WO2010077084A2 - 폴리이미드 필름 - Google Patents
폴리이미드 필름 Download PDFInfo
- Publication number
- WO2010077084A2 WO2010077084A2 PCT/KR2009/007946 KR2009007946W WO2010077084A2 WO 2010077084 A2 WO2010077084 A2 WO 2010077084A2 KR 2009007946 W KR2009007946 W KR 2009007946W WO 2010077084 A2 WO2010077084 A2 WO 2010077084A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solution
- molecular weight
- refractive index
- polyimide
- polyimide film
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 140
- 239000000843 powder Substances 0.000 claims description 70
- 229920005575 poly(amic acid) Polymers 0.000 claims description 62
- 239000004642 Polyimide Substances 0.000 claims description 57
- 229920000642 polymer Polymers 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 40
- 230000008859 change Effects 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 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 description 28
- 150000003949 imides Chemical class 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 24
- 150000004985 diamines Chemical class 0.000 claims description 24
- 238000006358 imidation reaction Methods 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000004458 analytical method Methods 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 19
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 125000006159 dianhydride group Chemical group 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000010287 polarization Effects 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 5
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000000930 thermomechanical effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 124
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 78
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 34
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 31
- 238000000569 multi-angle light scattering Methods 0.000 description 26
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 24
- 238000002347 injection Methods 0.000 description 22
- 239000007924 injection Substances 0.000 description 22
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 239000003480 eluent Substances 0.000 description 8
- 238000002203 pretreatment Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000149 argon plasma sintering Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 208000034628 Celiac artery compression syndrome Diseases 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 238000012284 sample analysis method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 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 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004262 Ethyl gallate Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- DUTLDPJDAOIISX-UHFFFAOYSA-N 3-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=CC(C(C(F)(F)F)C(F)(F)F)=C1 DUTLDPJDAOIISX-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- VNAOAABUWOXVLO-UHFFFAOYSA-N 3-[3-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(C=CC=2)C(C(F)(F)F)C(F)(F)F)=C1 VNAOAABUWOXVLO-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 description 1
- SSDBTLHMCVFQMS-UHFFFAOYSA-N 4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 SSDBTLHMCVFQMS-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- PJWQLRKRVISYPL-UHFFFAOYSA-N 4-[4-amino-3-(trifluoromethyl)phenyl]-2-(trifluoromethyl)aniline Chemical group C1=C(C(F)(F)F)C(N)=CC=C1C1=CC=C(N)C(C(F)(F)F)=C1 PJWQLRKRVISYPL-UHFFFAOYSA-N 0.000 description 1
- JYCTWJFSRDBYJX-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound O=C1OC(=O)CC1C1C2=CC=CC=C2C(C(=O)OC2=O)C2C1 JYCTWJFSRDBYJX-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-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
- 239000002313 adhesive film Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 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
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- -1 diethyl acetate Chemical compound 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 230000000007 visual effect Effects 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/78603—Thin film transistors, i.e. transistors with a channel being at least partly a thin film characterised by the insulating substrate or support
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0108—Transparent
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Definitions
- the present invention relates to a polyimide film which is colorless, transparent and excellent in heat resistance.
- Polyimide resin is an insoluble and insoluble ultra-high heat resistant resin, and has excellent characteristics such as thermal oxidation resistance, heat resistance, radiation resistance, low temperature property, chemical resistance, etc., and thus heat-resistant advanced materials and insulation materials for automobile materials, aviation materials, and spacecraft materials. It is used in a wide range of fields such as coating materials, insulating films, semiconductors, TFT-LCD electrode protective films, and the like. Recently, display materials such as optical fibers and liquid crystal alignment films and conductive fillers are contained in the film or coated on the surface to be used for transparent electrode films. .
- the present invention seeks to provide a polyimide film that satisfies transparency and is excellent in heat resistance.
- the present invention is an imide of a polyamic acid obtained by polymerizing diamines and acid dianhydrides, the imidation ratio is 80% or more, the absolute molecular weight (Mw) determined by the following formula 1 is 40,000 to 150,000 It provides a polyimide powder.
- the above equation causes the polarization of charges as the material interacts with light, and accordingly, the amount of charge transfer and the amount of radiation vary depending on the polarizability of the material in the phenomenon in which the vibrating charges radiate light radially.
- the principle of determining the molar mass and size of the polymer from the amount of scattered light and the angular variation measured by irradiating laser light to a solution containing any polymer and a solvent Is derived
- R ⁇ is the excess Rayleigh ratio
- K * 4 ⁇ 2 n 0 2 ( dn / dc ) 2 ⁇ 0 -4 N A -1 , where n 0 is the refractive index of the solvent, N A is the Avogadro's number, and dn / dc is the specific refractive index increment
- n 0 is the refractive index of the solvent
- N A is the Avogadro's number
- dn / dc is the specific refractive index increment
- c is the polymer concentration in solution (g / ml)
- M is the molar mass, which is the weight average molecular weight (Mw) for polydisperse samples,
- a 2 is the second virial coefficient
- Polyimide powder according to an embodiment of the present invention may have an absolute molecular weight (Mw) of 50,000 to 150,000.
- the polyimide powder according to one embodiment of the present invention may have an absolute molecular weight distribution (Polydispersity) of 1.1 to 1.5, in a preferred embodiment may have an absolute molecular weight distribution (Polydispersity) of 1.1 to 1.3.
- the acid dianhydride may include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride.
- 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride may be included in 30 mol% to 100 mol% of acid dianhydrides.
- the diamines may include 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl.
- 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl may be included in 20 to 100 mol% of diamines.
- the imide of the polyamic acid is prepared by first adding 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride in an acid anhydride. It may be an imide of the polyamic acid obtained.
- the imide of the polyamic acid is the last of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride in the acid anhydrides. It may be an imide of the polyamic acid obtained by the addition.
- the polymerization may be performed for 1 to 24 hours.
- the polymerization may be performed for 8 to 12 hours.
- Solutions containing imides include methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-propyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, phenol and precipitating by adding a solvent selected from t-butyl alcohol; And it comprises a step of filtering the precipitated solid content, the imidation ratio of 80% or more, and provides a method for producing a polyimide powder having an absolute molecular weight (Mw) of 40,000 to 150,000 determined by the following formula (1).
- Mw absolute molecular weight
- the above equation causes the polarization of charges as the material interacts with light, and accordingly, the amount of charge transfer and the amount of radiation vary depending on the polarizability of the material in the phenomenon in which the vibrating charges radiate light radially.
- the principle of determining the molar mass and size of the polymer from the amount of scattered light and the angular variation measured by irradiating laser light to a solution containing any polymer and a solvent Is derived
- R ⁇ is the excess Rayleigh ratio
- K * 4 ⁇ 2 n 0 2 ( dn / dc ) 2 ⁇ 0 -4 N A -1 , where n 0 is the refractive index of the solvent, N A is the Avogadro's number, and dn / dc is the specific refractive index increment
- n 0 is the refractive index of the solvent
- N A is the Avogadro's number
- dn / dc is the specific refractive index increment
- c is the polymer concentration in solution (g / ml)
- M is the molar mass, which is the weight average molecular weight (Mw) for polydisperse samples,
- a 2 is the second virial coefficient
- a polyimide film obtained by forming an imide of a polyamic acid obtained by polymerizing diamines and acid dianhydrides, and having an absolute molecular weight (Mw) of 30,000 to 170,000 determined by the following Formula 1 To provide.
- the above equation causes the polarization of charges as the material interacts with light, and accordingly, the amount of charge transfer and the amount of radiation vary depending on the polarizability of the material in the phenomenon in which the vibrating charges radiate light radially.
- the principle of determining the molar mass and size of the polymer from the amount of scattered light and the angular variation measured by irradiating laser light to a solution containing any polymer and a solvent Is derived
- R ⁇ is the excess Rayleigh ratio
- K * 4 ⁇ 2 n 0 2 ( dn / dc ) 2 ⁇ 0 -4 N A -1 , where n 0 is the refractive index of the solvent, N A is the Avogadro's number, and dn / dc is the specific refractive index increment
- n 0 is the refractive index of the solvent
- N A is the Avogadro's number
- dn / dc is the specific refractive index increment
- c is the polymer concentration in solution (g / ml)
- M is the molar mass, which is the weight average molecular weight (Mw) for polydisperse samples,
- a 2 is the second virial coefficient
- Polyimide film according to an embodiment of the present invention may be an imidation ratio of 95% or more.
- Polyimide film according to an embodiment of the present invention may have an absolute molecular weight (Mw) of 50,000 to 150,000.
- the polyimide film according to an embodiment of the present invention may have an absolute molecular weight distribution (Polydispersity) of 1.1 to 1.6, preferably may have an absolute molecular weight distribution (Polydispersity) of 1.1 to 1.3.
- Acid dianhydrides may be those containing 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride.
- the 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride may be included in 30 mol% to 100 mol% of acid dianhydrides.
- the diamines may include 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl.
- 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl may be included in 20 mol% to 100 mol% of diamines.
- an imide of a polyamic acid obtained by first introducing 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride among acid anhydrides It may be obtained from.
- a polyamic acid obtained by adding 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride obtained by adding 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride to the last of acid anhydrides It may be obtained from an imide.
- the polymerization may be performed for 1 to 24 hours.
- the polymerization can be carried out for 8 to 12 hours.
- the polyimide film according to one embodiment of the present invention may have a yellowness of 4.5 or less based on a film thickness of 50 to 100 ⁇ m.
- the polyimide film according to the embodiment of the present invention may have a mean coefficient of linear expansion (CTE) measured in the range of 50 to 250 ° C. by a thermomechanical analysis method based on a film thickness of 50 to 100 ⁇ m of 70 ppm / ° C. or less. .
- CTE mean coefficient of linear expansion
- a polyamic acid solution further comprising the steps of: polymerizing diamines and acid dianhydrides in an organic solvent to obtain a polyamic acid solution; Adding a chemical converting agent to a polyamic acid solution to imidize at an imidation ratio of 80% or more to prepare a solution containing an imide;
- Solutions containing imides include methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-propyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, phenol and precipitating by adding a solvent selected from t-butyl alcohol; Filtering the precipitated solids; Drying the filtrate to obtain a polyimide powder; Dissolving the polyimide powder in an organic solvent; Forming a polyimide solution; And it comprises a step of heat treatment at 100 to 500 °C, provides a method for producing a polyimide film having an absolute molecular
- the above equation causes the polarization of charges as the material interacts with light, and accordingly, the amount of charge transfer and the amount of radiation vary depending on the polarizability of the material in the phenomenon in which the vibrating charges radiate light radially.
- the principle of determining the molar mass and size of the polymer from the amount of scattered light and the angular variation measured by irradiating laser light to a solution containing any polymer and a solvent Is derived
- R ⁇ is the excess Rayleigh ratio
- K * 4 ⁇ 2 n 0 2 ( dn / dc ) 2 ⁇ 0 -4 N A -1 , where n 0 is the refractive index of the solvent, N A is the Avogadro's number, and dn / dc is the specific refractive index increment
- n 0 is the refractive index of the solvent
- N A is the Avogadro's number
- dn / dc is the specific refractive index increment
- c is the polymer concentration in solution (g / ml)
- M is the molar mass, which is the weight average molecular weight (Mw) for polydisperse samples,
- a 2 is the second virial coefficient
- the chemical converting agent may include a dehydrating agent and a catalyst.
- Polyimide film according to an embodiment of the present invention is excellent in transparency and excellent in heat resistance, and is expected to be useful for a transparent conductive film, a TFT substrate, a flexible printed circuit board, etc. due to a small change in dimension due to thermal stress.
- the polyimide powder according to one embodiment of the present invention is an imide of polyamic acid obtained by polymerizing diamines and acid dianhydrides in terms of satisfying heat resistance while ensuring transparency, having an imidation ratio of 80% or more,
- the absolute molecular weight (Mw) determined by 1 may be 40,000 to 150,000.
- the above equation causes the polarization of charges as the material interacts with light, and accordingly, the amount of charge transfer and the amount of radiation vary depending on the polarizability of the material in the phenomenon in which the vibrating charges radiate light radially.
- the principle of determining the molar mass and size of the polymer from the amount of scattered light and the angular variation measured by irradiating laser light to a solution containing any polymer and a solvent Is derived
- R ⁇ is the excess Rayleigh ratio
- K * 4 ⁇ 2 n 0 2 ( dn / dc ) 2 ⁇ 0 -4 N A -1 , where n 0 is the refractive index of the solvent, N A is the Avogadro's number, and dn / dc is the specific refractive index increment
- n 0 is the refractive index of the solvent
- N A is the Avogadro's number
- dn / dc is the specific refractive index increment
- c is the polymer concentration in solution (g / ml)
- M is the molar mass, which is the weight average molecular weight (Mw) for polydisperse samples,
- a 2 is the second virial coefficient
- Light scattering is caused by the polymer chain in the polymer solution because the coil size of the polymer is smaller or similar to the wavelength of the light and the polymer chains are polarized by the electric field of the incident light.
- the degree of scattering is not proportional to the amount of the material causing the scattering, and when there is the same amount of scattering material, scattering by large particles is much stronger than scattering by small particles. Therefore, the degree of scattering of light is influenced by the size of the particles, so using the degree of light scattering can obtain information on the molecular weight of the polymer.
- the light when light passes through a lean polymer solution where the refractive index of the solvent is different from the refractive index of the polymer dissolved in the solvent, the light will be scattered according to the intensity depending on the size and concentration of the dissolved polymer in addition to the difference in refractive index between the polymer and the solvent. . If the polymer solution is sufficient lean solution, the intensity of the scattered light will appear as the sum of the scattering contributions generated by the individual polymer coils well separated in the solution. If the size of the molten polymer coil is significantly smaller than the wavelength of light, they are isotropic or have the same polarization in all directions, so that the intensity of light scattered by each polymer coil in any direction is the square of the size of the scattered light wave vector. Is proportional to.
- Equation 1 is derived from this principle, and as an example of an apparatus for obtaining an absolute molecular weight by the above equation, there is a Multi Angle Light Scattering (MALS) system from Wyatt. Through this, various other data such as weight average molecular weight, size, and molecular weight distribution of the sample to be analyzed can be obtained.
- MALS Multi Angle Light Scattering
- polyimide powder having an absolute molecular weight (Mw) of 40,000 to 150,000 obtained by MALS provided in one embodiment of the present invention is excellent in transparency and excellent in heat resistance.
- the absolute molecular weight (Mw) obtained by MALS is less than 40,000, the viscosity is insufficient to form a film or the optical properties, the mechanical properties, and the heat resistance are degraded. If it is larger than 150,000, the viscosity is excessive to control the film thickness or depending on the film. Alternatively, physical properties may vary for each part of the film, and flexibility or productivity may be reduced when the film is produced.
- the absolute molecular weight is about 50,000 to 150,000 may be preferable in terms of transparency and heat resistance.
- the polyimide powder of the present invention is good in terms of storage stability if the imidation ratio is 80% or more. If the imidation ratio of the polyimide powder is less than 80%, there may be a storage stability problem.
- the polyimide powder according to one embodiment of the present invention may have an absolute molecular weight distribution (Polydispersity) of 1.1 to 1.5 determined by Equation 1, since the absolute molecular weight distribution affects optical properties, mechanical properties, and heat resistance. Absolute molecular weight distribution is preferably within the above range. More preferably, the absolute molecular weight distribution (Polydispersity) may be 1.1 to 1.3.
- An example of a method of obtaining a polyimide powder that satisfies the absolute molecular weight and the imidization ratio as described above may include a method of controlling the selection of a monomer, a polymerization order, a polymerization method, and the like, and different precipitation methods for obtaining a powder. There is also a method.
- the polyimide powder according to one embodiment of the present invention may be obtained by obtaining a polyamic acid by polymerization of an acid dianhydride and diamine, and imidizing it.
- the acid dianhydride preferably includes 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6-FDA).
- 6-FDA 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride
- PMDA pyromellitic dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- ODPA oxydiphthalic dianhydride
- the amount of 6-FDA in the acid dianhydride may be preferably 30 to 100 mol% in terms of expressing transparency and not impairing other physical properties such as heat resistance.
- diamines examples include 2,2-bis [4- (4-aminophenoxy) -phenyl] propane (6HMDA), 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-TFDB), 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3,3'-TFDB), 4,4'-bis (3-amino Phenoxy) diphenylsulfone (DBSDA), bis (3-aminophenyl) sulfone (3DDS), bis (4-aminophenyl) sulfone (4DDS), 1,3-bis (3-aminophenoxy) benzene (APB- 133), 1,4-bis (4-aminophenoxy) benzene (APB-134), 2,2'-bis [3 (3-aminophenoxy) phenyl] hexafluoropropane (3-BDAF), 2 , 2'-bis [4 (4-
- 2,2'-TFDB in 20 to 100 mol% of the total diamine in terms of maintaining transparency through free volume by the side chain.
- the acid dianhydride component and the diamine component described above are dissolved in a solvent to react in an equimolar amount to prepare a polyamic acid solution.
- the reaction temperature is preferably -20 to 80 ° C, and the polymerization time is preferably 1 to 24 hours, preferably 8 to 12 hours. Moreover, it is more preferable that it is inert atmosphere, such as argon and nitrogen at the time of reaction.
- a solvent for the solution polymerization of the monomers described above is not particularly limited as long as it is a solvent in which a polyamic acid is dissolved.
- Known reaction solvents selected from m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate
- NMP N-methyl-2-pyrrolidone
- DMF dimethylformamide
- DMAc dimethylacetamide
- DMSO dimethyl sulfoxide
- acetone diethyl acetate
- low boiling point solutions such as tetrahydrofuran (THF), chloroform or low absorbing solvents such as ⁇ -butyrolactone may be used.
- the content of the first solvent is preferably 50 to 95% by weight of the total polyamic acid solution, more preferably 70 to 90 It is more preferable that it is weight%.
- a polyimide powder using such a monomer there is no particular limitation in the method for producing a polyimide powder using such a monomer.
- examples thereof include polymerization of diamines and acid dianhydrides under a first solvent to obtain a polyamic acid solution. After the solution is imidized to prepare a solution containing the imide, the second solvent is added to the solution containing the imide to precipitate, and the precipitated solid is filtered and dried to obtain a solid content of the polyimide resin. Can be obtained.
- the second solvent may be lower in polarity than the first solvent, which is a solvent for precipitating resin solids.
- Examples include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-propyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, phenol, t-butyl alcohol Etc. can be mentioned.
- the polymerization by adding at the end rather than pre-injecting 6-FDA in acid dianhydride may increase the molecular weight. It may be preferable in that a polyimide powder having a higher absolute molecular weight can be obtained at the same polymerization time. As a result, the heat resistance of the film may be controlled by controlling the monomer input order, and thus, in the case of polyimide powder having a large absolute molecular weight, heat resistance may be further improved.
- the heat resistance of the film according to the polymerization time it may be possible to control the heat resistance of the film according to the polymerization time, the longer the polymerization time, the greater the absolute molecular weight value.
- the absolute molecular weight value decreases again as a certain polymerization time elapses. If the polymerization time becomes too long, the absolute molecular weight decreases due to depolymerization.
- the thermal stability (CTE) may be worsened by the molecular weight decrease, while if the polymerization time is too short, the distribution of molecular weight (PDI) is too wide, which may result in a decrease in the mechanical properties of the film.
- CTE thermal stability
- PDI distribution of molecular weight
- an imidation ratio of 80% or more, preferably 85% or more in terms of optical, mechanical and heat resistance it may be preferable to provide an imidation ratio of 80% or more, preferably 85% or more in terms of optical, mechanical and heat resistance.
- the conditions which dry after filtering the obtained polyimide resin solid content are 50-120 degreeC, and time is 3 to 24 hours, considering the boiling point of a 2nd solvent.
- a polyimide film having an absolute molecular weight of 30,000 to 170,000, obtained by forming an imide of a polyamic acid obtained by polymerizing diamines and acid dianhydrides, is provided by Equation 1 below. do.
- the above equation causes the polarization of charges as the material interacts with light, and accordingly, the amount of charge transfer and the amount of radiation vary depending on the polarizability of the material in the phenomenon in which the vibrating charges radiate light radially.
- the principle of determining the molar mass and size of the polymer from the amount of scattered light and the angular variation measured by irradiating laser light to a solution containing any polymer and a solvent Is derived
- R ⁇ is the excess Rayleigh ratio
- K * 4 ⁇ 2 n 0 2 ( dn / dc ) 2 ⁇ 0 -4 N A -1 , where n 0 is the refractive index of the solvent, N A is the Avogadro's number, and dn / dc is the specific refractive index increment
- n 0 is the refractive index of the solvent
- N A is the Avogadro's number
- dn / dc is the specific refractive index increment
- c is the polymer concentration in solution (g / ml)
- M is the molar mass, which is the weight average molecular weight (Mw) for polydisperse samples,
- a 2 is the second virial coefficient
- the polyimide film As described above, in the case of the polyimide film, it is difficult to measure the absolute molecular weight by light scattering, because it is difficult to polymerize the polymer due to the large amount of aromatic rings. If a large amount of the aromatic ring is present, the polyimide film is colored.
- the absolute molecular weight (Mw) obtained by MALS provided in one embodiment of the present invention is 30,000.
- Mw the absolute molecular weight obtained by MALS provided in one embodiment of the present invention.
- the polyimide film of 170,000 to 170,000 it is excellent in transparency and excellent in heat resistance.
- the polyimide film has an absolute molecular weight (Mw) obtained by MALS is less than 30,000, optical properties, mechanical properties and heat resistance are lowered, and if the polyimide film is larger than 170,000, flexibility and productivity of the film may be reduced.
- Mw absolute molecular weight
- the absolute molecular weight of about 30,000 to 170,000 may be preferable in view of transparency and heat resistance.
- the polyimide film of the present invention has an imidation ratio of 95% or more in terms of optical, mechanical properties and heat resistance.
- the imidation ratio of the polyimide film is less than 95%, there may be a problem in terms of optical, mechanical properties and heat resistance.
- the polyimide film according to one embodiment of the present invention may have an absolute molecular weight distribution (Polydispersity) is determined by the formula 1 1.1 to 1.6, the absolute molecular weight distribution affects the optical properties, mechanical properties and heat resistance of the film In this respect, the absolute molecular weight distribution is preferably within the above range. More preferably, the absolute molecular weight distribution (Polydispersity) may be 1.1 to 1.3.
- the process of manufacturing the polyimide film may include a process of dissolving the polyimide powder obtained by the above-described method in an organic solvent to obtain a polyimide solution, then forming a film and heat-treating it.
- the first solvent may be used as the organic solvent.
- the polyimide solution can be cast on a support and heated to a temperature of 40 to 400 ° C. for 1 minute to 8 hours to obtain a polyimide film.
- the polyimide solution is subjected to a heat treatment process in order to increase thermal stability and decrease thermal history. Can be.
- the temperature of the additional heat treatment step is preferably 100 to 500 ° C., and the heat treatment time is preferably 1 to 30 minutes.
- the residual volatile content of the film after heat treatment may be 5% or less, and preferably 3% or less.
- the chemical conversion agent may include an imidization catalyst represented by a dehydrating agent represented by an acid anhydride such as acetic anhydride and tertiary amines such as isoquinoline, ⁇ -picolin, pyridine, and the like. It may be preferable in terms of decreasing molecular weight reduction.
- the polyimide film according to one embodiment of the present invention preferably has a yellowness of 4.5 or less in terms of securing transparency.
- the average transmittance at 400 to 740 nm measured by UV spectrophotometer based on the film thickness of 50 ⁇ 100 ⁇ m is preferably 85% or more. If the average transmittance at 400 to 740 nm measured by the UV spectrophotometer based on the film thickness of 50 ⁇ 100 ⁇ m less than 85% there may be a problem that can not exhibit the proper visual effects in use for display applications.
- the polyimide film according to one embodiment of the present invention has an L value of 90 or more when the color coordinate is measured by UV spectrophotometer based on the film thickness of 50 ⁇ 100 ⁇ m, It is preferable that a value is 5 or less, and b value is 5 or less.
- the polyimide film has an average coefficient of linear expansion (CTE) of 70 ppm / ° C. or less measured in the range of 50 to 250 ° C. by thermomechanical analysis based on the film thickness of 50 to 100 ⁇ m. Do.
- CTE coefficient of linear expansion
- the linear expansion coefficient may be excessively large when the adhesive film is manufactured, and the difference between the linear expansion coefficient of the metal foil may increase, which may cause dimensional change.
- the average coefficient of linear expansion (CTE) is 15 ppm / ⁇ ⁇ to 60 ppm / ⁇ ⁇ .
- the reactor was filled with 587.54 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler.
- DMAc N, N-dimethylacetaamide
- 64.046 g (0.2 mol) of TFDB was then dissolved to maintain this solution at 25 ° C. 71.08 g (0.16 mol) of 6FDA was added thereto and stirred for 1 hour to completely dissolve 6FDA.
- the temperature of the solution was maintained at 25 °C. 11.76 g (0.04 mol) of BPDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.
- the polyamic acid solution was stirred at room temperature for 12 hours, and 31.64 g of pyridine and 40.91 g of acetic anhydride were added for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool to room temperature, which was then slowly added to a container containing 20 L of methanol. The precipitate was added and precipitated. The precipitated solid was filtered and ground, and then dried under vacuum at 80 ° C. for 6 hours to obtain 120 g of a solid powder (82% imidation ratio).
- the reactor was filled with 587.54 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler. 64.046 g (0.2 mol) of TFDB was then dissolved to maintain this solution at 25 ° C. 11.76 g (0.04 mol) of BPDA was added thereto and stirred for 1 hour to completely dissolve BPDA. At this time, the temperature of the solution was maintained at 25 °C. 71.08 g (0.16 mol) of 6FDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.
- DMAc N, N-dimethylacetaamide
- the polyamic acid solution was stirred at room temperature for 3 hours, 31.64 g of pyridine and 40.91 g of acetic anhydride were added and stirred for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool to room temperature, which was then slowly added to a container containing 20 L of methanol. The precipitate was added and precipitated. The precipitated solid was filtered and pulverized, and then dried under vacuum at 80 ° C. for 6 hours to obtain 90 g of solid powder (80% of imidization ratio).
- the reactor was filled with 587.54 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler. 64.046 g (0.2 mol) of TFDB was then dissolved to maintain this solution at 25 ° C. 11.76 g (0.04 mol) of BPDA was added thereto and stirred for 1 hour to completely dissolve BPDA. At this time, the temperature of the solution was maintained at 25 °C. 71.08 g (0.16 mol) of 6FDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.
- DMAc N, N-dimethylacetaamide
- the polyamic acid solution was stirred at room temperature for 12 hours, and 31.64 g of pyridine and 40.91 g of acetic anhydride were added for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool to room temperature. The precipitate was added and precipitated. The precipitated solid was filtered and ground, and then dried under vacuum at 80 ° C. for 6 hours to obtain 126 g of a solid powder (82% imidation ratio).
- the reactor was filled with 587.54 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler. 64.046 g (0.2 mol) of TFDB was then dissolved to maintain this solution at 25 ° C. 11.76 g (0.04 mol) of BPDA was added thereto and stirred for 1 hour to completely dissolve BPDA. At this time, the temperature of the solution was maintained at 25 °C. 71.08 g (0.16 mol) of 6FDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.
- DMAc N, N-dimethylacetaamide
- the polyamic acid solution was stirred at room temperature for 24 hours, and 31.64 g of pyridine and 40.91 g of acetic anhydride were added for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool down to room temperature, which was then slowly added to a container containing 20 L of methanol. The precipitate was added and precipitated. The precipitated solid was filtered and ground, and then dried under vacuum at 80 ° C. for 6 hours to obtain 125 g of a solid powder (83% imidation ratio).
- GPC & MALS Analytical Instruments GPC-Water 1525 Binary HPLC pump; RI detector-Wyatt optilab rEX; MALS-Wyatt Dawn 8+; Column- ⁇ -Styragel HT Linear (7.8 * 300mm) 2EA, Styragel HT 6E
- Dn / Dc is a specific refractive index increment.
- the value of the change rate of the refractive index according to the change rate of the lean solution concentration is detected. Is a value obtained by differentiating a value measured in a concentration range 0.001 to 0.1 g / ml, specifically, a value set by the following method.
- 0.2 g of the polyimide powder obtained in Examples 1 to 4 was dissolved in 50 ml of DMF (containing 0.05% LiCl) to prepare a high concentration sample. Because it does not melt well, put it in an oven at 50 °C and shake it for 2 hours while shaking.
- the obtained high concentration samples were diluted to prepare samples of concentrations of 0.0032 g / ml, 0.0024 g / ml, 0.0016 g / ml, and 0.0008 g / ml, respectively.
- Each sample was measured for refractive index according to the concentration using a 0.45 ⁇ m syringe filter.
- the polyimide powder obtained in Examples 1 to 4 had a Dn / Dc value of 0.1180 at 50 ° C. in DMF (containing 0.05% LiCl).
- Example 1 Dn / Dc Mn (g / mol) Mp (g / mol) Mw (g / mol) Mz (g / mol) Rz (nm) Polydispersity
- Example 2 0.1180 3.407 ⁇ 10 4 4.446 ⁇ 10 4 4.241 ⁇ 10 4 5.511 ⁇ 10 4 14.6 1.245
- Example 3 0.1180 1.138 ⁇ 10 5 1.438 ⁇ 10 5 1.385 ⁇ 10 5 1.810 ⁇ 10 5 24.0 1.217
- Example 4 0.1180 7.564 ⁇ 10 4 1.120 ⁇ 10 5 8.727 ⁇ 10 4 9.496 ⁇ 10 4 14.8 1.153
- the reactor was filled with 587.54 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler. Then 64.064 g (0.2 mol) of TFDB was dissolved to maintain this solution at 25 ° C. 71.08 g (0.16 mol) of 6FDA was added thereto and stirred for 1 hour to completely dissolve 6FDA. At this time, the temperature of the solution was maintained at 25 °C. 11.76 g (0.04 mol) of BPDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.
- DMAc N, N-dimethylacetaamide
- the polyamic acid solution was stirred at room temperature for 3 hours, 31.64 g of pyridine and 40.91 g of acetic anhydride were added and stirred for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool to room temperature, which was then slowly added to a container containing 20 L of methanol. The precipitate was added and precipitated. The precipitated solid was filtered and pulverized and dried in vacuo at 80 ° C. for 6 hours to obtain 120 g of a solid powder (80% imidization ratio).
- the obtained solid powder was dissolved in 480 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution (viscosity 70 poise).
- DMAc N, N-dimethylacetamide
- the obtained solution was applied to a stainless plate, then cast at 700 ⁇ m, dried for 1 hour with hot air at 150 ° C., and the film was peeled off from the stainless plate to fix the pin to the frame.
- the film on which the film was fixed was placed in a vacuum oven and slowly heated for 2 hours from 100 ° C to 300 ° C, and then slowly cooled to separate from the frame to obtain a polyimide film. Thereafter, the resultant was heat-treated again at 300 ° C. for 30 minutes to obtain a polyimide film (thickness 100 ⁇ m, imidation ratio 95%).
- a polyimide film was obtained in the same manner as in Example 5, except that the reaction time was changed to 5, 12, and 24 hours, respectively, in preparing the polyamic acid solution.
- the reactor was filled with 587.54 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler. 64.046 g (0.2 mol) of TFDB was then dissolved to maintain this solution at 25 ° C. 11.76 g (0.04 mol) of BPDA was added thereto and stirred for 1 hour to completely dissolve BPDA. At this time, the temperature of the solution was maintained at 25 °C. 71.08 g (0.16 mol) of 6FDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.
- DMAc N, N-dimethylacetaamide
- the polyamic acid solution was stirred at room temperature for 3 hours, 31.64 g of pyridine and 40.91 g of acetic anhydride were added and stirred for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool to room temperature, which was then slowly added to a container containing 20 L of methanol. The precipitate was added and precipitated. The precipitated solid was filtered and pulverized, and then dried under vacuum at 80 ° C. for 6 hours to obtain 90 g of solid powder (80% of imidization ratio).
- the obtained solid powder was dissolved in 360 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution (viscosity 70 poise).
- DMAc N, N-dimethylacetamide
- the obtained solution was applied to a stainless plate, then cast at 700 ⁇ m, dried for 1 hour with hot air at 150 ° C., and the film was peeled off from the stainless plate to fix the pin to the frame.
- the film on which the film was fixed was placed in a vacuum oven and slowly heated for 2 hours from 100 ° C to 300 ° C, and then slowly cooled to separate from the frame to obtain a polyimide film. Thereafter, as a final heat treatment process, heat treatment was again performed at 300 ° C. for 30 minutes (thickness 100 ⁇ m, imidation ratio 95%).
- Polyimide film was obtained in the same manner as in Example 9, except that the reaction time was changed to 12 and 24 hours, respectively, in preparing the polyamic acid solution.
- the reactor was filled with 587.54 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler. 64.046 g (0.2 mol) of TFDB was then dissolved to maintain this solution at 25 ° C. 11.76 g (0.04 mol) of BPDA was added thereto and stirred for 1 hour to completely dissolve BPDA. At this time, the temperature of the solution was maintained at 25 °C. 71.08 g (0.16 mol) of 6FDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.
- DMAc N, N-dimethylacetaamide
- the polyamic acid solution was stirred at room temperature for 12 hours, and 31.64 g of pyridine and 40.91 g of acetic anhydride were added for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool to room temperature, which was then slowly added to a vessel containing 20 L of water. The precipitate was added and precipitated. The precipitated solid was filtered and pulverized and dried in vacuo at 80 ° C. for 6 hours to obtain 123 g of solid powder (81% imidization ratio).
- the obtained solid powder was dissolved in 492 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution (viscosity 70 poise).
- DMAc N, N-dimethylacetamide
- the obtained solution was applied to a stainless plate, then cast at 700 ⁇ m, dried for 1 hour with hot air at 150 ° C., and the film was peeled off from the stainless plate to fix the pin to the frame.
- the film on which the film was fixed was placed in a vacuum oven and slowly heated for 2 hours from 100 ° C to 300 ° C, and then slowly cooled to separate from the frame to obtain a polyimide film. Thereafter, as a final heat treatment process, heat treatment was again performed at 300 ° C. for 30 minutes (thickness 100 ⁇ m, imidation ratio 95%).
- GPC & MALS Analytical Instruments GPC-Water 1525 Binary HPLC pump; RI detector-Wyatt optilab rEX; MALS-Wyatt Dawn 8+; Column- ⁇ -Styragel HT Linear (7.8 * 300mm) 2EA, Styragel HT 6E
- Dn / Dc is a specific refractive index increment
- a polyimide film is injected into a flow cell of a differential refractometer in the form of a lean solution in an organic solvent
- the refractive index value according to the lean solution concentration change rate is detected.
- 0.2 g of the polyimide film obtained in Examples 5 to 12 was dissolved in 50 ml of DMF (containing 0.05% LiCl) to prepare a high concentration sample. Because it does not melt well, put it in an oven at 50 °C and shake it for 2 hours while shaking.
- the obtained high concentration samples were diluted to prepare samples of concentrations of 0.0032 g / ml, 0.0024 g / ml, 0.0016 g / ml, and 0.0008 g / ml, respectively.
- Each sample was measured for refractive index according to the concentration using a 0.45 ⁇ m syringe filter.
- the Dn / Dc value at DMF 50 ° C. was 0.1216.
- the absolute molecular weight value by MALS can be computed by the method mentioned above from the obtained Dn / Dc value, and the result is shown in following Table 2.
- the prepared film was measured for visible light transmittance using a UV spectrometer (Varian, Cary 100).
- the color coordinates were measured according to the ASTM E 1347-06 standard using a UV spectrometer (Varian, Cary100), the light source (Illuminant) was based on the measured value by CIE D65.
- TMA (TA Instrument, Inc., Q400) was used to measure the average coefficient of linear expansion at 50-250 ° C. according to TMA-Method.
- Example 5 0.1216 1.454 ⁇ 10 4 1.606 ⁇ 10 4 1.734 ⁇ 10 4 2.052 ⁇ 10 4 1.6 1.192
- Example 6 0.1216 2.610 ⁇ 10 4 3.096 ⁇ 10 4 3.128 ⁇ 10 4 4.039 ⁇ 10 4 17.2 1.198
- Example 7 0.1216 4.995 ⁇ 10 4 6.967 ⁇ 10 4 6.190 ⁇ 10 4 7.972 ⁇ 10 4 17.3 1.213
- Example 8 0.1216 3.711 ⁇ 10 4 4.871 ⁇ 10 4 4.642 ⁇ 10 4 4.642 ⁇ 10 4 21.9 1.251
- Example 9 0.1216 3.730 ⁇ 10 4 4.510 ⁇ 10 4 4.552 ⁇ 10 4 5.890 ⁇ 10 4 20.1 1.220
- Example 10 0.1216 1.071 ⁇ 10 5 1.334
- the polyimide film of the present invention is excellent in transparency and excellent in dimensional stability against thermal stress.
- the yellowness is high in the case of a film whose absolute molecular weight is too small as in Example 5.
- the polyamic acid solution was stirred at room temperature for 12 hours, and 31.64 g of pyridine and 40.91 g of acetic anhydride were added for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool to room temperature, which was then slowly added to a container containing 20 L of methanol. The precipitate was added and precipitated. The precipitated solid was filtered and ground, and then dried under vacuum at 80 ° C. for 6 hours to obtain 147 g of solid powder (imidization rate 80.5%).
- the obtained solid powder was dissolved in 588 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution (viscosity 70 poise).
- DMAc N, N-dimethylacetamide
- the obtained solution was applied to a stainless plate, then cast at 700 ⁇ m, dried for 1 hour with hot air at 150 ° C., and the film was peeled off from the stainless plate to fix the pin to the frame.
- the film on which the film was fixed was placed in a vacuum oven and slowly heated for 2 hours from 100 ° C to 300 ° C, and then slowly cooled to separate from the frame to obtain a polyimide film. Thereafter, the resultant was heat-treated again at 300 ° C. for 30 minutes (thickness 100 ⁇ m, imidation ratio 99.8%).
- GPC & MALS Analytical Instruments GPC-Water 1525 Binary HPLC pump; RI detector-Wyatt optilab rEX; MALS-Wyatt Dawn 8+; Column-use Shodex K-803, K-804 and K-805
- 0.05 g of the resulting film is weighed and 10 ml of DMF (containing 0.05% LiCl) is added to the vial.
- the film containing DMF solution is placed in a 50 ° C. oven and dissolved for 2 hours while shaking. After the sample is completely dissolved, filter it using a 0.45 ⁇ m syringe filter and mount it on a MALS autosampler.
- Dn / Dc is a specific refractive index increment
- a polyimide film is injected into a flow cell of a differential refractometer in the form of a lean solution in an organic solvent
- the refractive index value according to the lean solution concentration change rate is detected.
- 0.2 g of the resulting polyimide film is dissolved in 50 ml of DMF (containing 0.05% LiCl) to make a high concentration sample. Because it does not melt well, put it in an oven at 50 °C and shake it for 2 hours while shaking.
- the obtained high concentration samples were diluted to prepare samples of concentrations of 0.0032 g / ml, 0.0024 g / ml, 0.0016 g / ml, and 0.0008 g / ml, respectively. Each sample was measured for refractive index according to the concentration using a 0.45 ⁇ m syringe filter.
- the polyimide film had a Dn / Dc value of 0.1348 ⁇ 0.0010 at 50 ° C. in DMF (containing 0.05% LiCl).
- a film was prepared in the same manner as in Example 13, except that BPDA mole% was changed compared to TFDB when preparing a polyamic acid solution as shown in Table 4 below.
- a film was prepared in the same manner as in Example 13 except that a polyamic acid solution was prepared by thermal curing using an azeotropic dehydrating agent such as toluene without performing a chemical curing using pyridine and acetic anhydride.
- an azeotropic dehydrating agent such as toluene
- Example 14 10 0.1158 ⁇ 0.0006 5.394 ⁇ 10 4 5.865 ⁇ 10 4 7.907 ⁇ 10 4 1.185 ⁇ 10 5 26.5 1.466
- Example 15 20 0.1246 ⁇ 0.0012 8.740 ⁇ 10 4 1.020 ⁇ 10 5 1.085 ⁇ 10 5 1.472 ⁇ 10 5 20.1 1.241
- Example 16 40 0.1284 ⁇ 0.0007 8.458 ⁇ 10 4 9.391 ⁇ 10 4 1.016 ⁇ 10 5 1.425 ⁇ 10 5 21.9 1.202
- Example 17 50 0.1390 ⁇ 0.0002 8.769
- Example 13 Yellow road Average transmittance Example 13 2.05 90.10
- Example 14 1.6522 90.08
- Example 15 3.63 90.08
- Example 16 3.07 90.06
- Example 17 3.40 89.50
- Example 18 3.66 89.00
- the reactor was filled with 587.54 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler. Then 64.064 g (0.2 mol) of TFDB was dissolved to maintain this solution at 25 ° C. 71.08 g (0.16 mol) of 6FDA was added thereto and stirred for 1 hour to completely dissolve 6FDA. At this time, the temperature of the solution was maintained at 25 °C. 11.76 g (0.04 mol) of BPDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.
- DMAc N, N-dimethylacetaamide
- the polyamic acid solution was stirred at room temperature for 3 hours, 31.64 g of pyridine and 40.91 g of acetic anhydride were added and stirred for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool to room temperature, which was then slowly added to a container containing 20 L of methanol. The precipitate was added and precipitated. The precipitated solid was filtered and pulverized and dried in vacuo at 80 ° C. for 6 hours to obtain 120 g of solid powder (81% imidization ratio).
- the obtained solid powder was dissolved in 480 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution (viscosity 70 poise).
- DMAc N, N-dimethylacetamide
- the obtained solution was applied to a stainless plate, then cast at 700 ⁇ m, dried for 1 hour with hot air at 150 ° C., and the film was peeled off from the stainless plate to fix the pin to the frame.
- the film on which the film was fixed was placed in a vacuum oven and slowly heated for 2 hours from 100 ° C to 300 ° C, and then slowly cooled to separate from the frame to obtain a polyimide film. After the heat treatment again at 300 °C 30 minutes as a final heat treatment process to obtain a polyimide film (thickness 100 ⁇ m, imidation rate 99%).
- GPC & MALS Analytical Instruments GPC-Water 1525 Binary HPLC pump; RI detector-Wyatt optilab rEX; MALS-Wyatt Dawn 8+; Column-use Shodex K-803, K-804 and K-805
- 0.05 g of the resulting film is weighed and 10 ml of DMF (containing 0.05% LiCl) is added to the vial.
- the film containing DMF solution is placed in a 50 ° C. oven and dissolved for 2 hours while shaking. After the sample is completely dissolved, filter it using a 0.45 ⁇ m syringe filter and mount it on a MALS autosampler.
- Dn / Dc is a specific refractive index increment
- a polyimide film is injected into a flow cell of a differential refractometer in the form of a lean solution in an organic solvent
- the refractive index value according to the lean solution concentration change rate is detected.
- 0.2 g of the resulting polyimide film is dissolved in 50 ml of DMF (containing 0.05% LiCl) to make a high concentration sample. Because it does not melt well, put it in an oven at 50 °C and shake it for 2 hours while shaking.
- the obtained high concentration samples were diluted to prepare samples of concentrations of 0.0032 g / ml, 0.0024 g / ml, 0.0016 g / ml, and 0.0008 g / ml, respectively. Each sample was measured for refractive index according to the concentration using a 0.45 ⁇ m syringe filter.
- the polyimide film had a Dn / Dc value of 0.1246 ⁇ 0.0012 at 50 ° C. in DMF (containing 0.05% LiCl).
- a film was prepared in the same manner as in Example 19, except that a polyamic acid solution was prepared and stirred for 5 hours, and then pyridine and acetic anhydride were added thereto.
- the Dn / Dc value and the absolute molecular weight value by MALS can be calculated by the same method as Example 19, and the results are shown in Table 6 below.
- a film was prepared in the same manner as in Example 19, except that a polyamic acid solution was prepared, followed by stirring for 12 hours, followed by addition of pyridine and acetic anhydride.
- the Dn / Dc value and the absolute molecular weight value by MALS can be calculated by the same method as Example 19, and the results are shown in Table 6 below.
- a film was prepared in the same manner as in Example 19, except that a polyamic acid solution was prepared and stirred for 24 hours, followed by addition of pyridine and acetic anhydride.
- the Dn / Dc value and the absolute molecular weight value by MALS can be calculated by the same method as Example 19, and the results are shown in Table 6 below.
- the reactor was filled with 587.54 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler. 64.046 g (0.2 mol) of TFDB was then dissolved to maintain this solution at 25 ° C. 11.76 g (0.04 mol) of BPDA was added thereto and stirred for 1 hour to completely dissolve BPDA. At this time, the temperature of the solution was maintained at 25 °C. 71.08 g (0.16 mol) of 6FDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.
- DMAc N, N-dimethylacetaamide
- the polyamic acid solution was stirred at room temperature for 1 hour, and 31.64 g of pyridine and 40.91 g of acetic anhydride were added for 30 minutes, and then stirred at 80 ° C. for 1 hour to cool to room temperature. The precipitate was added and precipitated. The precipitated solid was filtered and pulverized and dried in vacuo at 80 ° C. for 6 hours to obtain 90 g of solid powder (82% imidation ratio).
- the obtained solid powder was dissolved in 360 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution (viscosity 70 poise).
- DMAc N, N-dimethylacetamide
- the obtained solution was applied to a stainless plate, then cast at 700 ⁇ m, dried for 1 hour with hot air at 150 ° C., and the film was peeled off from the stainless plate to fix the pin to the frame.
- the film on which the film was fixed was placed in a vacuum oven and slowly heated for 2 hours from 100 ° C to 300 ° C, and then slowly cooled to separate from the frame to obtain a polyimide film. Thereafter, as a final heat treatment process, heat treatment was again performed at 300 ° C. for 30 minutes (thickness 100 ⁇ m, imidation ratio 95%).
- the Dn / Dc value and the absolute molecular weight value by MALS can be calculated by the same method as Example 19, and the results are shown in Table 6 below.
- a film was prepared in the same manner as in Example 23, except that a polyamic acid solution was prepared, followed by stirring for 12 hours, followed by addition of pyridine and acetic anhydride.
- the Dn / Dc value and the absolute molecular weight value by MALS can be calculated by the same method as Example 19, and the results are shown in Table 6 below.
- a film was prepared in the same manner as in Example 23, except that a polyamic acid solution was prepared and stirred for 24 hours, followed by addition of pyridine and acetic anhydride.
- the Dn / Dc value and the absolute molecular weight value by MALS can be calculated by the same method as Example 19, and the results are shown in Table 6 below.
- Example 19 0.1246 ⁇ 0.0012 1.249 ⁇ 10 4 1.709 ⁇ 10 4 1.845 ⁇ 10 4 4.716 ⁇ 10 4 - 1.478
- Example 20 0.1246 ⁇ 0.0012 2.556 ⁇ 10 4 2.929 ⁇ 10 4 3.290 ⁇ 10 4 3.133 ⁇ 10 5 34.7 1.287
- Example 21 0.1246 ⁇ 0.0012 4.767 ⁇ 10 4 5.785 ⁇ 10 4 5.942 ⁇ 10 4 1.145 ⁇ 10 5 25 1.246
- Example 22 0.1246 ⁇ 0.0012 3.430 ⁇ 10 4 4.524 ⁇ 10 4 4.493 ⁇ 10 4 8.112 ⁇ 10 4 22.6 1.310
- Example 23 0.1246 ⁇ 0.0012 1.803 ⁇ 10 4 2.363 ⁇ 10 4 2.395 ⁇ 10 4 3.161 ⁇
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Abstract
Description
Dn/Dc | Mn(g/mol) | Mp(g/mol) | Mw(g/mol) | Mz(g/mol) | Rz(nm) | Polydispersity | |
실시예 1 | 0.1180 | 5.004×104 | 7.513×104 | 5.655×104 | 6.132×104 | 9.9 | 1.130 |
실시예 2 | 0.1180 | 3.407×104 | 4.446×104 | 4.241×104 | 5.511×104 | 14.6 | 1.245 |
실시예 3 | 0.1180 | 1.138×105 | 1.438×105 | 1.385×105 | 1.810×105 | 24.0 | 1.217 |
실시예 4 | 0.1180 | 7.564×104 | 1.120×105 | 8.727×104 | 9.496×104 | 14.8 | 1.153 |
Dn/Dc | Mn(g/mol) | Mp(g/mol) | Mw(g/mol) | Mz(g/mol) | Rz(nm) | Polydispersity | |
실시예 5 | 0.1216 | 1.454×104 | 1.606×104 | 1.734×104 | 2.052×104 | 1.6 | 1.192 |
실시예 6 | 0.1216 | 2.610×104 | 3.096×104 | 3.128×104 | 4.039×104 | 17.2 | 1.198 |
실시예 7 | 0.1216 | 4.995×104 | 6.967×104 | 6.190×104 | 7.972×104 | 17.3 | 1.213 |
실시예 8 | 0.1216 | 3.711×104 | 4.871×104 | 4.642×104 | 4.642×104 | 21.9 | 1.251 |
실시예 9 | 0.1216 | 3.730×104 | 4.510×104 | 4.552×104 | 5.890×104 | 20.1 | 1.220 |
실시예 10 | 0.1216 | 1.071×105 | 1.334×105 | 1.278×105 | 1.625×105 | 23.6 | 1.193 |
실시예 11 | 0.1216 | 7.743×104 | 1.004×105 | 9.234×104 | 1.396×105 | 20.1 | 1.193 |
실시예 12 | 0.1216 | 3.868×104 | 7.050×104 | 5.877×104 | 8.011×104 | 3.3 | 1.520 |
구분 | 두께(㎛) | 선팽창계수(ppm/℃) | 황색도 | 투과도(%) | 색좌표 | |||||||
400㎚~740㎚ | 550㎚~740㎚ | 550㎚ | 500㎚ | 420㎚ | L | a | b | |||||
실시예 | 5 | 100 | - | 5.12 | 85.3 | 87.5 | 88.6 | 87.9 | 77.1 | 96.11 | -0.95 | 3.03 |
6 | 100 | 53.6 | 3.97 | 87.8 | 90.9 | 90.4 | 89.6 | 80.0 | 96.08 | -0.87 | 2.98 | |
7 | 100 | 48.8 | 2.94 | 87.9 | 90.5 | 90.0 | 89.3 | 82.1 | 95.92 | -0.59 | 2.25 | |
8 | 100 | 44.2 | 2.78 | 87.9 | 90.4 | 89.9 | 89.3 | 82.5 | 95.9 | -0.58 | 2.13 | |
9 | 100 | 52.2 | 4.39 | 87.7 | 90.8 | 90.3 | 89.3 | 79.5 | 96.0 | -0.90 | 3.23 | |
10 | 100 | 47.9 | 2.96 | 88.0 | 90.7 | 90.3 | 89.5 | 82.1 | 96.0 | -0.62 | 2.28 | |
11 | 100 | 51.2 | 2.85 | 88.0 | 90.6 | 90.2 | 89.5 | 82.2 | 96.0 | -0.61 | 2.2 | |
12 | 100 | 54.3 | 3.55 | 87.7 | 90.3 | 90.1 | 89.5 | 80.6 | 96.0 | -0.88 | 2.3 |
TFDB대비BPDA 몰% | Dn/Dc | Mn(g/mol) | Mp(g/mol) | Mw(g/mol) | Mz(g/mol) | Rz(nm) | Polydispersity | |
실시예 13 | 5 | 0.1348± 0.0010 | 5.616×105 | 7.643×104 | 7.557×104 | 1.055×106 | 10.5 | 1.346 |
실시예 14 | 10 | 0.1158± 0.0006 | 5.394×104 | 5.865×104 | 7.907×104 | 1.185×105 | 26.5 | 1.466 |
실시예 15 | 20 | 0.1246± 0.0012 | 8.740×104 | 1.020×105 | 1.085×105 | 1.472×105 | 20.1 | 1.241 |
실시예 16 | 40 | 0.1284± 0.0007 | 8.458×104 | 9.391×104 | 1.016×105 | 1.425×105 | 21.9 | 1.202 |
실시예 17 | 50 | 0.1390± 0.0002 | 8.769×104 | 9.258×104 | 1.037×105 | 1.433×105 | 21.3 | 1.183 |
실시예 18 | 5 | 0.1736± 0.0028 | 9.814×104 | 1.232×105 | 1.255×105 | 1.738×105 | 20.1 | 1.278 |
황색도 | 평균 투과도 | |
실시예 13 | 2.05 | 90.10 |
실시예 14 | 1.6522 | 90.08 |
실시예 15 | 3.63 | 90.08 |
실시예 16 | 3.07 | 90.06 |
실시예 17 | 3.40 | 89.50 |
실시예 18 | 3.66 | 89.00 |
Dn/Dc | Mn(g/mol) | Mp(g/mol) | Mw(g/mol) | Mz(g/mol) | Rz(nm) | Polydispersity | |
실시예 19 | 0.1246± 0.0012 | 1.249×104 | 1.709×104 | 1.845×104 | 4.716×104 | - | 1.478 |
실시예 20 | 0.1246± 0.0012 | 2.556×104 | 2.929×104 | 3.290×104 | 3.133×105 | 34.7 | 1.287 |
실시예 21 | 0.1246± 0.0012 | 4.767×104 | 5.785×104 | 5.942×104 | 1.145×105 | 25 | 1.246 |
실시예 22 | 0.1246± 0.0012 | 3.430×104 | 4.524×104 | 4.493×104 | 8.112×104 | 22.6 | 1.310 |
실시예 23 | 0.1246± 0.0012 | 1.803×104 | 2.363×104 | 2.395×104 | 3.161×104 | 12.9 | 1.328 |
실시예 24 | 0.1246± 0.0012 | 9.427×104 | 1.098×105 | 1.162×105 | 1.575×105 | 25.2 | 1.232 |
실시예 25 | 0.1246± 0.0012 | 7.268×104 | 8.199×104 | 8.805×104 | 1.199×105 | 19.5 | 1.212 |
Claims (30)
- 디아민류와 산 이무수물류를 중합하여 얻어지는 폴리아믹산의 이미드화물로,이미드화율 80 % 이상이며,다음 식 1에 의해 결정되는 절대분자량(Mw)이 40,000 내지 150,000인 폴리이미드 분말.식 1상기 식은 물질이 광(light)과의 상호작용에 따라 전하의 편극화를 일으키고 이에 따라 진동 전하들이 광을 방사상으로 퍼뜨리는 현상에 있어 물질의 편극도(polarizability)에 따라 전하의 이동량 및 광의 방사량이 달라지는 원리를 이용하여, 임의의 고분자 및 용매를 포함하는 용액에 레이저 광을 조사하여 측정되는 산란된 광의 양 및 각 변동(angular variation)으로부터 고분자의 몰 질량(molar mass) 및 크기를 결정하는 원리에 의해 도출되는 것으로,Rθ는 과잉 레일리 비(the excess Rayleigh ratio)이고,K*=4π2n0 2(dn/dc)2λ0 -4NA -1으로, 여기서 n0는 용매의 굴절율, NA는 아보가드로 수(Avogadro's number), dn/dc는 특이적 굴절율 증분으로, 폴리이미드 분말을 유기용매 중의 희박용액 상태로 미분 굴절계(differential refractometer)의 플로우 셀 내에 주입하여 굴절율을 검출하였을 때, 희박용액 농도 변화율에 따른 굴절율의 변화율 값을 미분한 값으로, 농도 변화 구간 0.001 내지 0.1g/㎖ 범위에서 측정한 값이고,c는 용액 중의 고분자 농도(g/㎖)이고,M은 몰 질량(molar mass)으로, 다분산 시료의 경우 중량평균분자량(Mw)이고,A2는 2차 비리얼 계수(the second virial coefficient)이며,P(θ)=Rθ/R0이다.
- 제 1 항에 있어서, 절대분자량(Mw)이 50,000 내지 150,000인 것을 특징으로 하는 폴리이미드 분말.
- 제 1 항에 있어서, 절대 분자량분포도(Polydispersity)가 1.1 내지 1.5인 것을 특징으로 하는 폴리이미드 분말.
- 제 3 항에 있어서, 절대 분자량분포도(Polydispersity)가 1.1 내지 1.3인 것을 특징으로 하는 폴리이미드 분말.
- 제 1 항에 있어서, 산 이무수물류는 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드를 포함하는 것을 특징으로 하는 폴리이미드 분말.
- 제 5 항에 있어서, 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드는 산 이무수물류 중 30몰% 내지 100몰%로 포함되는 것을 특징으로 하는 폴리이미드 분말.
- 제 1 항에 있어서, 디아민류는 2,2′-비스(트리플루오로메틸)-4,4′-디아미노비페닐을 포함하는 것을 특징으로 하는 폴리이미드 분말.
- 제 7 항에 있어서, 2,2′-비스(트리플루오로메틸)-4,4′-디아미노비페닐은 디아민류 중 20몰% 내지 100몰%로 포함되는 것을 특징으로 하는 폴리이미드 분말.
- 제 5 항에 있어서, 폴리아믹산의 이미드화물은 중합시 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드를 산 무수물류 중 먼저 투입하여 얻어지는 폴리아믹산의 이미드화물인 것을 특징으로 하는 폴리이미드 분말.
- 제 5 항에 있어서, 폴리아믹산의 이미드화물은 중합시 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드를 산 무수물류 중 마지막으로 투입하여 얻어지는 폴리아믹산의 이미드화물인 것을 특징으로 하는 폴리이미드 분말.
- 제 1 항에 있어서, 중합은 1 내지 24시간 동안 수행되는 것임을 특징으로 하는 폴리이미드 분말.
- 제 11 항에 있어서, 중합은 8 내지 12시간 동안 수행되는 것임을 특징으로 하는 폴리이미드 분말.
- 유기용매 중에서 디아민류와 산 이무수물류를 중합하여 폴리아믹산 용액을 얻는 공정;폴리아믹산 용액에 화학적 변환제를 투입하여 80% 이상의 이미드화율로 이미드화하여 이미드화물을 포함하는 용액을 제조하는 공정;이미드화물을 포함하는 용액에 메틸 알코올, 에틸 알코올, 이소프로필 알코올, 에틸렌 글리콜, 트리에틸렌 글리콜, 2-부틸 알코올, 2-프로필 알코올, 2-헥실 알코올, 사이클로펜틸 알코올, 사이클로헥실 알코올, 페놀 및 t-부틸 알코올 중에서 선택되는 용매를 첨가하여 침전시키는 공정; 및침전된 고형분을 여과하는 공정을 포함하며,이미드화율 80 % 이상이며, 다음 식 1에 의해 결정되는 절대분자량(Mw)이 40,000 내지 150,000인 폴리이미드 분말의 제조방법.식 1상기 식은 물질이 광(light)과의 상호작용에 따라 전하의 편극화를 일으키고 이에 따라 진동 전하들이 광을 방사상으로 퍼뜨리는 현상에 있어 물질의 편극도(polarizability)에 따라 전하의 이동량 및 광의 방사량이 달라지는 원리를 이용하여, 임의의 고분자 및 용매를 포함하는 용액에 레이저 광을 조사하여 측정되는 산란된 광의 양 및 각 변동(angular variation)으로부터 고분자의 몰 질량(molar mass) 및 크기를 결정하는 원리에 의해 도출되는 것으로,Rθ는 과잉 레일리 비(the excess Rayleigh ratio)이고,K*=4π2n0 2(dn/dc)2λ0 -4NA -1으로, 여기서 n0는 용매의 굴절율, NA는 아보가드로 수(Avogadro's number), dn/dc는 특이적 굴절율 증분으로, 폴리이미드 분말을 유기용매 중의 희박용액 상태로 미분 굴절계(differential refractometer)의 플로우 셀 내에 주입하여 굴절율을 검출하였을 때, 희박용액 농도 변화율에 따른 굴절율의 변화율 값을 미분한 값으로, 농도 변화 구간 0.001 내지 0.1g/㎖ 범위에서 측정한 값이고,c는 용액 중의 고분자 농도(g/㎖)이고,M은 몰 질량(molar mass)으로, 다분산 시료의 경우 중량평균분자량(Mw)이고,A2는 2차 비리얼 계수(the second virial coefficient)이며,P(θ)=Rθ/R0이다.
- 디아민류와 산 이무수물류를 중합하여 얻어지는 폴리아믹산의 이미드화물을 제막하여 얻어지고,다음 식 1에 의해 결정되는 절대분자량(Mw)이 30,000 내지 170,000인 폴리이미드 필름.식 1상기 식은 물질이 광(light)과의 상호작용에 따라 전하의 편극화를 일으키고 이에 따라 진동 전하들이 광을 방사상으로 퍼뜨리는 현상에 있어 물질의 편극도(polarizability)에 따라 전하의 이동량 및 광의 방사량이 달라지는 원리를 이용하여, 임의의 고분자 및 용매를 포함하는 용액에 레이저 광을 조사하여 측정되는 산란된 광의 양 및 각 변동(angular variation)으로부터 고분자의 몰 질량(molar mass) 및 크기를 결정하는 원리에 의해 도출되는 것으로,Rθ는 과잉 레일리 비(the excess Rayleigh ratio)이고,K*=4π2n0 2(dn/dc)2λ0 -4NA -1으로, 여기서 n0는 용매의 굴절율, NA는 아보가드로 수(Avogadro's number), dn/dc는 특이적 굴절율 증분으로, 폴리이미드 필름을 유기용매 중의 희박용액 상태로 미분 굴절계(differential refractometer)의 플로우 셀 내에 주입하여 굴절율을 검출하였을 때, 희박용액 농도 변화율에 따른 굴절율의 변화율 값을 미분한 값으로, 농도 변화 구간 0.001 내지 0.1g/㎖ 범위에서 측정한 값이고,c는 용액 중의 고분자 농도(g/㎖)이고,M은 몰 질량(molar mass)으로, 다분산 시료의 경우 중량평균분자량(Mw)이고,A2는 2차 비리얼 계수(the second virial coefficient)이며,P(θ)=Rθ/R0이다.
- 제 14 항에 있어서, 이미드화율이 95% 이상인 것을 특징으로 하는 폴리이미드 필름.
- 제 14 항에 있어서, 절대분자량(Mw)이 50,000 내지 150,000인 것을 특징으로 하는 폴리이미드 필름.
- 제 14 항에 있어서, 절대 분자량분포도(Polydispersity)가 1.1 내지 1.6인 것을 특징으로 하는 폴리이미드 필름.
- 제 17 항에 있어서, 절대 분자량분포도(Polydispersity)가 1.1 내지 1.3인 것을 특징으로 하는 폴리이미드 필름.
- 제 14 항에 있어서, 산 이무수물류는 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드를 포함하는 것을 특징으로 하는 폴리이미드 필름.
- 제 19 항에 있어서, 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드는 산 이무수물류 중 30몰% 내지 100몰%로 포함되는 것을 특징으로 하는 폴리이미드 필름
- 제 14 항에 있어서, 디아민류는 2,2′-비스(트리플루오로메틸)-4,4′-디아미노비페닐을 포함하는 것을 특징으로 하는 폴리이미드 필름.
- 제 21 항에 있어서, 2,2′-비스(트리플루오로메틸)-4,4′--아미노비페닐은 디아민류 중 20몰% 내지 100몰%로 포함되는 것을 특징으로 하는 폴리이미드 필름.
- 제 19 항에 있어서, 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드를 산 무수물류 중 먼저 투입하여 얻어지는 폴리아믹산의 이미드화물로부터 얻어지는 것을 특징으로 하는 폴리이미드 필름.
- 제 19 항에 있어서, 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드를 산 무수물류 중 마지막으로 투입하여 얻어지는 폴리아믹산의 이미드화물로부터 얻어지는 것을 특징으로 하는 폴리이미드 필름.
- 제 14 항에 있어서, 중합은 1 내지 24시간 동안 수행되는 것임을 특징으로 하는 폴리이미드 필름.
- 제 25 항에 있어서, 중합은 8 내지 12시간 동안 수행되는 것임을 특징으로 하는 폴리이미드 필름.
- 제 14 항에 있어서, 필름 두께 50~100㎛를 기준으로 황색도가 4.5 이하인 것인 폴리이미드 필름.
- 제 14 항에 있어서, 필름 두께 50~100㎛를 기준으로 열기계분석법에 의해 50 내지 250℃ 범위에서 측정한 평균 선팽창계수(CTE)가 70 ppm/℃이하인 것을 특징으로 하는 폴리이미드 필름.
- 유기용매 중에서 디아민류와 산 이무수물류를 중합하여 폴리아믹산 용액을 얻는 공정;폴리아믹산 용액에 화학적 변환제를 투입하여 80% 이상의 이미드화율로 이미드화하여 이미드화물을 포함하는 용액을 제조하는 공정;이미드화물을 포함하는 용액에 메틸 알코올, 에틸 알코올, 이소프로필 알코올, 에틸렌 글리콜, 트리에틸렌 글리콜, 2-부틸 알코올, 2-프로필 알코올, 2-헥실 알코올, 사이클로펜틸 알코올, 사이클로헥실 알코올, 페놀 및 t-부틸 알코올 중에서 선택되는 용매를 첨가하여 침전시키는 공정;침전된 고형분을 여과하는 공정;여과물을 건조하여 폴리이미드 분말을 얻는 공정;폴리이미드 분말을 유기용매에 용해하는 공정;폴리이미드 용액을 제막하는 공정; 및100 내지 500℃에서 열처리하는 공정을 포함하며,다음 식 1에 의해 결정되는 절대분자량(Mw)이 30,000 내지 170,000인 폴리이미드 필름의 제조방법.식 1상기 식은 물질이 광(light)과의 상호작용에 따라 전하의 편극화를 일으키고 이에 따라 진동 전하들이 광을 방사상으로 퍼뜨리는 현상에 있어 물질의 편극도(polarizability)에 따라 전하의 이동량 및 광의 방사량이 달라지는 원리를 이용하여, 임의의 고분자 및 용매를 포함하는 용액에 레이저 광을 조사하여 측정되는 산란된 광의 양 및 각 변동(angular variation)으로부터 고분자의 몰 질량(molar mass) 및 크기를 결정하는 원리에 의해 도출되는 것으로,Rθ는 과잉 레일리 비(the excess Rayleigh ratio)이고,K*=4π2n0 2(dn/dc)2λ0 -4NA -1으로, 여기서 n0는 용매의 굴절율, NA는 아보가드로 수(Avogadro's number), dn/dc는 특이적 굴절율 증분으로, 폴리이미드 필름을 유기용매 중의 희박용액 상태로 미분 굴절계(differential refractometer)의 플로우 셀 내에 주입하여 굴절율을 검출하였을 때, 희박용액 농도 변화율에 따른 굴절율의 변화율 값을 미분한 값으로, 농도 변화 구간 0.001 내지 0.1g/㎖ 범위에서 측정한 값이고,c는 용액 중의 고분자 농도(g/㎖)이고,M은 몰 질량(molar mass)으로, 다분산 시료의 경우 중량평균분자량(Mw)이고,A2는 2차 비리얼 계수(the second virial coefficient)이며,P(θ)=Rθ/R0이다.
- 제 29 항에 있어서, 화학적 변환제는 탈수제 및 촉매를 포함하는 것을 특징으로 하는 폴리이미드 필름의 제조방법.
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KR20080055531A (ko) * | 2006-12-15 | 2008-06-19 | 주식회사 코오롱 | 무색투명한 폴리이미드 필름 |
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