be formed by coating a polyamic acid on a support, heating the resulting film to complete imidization, and then sufficiently drying the film.
The viscosity of the polyimide solution is not particularly limited, and is selected according to the coating thickness and the application of coating, and the polyimide solution is neither too low nor too high, has too low viscosity, strong solution fluidity, is not easy to form a film, cannot ensure the uniformity of the film thickness, has too high viscosity, is easy to cause the problems of large coating resistance, gel defect after drying and the like.
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 3.2023g (10mmol) of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, 0.8885g (2mmol) of 4, 4' - (hexafluoroisopropylene) diphthalic anhydride (6FDA), 1.9206g (5mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha '-spirolactone-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride (CpODA) and 0.6091g (3mmol) of terephthaloyl chloride (TPC) are sequentially added, and the mixture is stirred and reacted for 8 hours at room temperature to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring and reacting for 1h at room temperature, then heating to 70 ℃, stirring and reacting for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ to be dried for 0.5h, heating to 180 ℃ to be dried for 1h, then heating to 260 ℃ to be dried for 0.5h, taking out the glass plate after the temperature is reduced to the room temperature, placing the glass plate in water to remove a film, then placing the obtained film in the drying box to be dried for removing water to obtain the polyimide film, and controlling the thickness of the polyimide film to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
Example 2
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 3.2023g (10mmol) of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, 0.6204g (2mmol) of 4, 4' -oxydiphthalic anhydride (ODPA), 1.9206g (5mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha '-spirolactone-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride (CpODA) and 0.6091g (3mmol) of terephthaloyl chloride (TPC) are sequentially added, and the mixture is stirred and reacted for 8 hours at room temperature to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring and reacting for 1h at room temperature, then heating to 70 ℃, stirring and reacting for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ to be dried for 0.5h, heating to 180 ℃ to be dried for 1h, then heating to 260 ℃ to be dried for 0.5h, taking out the glass substrate after the temperature is reduced to the room temperature, placing the glass substrate in water to remove a film, then placing the obtained film in the drying box to be dried for removing water to obtain the polyimide film, and controlling the thickness of the polyimide film to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
Example 3
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 3.2023g (10mmol) of 2, 2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, 0.6445g (2mmol) of 3, 3', 4, 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 1.9206g (5mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6, 6 ' -tetracarboxylic dianhydride (CpODA) and 0.6091g (3mmol) of terephthaloyl chloride (TPC) are sequentially added, and stirring reaction is carried out at room temperature for 8 hours to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring and reacting for 1h at room temperature, then heating to 70 ℃, stirring and reacting for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ to be dried for 0.5h, heating to 180 ℃ to be dried for 1h, then heating to 260 ℃ to be dried for 0.5h, taking out the glass plate after the temperature is reduced to the room temperature, placing the glass plate in water to remove a film, then placing the obtained film in the drying box to be dried for removing water to obtain the polyimide film, and controlling the thickness of the polyimide film to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
Example 4
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 2.0024g (10mmol) of 4, 4 '-diaminodiphenyl ether (ODA) is dissolved in 50mL of N, N-dimethylacetamide, 0.8885g (2mmol) of 4, 4' - (hexafluoroisopropylene) diphthalic anhydride (6FDA), 1.9206g (5mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha '-spirolactone-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride (CpODA) and 0.6091g (3mmol) of terephthaloyl chloride (TPC) are sequentially added, and the mixture is stirred and reacted for 8 hours at room temperature to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring and reacting for 1h at room temperature, then heating to 70 ℃, stirring and reacting for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ to be dried for 0.5h, heating to 180 ℃ to be dried for 1h, then heating to 260 ℃ to be dried for 0.5h, taking out the glass substrate after the temperature is reduced to the room temperature, placing the glass substrate in water to remove a film, placing the obtained film in the drying box to be dried for removing water to obtain the polyimide film, and controlling the film thickness of the polyimide film to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
Example 5
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 3.2023g (10mmol) of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, 0.8885g (2mmol) of 4, 4' - (hexafluoroisopropylene) diphthalic anhydride (6FDA), 1.9206g (5mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha '-spirolactone-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride (CpODA) and 0.6091g (3mmol) of isophthaloyl dichloride (IPC) are sequentially added, and the mixture is stirred and reacted for 8 hours at room temperature to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring and reacting for 1h at room temperature, then heating to 70 ℃, stirring and reacting for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ to be dried for 0.5h, heating to 180 ℃ to be dried for 1h, then heating to 260 ℃ to be dried for 0.5h, taking out the glass substrate after the temperature is reduced to the room temperature, placing the glass substrate in water to remove a film, then placing the obtained film in the drying box to be dried for removing water to obtain the polyimide film, and controlling the thickness of the polyimide film to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
Example 6
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 3.2023g (10mmol) of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, 1.3327g (3mmol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 1.1524g (3mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha '-spirolactone-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride (CpODA) and 0.8121g (4mmol) of terephthaloyl chloride (TPC) are sequentially added, and the mixture is stirred and reacted for 8 hours at room temperature to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring at room temperature for 1h, then heating to 70 ℃, stirring for reaction for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ to be dried for 0.5h, heating to 180 ℃ to be dried for 1h, then heating to 260 ℃ to be dried for 0.5h, taking out the glass substrate after the temperature is reduced to the room temperature, placing the glass substrate in water to remove a film, then placing the obtained film in the drying box to be dried for removing water to obtain the polyimide film, and controlling the thickness of the polyimide film to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
Example 7
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 3.2023g (10mmol) of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, 1.3327g (3mmol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 2.3047g (6mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha '-spirolactone-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride (CpODA) and 0.2030g (1mmol) of terephthaloyl chloride (TPC) are sequentially added, and the mixture is stirred and reacted for 8 hours at room temperature to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring and reacting for 1h at room temperature, then heating to 70 ℃, stirring and reacting for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ to be dried for 0.5h, heating to 180 ℃ to be dried for 1h, then heating to 260 ℃ to be dried for 0.5h, taking out the glass plate after the temperature is reduced to the room temperature, placing the glass plate in water to remove a film, then placing the obtained film in the drying box to be dried for removing water to obtain the polyimide film, and controlling the thickness of the polyimide film to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
Comparative example 1
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 3.2023g (10mmol) of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, 0.8885g (2mmol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 0.9806g (5mmol) of cyclobutanetetracarboxylic dianhydride (CBDA) and 0.6091g (3mmol) of terephthaloyl chloride (TPC) are sequentially added, and the mixture is stirred and reacted for 8 hours at room temperature to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring and reacting for 1h at room temperature, then heating to 70 ℃, stirring and reacting for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ to be dried for 0.5h, heating to 180 ℃ to be dried for 1h, then heating to 260 ℃ to be dried for 0.5h, taking out the glass plate after the temperature is reduced to the room temperature, placing the glass plate in water to remove a film, then placing the obtained film in the drying box to be dried for removing water to obtain the polyimide film, and controlling the thickness of the polyimide film to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
Comparative example 2
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 3.2023g (10mmol) of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, 1.3327g (3mmol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 0.7682g (2mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha '-spirolactone-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride (CpODA) and 1.0151g (5mmol) of terephthaloyl chloride (TPC) are sequentially added, and the mixture is stirred and reacted for 8 hours at room temperature to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring and reacting for 1h at room temperature, then heating to 70 ℃, stirring and reacting for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ for drying for 0.5h, heating to 180 ℃ for drying for 1h, then heating to 260 ℃ for drying for 0.5h, taking out the glass substrate after the temperature is reduced to the room temperature, placing the glass substrate in water for demoulding, and then placing the obtained film in a drying box at 100 ℃ for drying and removing water to obtain the polyimide film, wherein the thickness of the polyimide film is controlled to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
Comparative example 3
A polyimide film, the preparation method of which comprises:
under the protection of nitrogen, 3.2023g (10mmol) of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, 0.4442g (1mmol) of 4, 4' - (hexafluoroisopropylene) diphthalic anhydride (6FDA), 2.6888g (7mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha '-spirolactone-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride (CpODA) and 0.4060g (2mmol) of terephthaloyl chloride (TPC) are sequentially added, and the mixture is stirred and reacted for 8 hours at room temperature to obtain a polyamic acid solution;
adding 2.18g of pyridine and 2.82g of acetic anhydride into the polyamic acid solution, stirring and reacting for 1h at room temperature, then heating to 70 ℃, stirring and reacting for 1h, cooling to room temperature, transferring the reaction solution into a dropping funnel, dropping the reaction solution into a container filled with 1L of methanol at the speed of 2 drops/second to gradually separate out a precipitate, filtering the precipitate, washing with a large amount of methanol, crushing the obtained solid, and performing vacuum drying at 100 ℃ to obtain polyimide;
adding the polyimide into N-methyl pyrrolidone to be completely dissolved to obtain a polyimide solution with the solid content of 15 wt%, coating the polyimide solution on a glass substrate, placing the glass substrate in a drying box at 80 ℃ to be dried for 0.5h, heating to 180 ℃ to be dried for 1h, then heating to 260 ℃ to be dried for 0.5h, taking out the glass plate after the temperature is reduced to the room temperature, placing the glass plate in water to remove a film, then placing the obtained film in the drying box to be dried for removing water to obtain the polyimide film, and controlling the thickness of the polyimide film to be 50 mu m.
The results of the performance test on the polyimide film are shown in table 1.
The results of the tests for the thermal properties and the optical properties of the polyimide films obtained in examples 1 to 7 and comparative examples 1 to 3 are shown in the following table.
Thermal properties include glass transition temperature and coefficient of linear thermal expansion:
coefficient of linear thermal expansion CTE: measuring at a temperature range of 50-250 deg.C at a heating rate of 10 deg.C/min by applying a 50mN load under nitrogen atmosphere with a thermomechanical analyzer to obtain an average value;
glass transition temperature Tg: DSC measurement was carried out at a temperature rise rate of 10 ℃/min in a nitrogen atmosphere at a temperature range of 50 to 450 ℃ by using a differential scanning calorimeter apparatus to determine the glass transition temperature.
Optical properties include light transmittance and yellowness index:
total light transmittance TT: total light transmission was determined using uv-vis spectroscopy;
transmittance T at 400nm400: measuring the transmittance at 400nm by using an ultraviolet spectrophotometer;
yellowness index YI: the yellowness index was determined according to the ASTM E313 standard using an ultraviolet spectrophotometer.
TABLE 1 test results of polyimide films obtained in examples and comparative examples
As can be seen from the above table, the polyimide film according to the example of the present invention exhibits high light transmittance in the short wavelength region of 400nm, and has a low yellowness index and a linear thermal expansion coefficient.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The polyimide is characterized by being prepared by carrying out polycondensation on alicyclic dianhydride, aromatic diacid chloride and aromatic diamine;
wherein the structural formula of the alicyclic dianhydride is shown as follows:
2. the polyimide according to claim 1, wherein the aromatic dianhydride is at least one of 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride, 4, 4' -oxydiphthalic anhydride, 3', 4, 4' -benzophenone tetracarboxylic dianhydride, and 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride.
3. The polyimide according to claim 1 or 2, wherein the aromatic diacid chloride is at least one of terephthaloyl chloride or isophthaloyl chloride.
4. The polyimide according to any one of claims 1 to 3, wherein the aromatic diamine is at least one of 2, 2' -bis (trifluoromethyl) diaminobiphenyl, 4' -diaminodiphenyl ether, or 4, 4' -diaminooctafluorobiphenyl.
5. The polyimide according to any one of claims 1 to 4, wherein the alicyclic dianhydride is used in an amount of 30 to 60 mol% based on the aromatic diamine, and the aromatic diacid chloride is used in an amount of 10 to 40 mol% based on the aromatic diamine.
6. The polyimide according to any one of claims 1 to 5, wherein the polyimide is prepared by a method comprising:
carrying out polymerization reaction on alicyclic dianhydride, aromatic diacid chloride and aromatic diamine in an organic solvent to obtain polyamic acid;
and carrying out imidization reaction on the polyamic acid to obtain the polyimide.
7. The polyimide of claim 6, wherein the organic solvent is at least one of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidinone, or xylene.
8. A colorless transparent polyimide film obtained by forming the polyimide film according to any one of claims 1 to 7.
9. The colorless transparent polyimide film according to claim 8, wherein the polyimide film has a coefficient of linear thermal expansion of 25ppm/K or less, a transmittance of light having a wavelength of 400nm of 85% or more, and a yellowness index of 3 or less.
10. An image display device comprising the polyimide according to any one of claims 1 to 7, or the polyimide film according to any one of claims 8 to 9.
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| CN105492496A (en) * | 2013-06-27 | 2016-04-13 | 宇部兴产株式会社 | Polyimide precursor and polyimide |
| CN111989353A (en) * | 2018-05-10 | 2020-11-24 | 三菱瓦斯化学株式会社 | Polyamide-imide resin, polyamide-imide varnish and polyamide-imide film |
| US20210095121A1 (en) * | 2019-09-30 | 2021-04-01 | Sk Innovation Co., Ltd. | Polyimide-Based Film and Flexible Display Panel Including the Same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105492496A (en) * | 2013-06-27 | 2016-04-13 | 宇部兴产株式会社 | Polyimide precursor and polyimide |
| CN111989353A (en) * | 2018-05-10 | 2020-11-24 | 三菱瓦斯化学株式会社 | Polyamide-imide resin, polyamide-imide varnish and polyamide-imide film |
| US20210095121A1 (en) * | 2019-09-30 | 2021-04-01 | Sk Innovation Co., Ltd. | Polyimide-Based Film and Flexible Display Panel Including the Same |
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