WO2022114136A1 - ポリイミド前駆体組成物、ポリイミドフィルム、およびポリイミドフィルム/基材積層体 - Google Patents
ポリイミド前駆体組成物、ポリイミドフィルム、およびポリイミドフィルム/基材積層体 Download PDFInfo
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- WO2022114136A1 WO2022114136A1 PCT/JP2021/043417 JP2021043417W WO2022114136A1 WO 2022114136 A1 WO2022114136 A1 WO 2022114136A1 JP 2021043417 W JP2021043417 W JP 2021043417W WO 2022114136 A1 WO2022114136 A1 WO 2022114136A1
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- WIPO (PCT)
- Prior art keywords
- polyimide
- polyimide precursor
- film
- precursor composition
- polyimide film
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 306
- 239000004642 Polyimide Substances 0.000 title claims abstract description 183
- 239000002243 precursor Substances 0.000 title claims abstract description 163
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 239000000758 substrate Substances 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims description 63
- 239000000463 material Substances 0.000 claims description 57
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 239000011521 glass Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000004065 semiconductor Substances 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 20
- 239000004020 conductor Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 230000004580 weight loss Effects 0.000 claims description 9
- 238000002834 transmittance Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- -1 imidazole compound Chemical class 0.000 description 94
- 150000004985 diamines Chemical class 0.000 description 69
- 239000010408 film Substances 0.000 description 59
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 58
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 55
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000002585 base Substances 0.000 description 35
- 229920005575 poly(amic acid) Polymers 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 19
- 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 16
- 125000002723 alicyclic group Chemical group 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
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- 239000000126 substance Substances 0.000 description 11
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 7
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- 238000003756 stirring Methods 0.000 description 7
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
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- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- UIZIZIPEEWDBCL-UHFFFAOYSA-N (4-aminophenyl) 4-[4-(4-aminophenoxy)carbonylphenyl]benzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(C=2C=CC(=CC=2)C(=O)OC=2C=CC(N)=CC=2)C=C1 UIZIZIPEEWDBCL-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
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- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 2
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 2
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 2
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- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 2
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CZRKJHRIILZWRC-UHFFFAOYSA-N methyl acetate;propane-1,2-diol Chemical compound COC(C)=O.CC(O)CO CZRKJHRIILZWRC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a polyimide precursor composition suitably used for electronic device applications such as substrates for flexible devices, a polyimide film having various improved properties, and a polyimide film / base material laminate.
- the present invention relates to a method for manufacturing a flexible electronic device using the composition.
- Polyimide film has been widely used in fields such as electrical / electronic device fields and semiconductor fields because it has excellent heat resistance, chemical resistance, mechanical strength, electrical characteristics, and dimensional stability.
- optical materials such as optical fibers and optical waveguides in the optical communication field, liquid crystal alignment films in the display device field, and protective films for color filters has been progressing.
- a lightweight and highly flexible plastic substrate is being studied as an alternative to a glass substrate, and a display that can be bent or rolled is being actively developed.
- polyimide Since polyimide is generally colored yellowish brown, its use in transmissive devices such as liquid crystal displays equipped with a backlight has been restricted, but in recent years, in addition to mechanical and thermal properties, it has been restricted. A polyimide film having excellent transparency has been developed, and expectations are further increasing as a substrate for display applications (see Patent Documents 1 to 3).
- Patent Document 4 describes, "A step of applying a specific precursor resin composition on a carrier substrate to form a solid polyimide resin film, a step of forming a circuit on the resin film, and the circuit.
- a method for manufacturing a flexible device, which is a display device or a light receiving device, including each step of peeling a solid resin film formed on the surface of the carrier substrate from the carrier substrate is described.
- Patent Document 5 as a method for manufacturing a flexible device, elements and circuits necessary for the device are formed on a polyimide film / glass base material laminate obtained by forming a polyimide film on a glass substrate. Later, a method including irradiating a laser from the glass substrate side to peel off the glass substrate is disclosed.
- Patent Document 6 contains a polyimide precursor composition and an imidazole compound containing a repeating unit derived from a compound in which one of the tetracarboxylic acid component and the diamine component has an alicyclic structure and the other has an aromatic ring. It is disclosed that a polyimide precursor composition and a polyimide film / glass base material laminate are produced using the polyimide precursor composition.
- the polyimide film obtained by the invention of Patent Document 6 has a small retardation in the thickness direction, is excellent in mechanical properties, and is also excellent in transparency.
- Patent Document 7 describes a polyimide precursor obtained from a tetracarboxylic acid and a specific diamine compound and having an imidization ratio of 30 mol% or more and 90 mol% or less (see claim 1).
- a polyimide film is produced using this polyimide precursor, an advantageous effect that the coefficient of linear thermal expansion can be lowered can be obtained without the stretching operation often performed in the production of a poly film.
- Patent Document 7 enables the production of a polyimide film having excellent properties, but various properties such as thermal properties, heat resistance, mechanical properties and transparency are further improved in a well-balanced manner. Is desirable.
- the present invention has been made in view of conventional problems, and a main object thereof is a polyimide precursor capable of producing a polyimide film having excellent thermal properties and / or heat resistance and also excellent transparency. Is to provide the composition. Further, an object of one aspect of the present invention is to provide a polyimide film obtained by using the polyimide precursor composition and a polyimide film / base material laminate, and further, an object of another aspect of the present invention is. , A method for manufacturing a flexible electronic device using the polyimide precursor composition, and a flexible electronic device.
- the repeating unit comprises a repeating unit represented by the following general formula (I) and a repeating unit further imidized by the general formula (I), and the imidization ratio is more than 0% and less than 50%.
- a polyimide precursor composition comprising a solvent.
- X 1 is a tetravalent aliphatic group or an aromatic group
- Y 1 is a divalent aliphatic group or an aromatic group
- R 1 and R 2 are independent of each other and hydrogen.
- Y1 is the formula (D- 1 ) and / or (D-2) :.
- Item 2 The polyimide precursor composition according to Item 1, wherein the polyimide film obtained from this polyimide precursor composition has a light transmittance of 79% or more at a wavelength of 400 nm in a film having a thickness of 10 ⁇ m.
- polyimide film obtained from this polyimide precursor composition is a film having a thickness of 10 ⁇ m and has a linear thermal expansion coefficient of 20 ppm / K or less between 150 ° C. and 250 ° C.
- Item 2 The polyimide precursor according to any one of Items 1 to 4, wherein the polyimide film obtained from this polyimide precursor composition has a breaking elongation of 10% or more in a film having a thickness of 10 ⁇ m. Composition.
- Item 2 The laminate according to Item 8, wherein the base material is a glass substrate.
- Item 2 The manufacturing method according to Item 10, wherein the base material is a glass substrate.
- B A step of heat-treating the polyimide precursor on the base material to produce a polyimide film / base material laminate in which the polyimide film is laminated on the base material.
- C Flexible electrons having a step of forming at least one layer selected from a conductor layer and a semiconductor layer on the polyimide film of the laminated body, and (d) a step of peeling the base material and the polyimide film. How to make the device.
- Item 12 The manufacturing method according to Item 12, wherein the base material is a glass substrate.
- a polyimide precursor capable of producing a polyimide film having excellent thermal properties (low linear thermal expansion coefficient, etc.) and / or heat resistance (5% weight loss temperature, etc.) and excellent transparency.
- the composition can be provided.
- it is transparent with at least one property of (i) thermal properties such as a low coefficient of linear thermal expansion and (ii) heat resistance such as a 5% weight loss temperature. It also has the effect that it is possible to produce an excellent polyimide film.
- a polyimide film obtained by using the polyimide precursor composition and a polyimide film / base material laminate it is possible to provide a method for manufacturing a flexible electronic device using the polyimide precursor composition and a flexible electronic device.
- “flexible (electronic) device” means that the device itself is flexible, and a semiconductor layer (transistor, diode, etc. as an element) is usually formed on a substrate to complete the device.
- the “flexible (electronic) device” is distinguished from a device such as a COF (Chip On Film) in which a "hard” semiconductor element such as an IC chip is mounted on a conventional FPC (flexible printed wiring board).
- a “hard” semiconductor element such as an IC chip may be mounted on a flexible substrate or electrically connected to be fused and used. There is nothing wrong with doing it.
- Flexible (electronic) devices that are preferably used include liquid crystal displays, organic EL displays, display devices such as electronic paper, solar cells, and light receiving devices such as CMOS.
- the polyimide precursor composition of the present invention will be described below, and then a method for manufacturing a flexible electronic device will be described.
- the polyimide precursor composition for forming the polyimide film contains a polyimide precursor and a solvent. The polyimide precursor is dissolved in the solvent.
- the polyimide precursor contains a repeating unit represented by the following general formula (I) and a repeating unit in which the general formula (I) is further imidized.
- X 1 is a tetravalent aliphatic group or an aromatic group
- Y 1 is a divalent aliphatic group or an aromatic group
- R 1 and R 2 are independent of each other and hydrogen.
- Atom an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms.
- the repeating unit in which the general formula (I) is further imidized is a structure in which one or two of the two amide bonds present in the general formula (I) are converted into an imide bond, and specifically, the following General formulas (Ib), (Ic) and (II):
- the imidization rate is the rate at which the amide bond in the general formula (I) is converted into an imide bond. Therefore, if all of the repeating units in the polyimide precursor are of the general formula (I), the imidization rate is 0%, and if all of the repeating units are of the general formula (Ib) and / or (Ic), the imidization rate is 0%.
- the imidization rate is 50%, and if all the repeating units are of the general formula (II), the imidization rate is 100% (that is, polyimide).
- the imidization ratio of more than 0% and less than 50% means that one or more of the general formulas (Ib), (Ic) and (II) are predetermined in addition to the structure of the general formula (I). It means that it exists so as to have an imidization ratio.
- the 1 H-NMR spectrum of the polyimide precursor (solution) was measured, and the integral value of the aromatic proton peak (7 to 8.3 ppm) and the amide proton peak (9.5 to 10.5 ppm) were measured. ) Can be calculated from the ratio of the integrated values.
- the polyimide precursor having an adjusted imidization ratio is a precursor having a repeating unit represented by the general formula (I) at the time of reaction between the tetracarboxylic acid component and the diamine component, or from the tetracarboxylic acid component and the diamine component. After that, it can be produced by a production method including a step of reacting for an appropriate time so as to obtain a desired imidization ratio under appropriate conditions under which the imidization reaction proceeds.
- the target imide is obtained during the reaction between the tetracarboxylic acid component and the diamine component, or after obtaining a precursor having a repeating unit represented by the general formula (I) from the tetracarboxylic acid component and the diamine component.
- the reaction is carried out at an appropriate temperature for an appropriate time so that imidization proceeds to the conversion rate.
- the temperature range is, for example, 0 ° C. or higher, preferably 15 ° C. or higher, for example, 180 ° C. or lower, preferably 150 ° C. or lower, and more preferably 130 ° C. or lower.
- the imidization rate can be adjusted in a short time as the temperature is high and in a long time as the temperature is low. It is preferable to do so. Further, it is preferable to change the reaction temperature and the reaction time depending on the presence / absence of addition of the imidazole compound described later, the type thereof, and the amount thereof.
- the one-step feeding method is preferably carried out by thermal imidization and preferably does not contain a dehydrating agent for chemical imidization.
- the tetracarboxylic acid component and the diamine component are divided and supplied to a plurality of steps, and the imidization rate is adjusted by a method in which the reaction is carried out under different conditions in the plurality of steps.
- the first step includes high-temperature heating in which only a part of the tetracarboxylic acid component and a part of the diamine component are supplied and the imidization reaction proceeds rapidly, and as a result,
- the high temperature heating condition of the first step is preferably 100 ° C. or higher, more preferably 120 ° C.
- the temperature condition of the second step is less than 100 ° C., more preferably less than 90 ° C. It is usually 0 ° C. or higher, preferably 15 ° C. or higher.
- the imidization rate can be adjusted by the distribution ratio of the tetracarboxylic acid component and the diamine component in the first step and the second step. This method is also preferably carried out by thermal imidization and preferably does not contain a dehydrating agent for chemical imidization.
- the precursor represented by the general formula (I) is particularly preferably a polyamic acid in which R 1 and R 2 are hydrogen atoms.
- R 1 and R 2 are hydrogen atoms.
- the aliphatic group is preferably a group having an alicyclic structure.
- X 1 preferably contains 70 mol% or more of the structure represented by the following formula (1-1), that is, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '. -Spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid dianhydride (hereinafter, abbreviated as CpODA if necessary).
- Y1 preferably has a structure represented by the following formulas (D- 1 ) and / or (D-2) in an amount of 70 mol% or more, that is, 4,4'-. It is a structure derived from diaminobenzanilide (abbreviated as DABAN if necessary).
- composition containing such a polyimide precursor By using a composition containing such a polyimide precursor, it is possible to produce a polyimide film having excellent thermal properties such as a low coefficient of linear thermal expansion and also having excellent transparency.
- the polyimide precursor will be described by the monomers giving X 1 and Y 1 in the general formula (I) (tetracarboxylic acid component, diamine component, and other components), followed by a description of the production method.
- the tetracarboxylic acid component is tetracarboxylic acid, tetracarboxylic acid dianhydride, other tetracarboxylic acid silyl ester, tetracarboxylic acid ester, tetracarboxylic acid chloride and the like used as raw materials for producing polyimide.
- tetracarboxylic acid dianhydride it is convenient to use tetracarboxylic acid dianhydride in production, and the following description describes an example in which tetracarboxylic acid dianhydride is used as the tetracarboxylic acid component.
- the diamine component is a diamine compound having two amino groups (-NH 2 ), which is used as a raw material for producing polyimide.
- the polyimide film means both a film formed on a (carrier) base material and existing in a laminate, and a film after the base material is peeled off.
- the material constituting the polyimide film that is, the material obtained by heat-treating (imidizing) the polyimide precursor composition may be referred to as "polyimide material”.
- X 1 preferably has a structure represented by the formula (1-1) in an amount of 70 mol% or more, more preferably 80 mol% or more, still more preferably.
- the structure represented by the formula (1-1) is 90 mol% or more, most preferably 95 mol% or more (100 mol% is also very preferable).
- the tetracarboxylic acid dianhydride that gives the structure of formula (1-1) as X 1 is CpODA.
- CpODA may be a mixture of stereoisomers or a specific stereoisomer.
- preferred stereoisomers include trans-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2 "-norbornane-5,5", 6,6 "-.
- Tetracarboxylic acid dianhydride (CpODA-tee) and cis-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2 "-norbornane-5,5", 6,6 "- Tetracarboxylic acid dianhydride (CpODA-cee) can be mentioned.
- CpODA-tee is at least 50 mol% or more, and even more preferably 63 mol% or more in CpODA. In one preferred different embodiment, at least 30 mol% or more, and even more preferably 37 mol% or more, of CpODA is CpODA-cee. In one preferred further different embodiment, the total of CpODA-tee and CpODA-cee in CpODA is at least 80 mol% or more, and even more preferably 83 mol% or more.
- X 1 a tetravalent aliphatic group or aromatic group (abbreviated as “other X 1 ”) other than the structure represented by the formula (1-1) does not impair the effect of the present invention. It can be contained in a range of amounts. That is, the tetracarboxylic acid component can contain other tetracarboxylic acid derivatives in addition to CpODA in an amount within a range that does not impair the effects of the present invention.
- the amount of the other tetracarboxylic acid derivative is less than 30 mol%, more preferably less than 20 mol%, still more preferably less than 10 mol% (preferably 0 mol%) with respect to 100 mol% of the tetracarboxylic acid component. be.
- Examples of the tetravalent group having an aromatic ring include the following.
- Z 1 is a direct bond, or the following divalent group:
- Z 2 in the formula is a divalent organic group
- Z 3 and Z 4 are independently amide bonds, ester bonds and carbonyl bonds, respectively
- Z 5 is an organic group containing an aromatic ring.
- Z 2 include an aliphatic hydrocarbon group having 2 to 24 carbon atoms and an aromatic hydrocarbon group having 6 to 24 carbon atoms.
- Z 5 include aromatic hydrocarbon groups having 6 to 24 carbon atoms.
- the tetravalent group having an aromatic ring is particularly preferable because it can achieve both high heat resistance and high transparency of the obtained polyimide film.
- Z 1 is a direct bond or a hexafluoroisopropyrine bond.
- Z 1 is a direct bond because it can achieve both high heat resistance, high transparency, and a low coefficient of linear thermal expansion of the obtained polyimide film.
- Z 1 is the following formula (3A):
- Z 11 and Z 12 are independent, preferably identical, single-bonded or divalent organic groups, respectively.
- Z 11 and Z 12 organic groups containing an aromatic ring are preferable, and for example, the formula (3A1)::
- Z 13 and Z 14 are single bonds independently of each other, -COO-, -OCO- or -O-, where if Z 14 is attached to a fluorenyl group, then Z 13 is -COO-, -OCO-.
- a structure in which Z 14 is a single bond in —O— is preferable;
- R 91 is an alkyl group or a phenyl group having 1 to 4 carbon atoms, preferably methyl, and n is an integer of 0 to 4, preferably. It is 1.
- the structure represented by is preferable.
- Examples of the tetracarboxylic acid component that gives the repeating unit of the general formula (I) in which X 1 is a tetravalent group having an aromatic ring include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane.
- Examples of the tetracarboxylic acid component that gives the repeating unit of the general formula (I) in which X 1 is a tetravalent group having an aromatic ring containing a fluorine atom include 2,2-bis (3,4-dicarboxy). Examples thereof include phenyl) hexafluoropropane and derivatives thereof such as tetracarboxylic acid dianhydride, tetracarboxylic acid silyl ester, tetracarboxylic acid ester and tetracarboxylic acid chloride.
- (9H-fluorene-9,9-diyl) bis (2-methyl-4,1-phenylene) bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) can be mentioned.
- the tetracarboxylic acid component may be used alone or in combination of two or more.
- X 1 is a tetravalent group having an alicyclic structure
- a tetravalent group having an alicyclic structure having 4 to 40 carbon atoms is preferable, and at least one aliphatic 4- to 12-membered ring, It is more preferable to have an aliphatic 4-membered ring or an aliphatic 6-membered ring.
- Examples of the tetravalent group having a preferable aliphatic 4-membered ring or aliphatic 6-membered ring include the following.
- R 31 to R 38 are independently directly bonded or divalent organic groups.
- R 41 to R 47 and R 71 to R 73 are independently formulas: -CH 2-- , respectively.
- -CH CH-, -CH 2 CH 2- , -O-, -S- represents one selected from the group consisting of groups.
- R 48 is an organic containing an aromatic ring or an alicyclic structure. Is the basis.
- R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , and R 38 include a direct bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples thereof include an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl bond, an ester bond, and an amide bond.
- Examples of the organic group containing an aromatic ring as R 48 include the following.
- W 1 is a directly bonded or divalent organic group
- n 11 to n 13 each independently represent an integer of 0 to 4
- R 51 , R 52 , and R 53 are independent of each other. It is an alkyl group, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group having 1 to 6 carbon atoms.
- W 1 examples include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).
- R 61 to R 68 in the formula (6) each independently represent either a direct bond or a divalent group represented by the above formula (5)).
- the following ones are particularly preferable because they can achieve both high heat resistance, high transparency, and a low coefficient of linear thermal expansion of the obtained polyimide.
- Examples of the tetracarboxylic acid component that gives the repeating unit of the formula (I) in which X 1 is a tetravalent group having an alicyclic structure include 1,2,3,4-cyclobutanetetracarboxylic acid and isopropyridene diphenoxybis.
- Y1 preferably has a structure represented by the formulas (D- 1 ) and / or (D-2) in an amount of 70 mol% or more, more preferably 80. More than mol%, even more preferably 90 mol% or more (preferably 100 mol%) is the structure represented by the formulas (D-1) and / or (D-2).
- the diamine compound giving the structure of the formula (D-1) and the formula (D-2) as Y 1 is 4,4'-diaminobenzanilide (abbreviation: DABAN).
- Y 1 a divalent aliphatic group or aromatic group (abbreviated as “other Y 1 ”) other than the structures represented by the formulas (D-1) and (D-2) is referred to as the present invention. It can be contained in an amount within a range that does not impair the effects of the invention. That is, the diamine component can contain other diamine compounds in addition to DABAN in an amount within a range that does not impair the effects of the present invention.
- the amount of the other diamine compound is less than 30 mol%, more preferably less than 20 mol%, still more preferably less than 10 mol% (preferably 0 mol%) with respect to 100 mol% of the diamine component.
- Y 1 is a divalent group having an aromatic ring
- a divalent group having an aromatic ring having 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms is preferable.
- Examples of the divalent group having an aromatic ring include the following.
- W 1 is a directly bonded or divalent organic group
- n 11 to n 13 each independently represent an integer of 0 to 4
- R 51 , R 52 , and R 53 are independent of each other. It is an alkyl group, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group having 1 to 6 carbon atoms.
- W 1 examples include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).
- R 61 to R 68 in the formula (6) represent either a direct bond independently or a divalent group represented by the formula (5).
- W 1 can be directly bonded, or the formulas: -NHCO-, -CONH-, -COO-, -OCO-. It is particularly preferable that it is one selected from the group consisting of the groups represented by. Further, W 1 is one selected from the group consisting of groups in which R 61 to R 68 are directly bonded or represented by the formulas: -NHCO-, -CONH-, -COO-, -OCO-. It is also particularly preferable that it is one of the divalent groups represented by the formula (6). However, when -NHCO- or -CONH- is selected, "other Y1" is selected so as to be different from the formula (D-1) or the formula (D-2).
- W 1 is the following formula (3B):
- Z 11 and Z 12 are independent, preferably identical, single-bonded or divalent organic groups, respectively.
- Z 11 and Z 12 organic groups containing an aromatic ring are preferable, and for example, the formula (3B1)::
- Z 13 and Z 14 are single bonds independently of each other, -COO-, -OCO- or -O-, where if Z 14 is attached to a fluorenyl group, then Z 13 is -COO-, -OCO-.
- a structure in which Z 14 is a single bond in —O— is preferable;
- R 91 is an alkyl group or a phenyl group having 1 to 4 carbon atoms, preferably phenyl, and n is an integer of 0 to 4, preferably. It is 1.
- the structure represented by is preferable.
- a compound in which W 1 is a phenylene group, that is, a terphenyldiamine compound can be mentioned, and a compound having all parabonds is particularly preferable.
- Another preferred group is a compound in which W 1 is the first phenyl ring of the formula (6) and R 61 and R 62 are 2,2-propyridene groups in the above formula (4).
- W 1 is the following formula (3B2):
- Examples thereof include compounds represented by.
- Examples of the diamine component that gives the repeating unit of the general formula (I) in which Y 1 is a divalent group having an aromatic ring include p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-.
- Biphenyl 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, m-tridin, 3,4'-diaminobenzanilide, N, N'-bis (4- Aminophenyl) terephthalamide, N, N'-p-phenylenebis (p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4,4'-dicarboxylic acid Bis (4-aminophenyl) ester, p-phenylene bis (p-aminobenzoate), bis (4-aminophenyl)-[1,1'-biphenyl] -4,4'-dicarboxylate, [1,1 '-Biphenyl] -4,4'-diylbis (4-aminobenzoate), 4,4'-oxydianiline, 3,4'-
- Examples of the diamine component that gives the repeating unit of the general formula (I) in which Y 1 is a divalent group having an aromatic ring containing a fluorine atom include 2,2'-bis (trifluoromethyl) benzidine, 3 , 3'-bis (trifluoromethyl) benzidine, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2 '-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane can be mentioned.
- preferred diamine compounds include 9,9-bis (4-aminophenyl) fluorene and 4,4'-(((9H-fluoren-9,9-diyl) bis ([1,1'-biphenyl] -5). , 2-diyl)) bis (oxy)) diamine, [1,1': 4', 1 "-terphenyl] -4,4" -diamine, 4,4'-([1,1'-binaphthalene] -2,2'-Diylbis (oxy) diamine can be mentioned.
- the diamine component may be used alone or in combination of two or more.
- Y 1 is a divalent group having an alicyclic structure
- a divalent group having an alicyclic structure having 4 to 40 carbon atoms is preferable, and at least one aliphatic 4- to 12-membered ring, It is more preferable to have an aliphatic 6-membered ring.
- divalent group having an alicyclic structure examples include the following.
- V 1 and V 2 are independently directly bonded or divalent organic groups, and n 21 to n 26 each independently represent an integer of 0 to 4, and R 81 to R 86 .
- R 91 , R 92 , and R 93 are independently represented by the formulas: -CH 2- , respectively.
- -CH CH-, -CH 2 CH 2- , -O-, -S- is one selected from the group consisting of groups represented by.
- V 1 and V 2 include a direct bond and a divalent group represented by the above formula (5).
- the divalent group having an alicyclic structure the following are particularly preferable because both the high heat resistance of the obtained polyimide and the low coefficient of linear thermal expansion can be achieved.
- the divalent group having an alicyclic structure the following are preferable.
- Examples of the diamine component that gives the repeating unit of the general formula (I) in which Y 1 is a divalent group having an alicyclic structure include 1,4-diaminocyclohexane and 1,4-diamino-2-methylcyclohexane.
- 1,4-Diamino-2-ethylcyclohexane 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1, , 4-Diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diamino Cyclobutane, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane, di
- any of aliphatic tetracarboxylic acids (particularly dianhydride) and / or aliphatic diamines other than the alicyclic type are used.
- the content thereof is preferably less than 30 mol%, more preferably less than 20 mol%, still more preferably less than 10 mol%, based on 100 mol% of the total of the tetracarboxylic acid component and the diamine component. (Including 0%) is preferable.
- Y 1 the structure represented by the formula (4), specific compounds include p-phenylenediamine, 3,3'-bis (trifluoromethyl) benzidine, m-trizine, 4,4'. -By containing a diamine compound such as bis (4-aminophenoxy) biphenyl, the transparency of the obtained polyimide film may be improved.
- a diamine compound such as 9,9-bis (4-aminophenyl) fluorene is contained to obtain Tg. It may be possible to improve or reduce the retardation in the film thickness direction.
- the polyimide precursor can be produced from the above-mentioned tetracarboxylic acid component and diamine component.
- the polyimide precursor used in the present invention (a polyimide precursor containing at least one of the repeating units represented by the above formula (I)) has a chemical structure taken by R1 and R2 .
- the polyimide precursor can be easily produced by the following production methods for each of these categories. However, the method for producing the polyimide precursor used in the present invention is not limited to the following production method.
- the repeating unit represented by the formula (I) is a polyamic acid
- a one-step feeding method in which the imidization reaction proceeds evenly (or randomly) in the molecule, and a tetracarboxylic acid component and a diamine are used.
- Either a multi-stage feeding method in which each of the components is divided and supplied and the imidization reaction proceeds only between a part of the tetracarboxylic acid component and a part of the diamine component (or in a block manner) can be adopted.
- the tetracarboxylic acid dianhydride as the tetracarboxylic acid component and the diamine component are approximately equimolar, preferably the molar ratio of the diamine component to the tetracarboxylic acid component [the number of moles of the diamine component / the number of moles of the tetracarboxylic acid component]. ] Is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, and reacts at a relatively low temperature of, for example, 120 ° C. or lower while suppressing excessive imidization.
- diamine is dissolved in an organic solvent or water, and tetracarboxylic acid dianhydride is gradually added while stirring to this solution, and the temperature is 0 to 120 ° C., preferably 5. Stir in the range of -80 ° C for 1-72 hours.
- the imidization rate may be adjusted by storing at a predetermined time, for example, about 1 day to 1 year, for example, at 5 ° C to 40 ° C to further promote imidization.
- the order of addition of diamine and tetracarboxylic acid dianhydride is preferable because the molecular weight of the polyimide precursor tends to increase.
- imidazoles such as 1,2-dimethylimidazole or a base such as triethylamine is preferably 0.8 times equivalent to the carboxyl group of the polyamic acid (polyimide precursor) to be produced. It is preferable to add in the above amount.
- the reaction between the tetracarboxylic acid component and the diamine component is carried out at a relatively high temperature, for example, when the temperature is 80 ° C. or higher, 90 ° C. or higher, or 100 ° C. or higher, the desired imidization rate is relatively high while suppressing an excessive imidization reaction. Since it can be achieved in a short time, the "polyimide precursor composition of the present invention" can be used as it is.
- the reaction temperature (heating) stage can be divided into two stages.
- the reaction of the tetracarboxylic acid component and the diamine component is carried out at a relatively low temperature (for example, 0 ° C. or higher, for example, 80 ° C. or lower, further 70 ° C. or lower, etc.) in the first step to reduce the imidization rate (imidization).
- a polyimide precursor (containing 0%) is obtained, and in the second step, it is heated at a relatively high temperature, for example, 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, for example, for 5 minutes to 72 hours.
- the reaction between the tetracarboxylic acid component and the diamine component is carried out at a relatively low temperature (for example, 0 ° C. or higher, for example, 80 ° C. or lower, further 70 ° C. or lower, etc.) in the first step to reduce the imidization rate (for example, 0 ° C. or higher, for example, 80 ° C. or lower, further 70 ° C. or lower).
- a relatively low temperature for example, 0 ° C. or higher, for example, 80 ° C. or lower, further 70 ° C. or lower.
- a polyimide precursor having an imidization rate of 0% is obtained, and even in the second step, at a relatively low temperature, for example, 0 ° C. or higher and 80 ° C.
- the imidization rate can be adjusted by advancing imidization for about 1 day to 1 year. Dividing the reaction temperature (heating) step into two steps is advantageous in that a stable polymerization reaction can be performed by carrying out the reaction of the tetracarboxylic acid component and the diamine component at a relatively low temperature in the first step.
- the tetracarboxylic acid dianhydride as the tetracarboxylic acid component is reacted with the diamine component under the condition that the imidization reaction proceeds, specifically, at a temperature of, for example, 100 ° C. or higher. More specifically, diamine is dissolved in a solvent, tetracarboxylic acid dianhydride is gradually added while stirring to this solution, and the temperature is 100 ° C. or higher, preferably 0.5 to 72 ° C. in the range of 120 to 250 ° C. Stir for hours to give a soluble imide compound.
- the order of addition of diamine and tetracarboxylic acid dianhydride may be reversed.
- the degree of polymerization of the imide compound can be determined so as to be soluble by the molar ratio of the tetracarboxylic acid component and the diamine component to be reacted. Both ends of the soluble imide compound may be an acid anhydride group, a carboxyl group, or an amino group.
- the chemical imidizing agent is an acid anhydride (dehydrating agent) such as acetic anhydride, and an amine compound (catalyst) such as pyridine and isoquinoline.
- a tetracarboxylic acid component and / or a diamine component is added to the reaction solution containing the soluble imide compound obtained in the first step to carry out a reaction to obtain the polyimide precursor of the present invention.
- the molar ratio of the total amount of the tetracarboxylic acid component to be reacted in the first step and the second step to the total amount of the diamine component is approximately equimolar, preferably the molar ratio of the diamine component to the tetracarboxylic acid component [diamine component].
- the number of moles of the tetracarboxylic acid component / the number of moles of the tetracarboxylic acid component] is 0.90 to 1.10, more preferably 0.95 to 1.05, and the tetracarboxylic acid component and / or the diamine component is added.
- the reaction is carried out under conditions that suppress imidization, specifically at a temperature of less than 100 ° C. More specifically, diamine is added to the reaction solution containing the soluble imide compound obtained in the first step, and the mixture is stirred at a temperature of less than 100 ° C., preferably -20 to 80 ° C. for 1 to 72 hours, and then tetra.
- the polyimide precursor of the present invention can be obtained by adding a carboxylic acid dianhydride and stirring at a temperature of less than 100 ° C., preferably ⁇ 20 to 80 ° C. for 1 to 72 hours.
- the order of adding the diamine and the tetracarboxylic acid dianhydride may be reversed, or the diamine and the tetracarboxylic acid dianhydride may be added at the same time.
- the total amount of the tetracarboxylic acid component to be reacted was added to the solvent in the first step, only the diamine was added, and when the total amount of the diamine component to be reacted was added to the solvent in the first step, the tetracarboxylic acid was added. Only acid dianhydride is added.
- Imidization may proceed in the second step as well, but the reaction temperature and reaction time are appropriately selected so that the imidization rate of the finally obtained polyimide precursor is within a predetermined range.
- the repeating unit of the imide structure structure of the general formula (II)
- the repeating unit of the amic acid structure mainly represented by the chemical formula (I) is generated in the second step.
- a polyamic acid ester whose repeating unit is represented by the formula (I) is obtained by the following reaction. First, tetracarboxylic acid dianhydride is reacted with an arbitrary alcohol to obtain a diester dicarboxylic acid, and then reacted with a chlorination reagent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride.
- a polyimide precursor can be obtained by stirring the diester dicarboxylic acid chloride and diamine in the range of ⁇ 20 to 120 ° C., preferably ⁇ 5 to 80 ° C. for 1 to 72 hours.
- a polyimide precursor can be easily obtained by dehydrating and condensing a diesterdicarboxylic acid and a diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.
- the polyimide precursor obtained by this method is stable, it can be purified by adding a solvent such as water or alcohol to reprecipitate.
- the obtained polyimide precursor (polyamic acid ester) was used in the same manner as in the section of 1) polyamic acid (one-stage supply method, that is, first-stage temperature low-second stage temperature high and first-stage temperature low-second stage. (See the second step at low temperature) can be reacted. That is, in one embodiment, the object is heated at a relatively high temperature, for example, 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, for example, for 5 minutes to 72 hours while suppressing an excessive imidization reaction. The imidization rate can be achieved. Further, in different embodiments, imidization is allowed to proceed at a relatively low temperature, for example, 0 ° C. or higher and 80 ° C. or lower (or lower), preferably 70 ° C. or lower, for a predetermined time, for example, from 1 day to 1 year. The imidization rate can also be adjusted.
- a relatively high temperature for example, 80 ° C. or higher,
- the polyamic acid silyl ester whose repeating unit is represented by the formula (I) is obtained by the reaction of the indirect method described in this section or the direct method described in the next section.
- a diamine is reacted with a silylating agent in advance to obtain a silylated diamine. If necessary, the silylated diamine is purified by distillation or the like. Then, the silylated diamine is dissolved in the dehydrated solvent, and the tetracarboxylic acid dianhydride is gradually added while stirring, and the temperature is in the range of 0 to 120 ° C, preferably 5 to 80 ° C.
- a polyimide precursor can be obtained by stirring for about 72 hours.
- the reaction is carried out at 80 ° C. or higher, the molecular weight fluctuates depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so that the polyimide precursor may not be stably produced.
- the obtained polyimide precursor (polyamic acid silyl ester) was used in the same manner as in the 1) polyamic acid section (one-stage supply method, that is, first-stage temperature low-second stage temperature high and first-stage temperature low-second stage). (See Stage 2 at low stage temperature) Can be reacted. That is, in one embodiment, the object is heated at a relatively high temperature, for example, 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, for example, for 5 minutes to 72 hours while suppressing an excessive imidization reaction. The imidization rate can be achieved. Further, in different embodiments, imidization is allowed to proceed at a relatively low temperature, for example, 0 ° C. or higher and 80 ° C. or lower (or lower), preferably 70 ° C. or lower, for a predetermined time, for example, from 1 day to 1 year. The imidization rate can also be adjusted.
- a relatively high temperature for example, 80 ° C. or higher
- Polyamic acid silyl ester (direct method)
- the polyamic acid solution having a predetermined imidization ratio obtained by the method 1) and the silylating agent are mixed and stirred in the range of 0 to 120 ° C., preferably 5 to 80 ° C. for 1 to 72 hours.
- a polyamic acid silyl ester having an imidization ratio of the above can be obtained.
- the tetracarboxylic acid dianhydride as the tetracarboxylic acid component and the diamine component are reacted under conditions that suppress imidization, for example, at a temperature of less than 100 ° C. to obtain a polyamic acid having a low imidization rate (1 above).
- a silylating agent is mixed with the obtained polyamic acid solution, and the mixture is stirred in the range of 0 to 120 ° C., preferably 5 to 80 ° C. for 1 to 72 hours to obtain a polyamic acid silyl ester having a low imidization rate.
- the obtained polyimide precursor polyamic acid silyl ester
- silylating agent used in the method 3) and the method 4 it is not necessary to purify the silylated polyamic acid or the obtained polyimide.
- the silylating agent containing no chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane.
- N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable because they do not contain a fluorine atom and are low in cost.
- an amine-based catalyst such as pyridine, piperidine, or triethylamine can be used to promote the reaction.
- This catalyst can be used as it is as a polymerization catalyst for the polyimide precursor.
- the solvent used in preparing the polyimide precursor is water or, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3. -Dimethyl-2-imidazolidinone, dimethyl sulfoxide and other aprotic solvents are preferable, and any kind of solvent can be used without problems as long as the raw material monomer component and the polyimide precursor to be produced are dissolved. It is not limited to its structure.
- an amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone , ⁇ -Caprolactone, ⁇ -caprolactone, cyclic ester solvent such as ⁇ -methyl- ⁇ -butyrolactone, carbonate solvent such as ethylene carbonate and propylene carbonate, glycol solvent such as triethylene glycol, m-cresol, p-cresol, 3 -Pharmonic solvents such as chlorophenol and 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide and the like are preferably adopted.
- an amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N
- the solvent may be used in combination of a plurality of types.
- the production of the polyimide precursor is not particularly limited, but the reaction is carried out by charging a monomer and a solvent at a concentration such that the solid content concentration (polyimide-equivalent mass concentration) of the polyimide precursor is, for example, 5 to 45% by mass.
- the logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5 g / dL at 30 ° C. is 0.2 dL / g or more, more preferably 0.3 dL / g. Above, it is particularly preferable that it is 0.4 dL / g or more.
- the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyimide precursor is high, and the mechanical strength and heat resistance of the obtained polyimide are excellent.
- the polyimide precursor composition may contain an imidazole compound.
- the addition of the imidazole compound may be effective in improving the light transmittance and / or in lowering the coefficient of linear thermal expansion, but in some cases, the imidization rate tends to be high depending on the selection of the compound. Therefore, when adding an imidazole compound, it is preferable to appropriately select the compound and / or adjust the imidization ratio appropriately.
- the imidazole compound is not particularly limited, and examples thereof include 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, imidazole, and benzimidazole. From the stability of the polyimide precursor composition, it is preferable to use at least one imidazole compound selected from 2-phenylimidazole and benzimidazole.
- the content of the imidazole compound in the polyimide precursor composition can be appropriately selected in consideration of the balance between the addition effect and the stability of the polyimide precursor composition.
- the amount of the imidazole compound is preferably more than 0.01 mol and less than 1 mol per 1 mol of repeating unit of the polyimide precursor.
- the addition of the imidazole compound generally improves mechanical properties such as elongation at break.
- the content of the imidazole compound is too large, the storage stability of the polyimide precursor composition may deteriorate.
- the content of the imidazole compound is more preferably 0.02 mol or more, still more preferably 0.025 mol or more, still more preferably 0.05 mol or more, and more preferably 0.02 mol or more, based on 1 mol of the repeating unit. It is preferably 0.8 mol or less, still more preferably 0.6 mol or less, even more preferably 0.4 mol or less, still more preferably less than 0.4 mol, and most preferably 0.3 mol or less.
- Patent Document 6 International Publication No. 2015/08158 describes a polyimide precursor composition containing an imidazole compound, a polyimide precursor containing 2-phenylimidazole and / or benzimidazole is described. There is no disclosure about the excellent storage stability of the composition. Further, in the examples of the same document, 400 nm light of a polyimide film produced from a composition containing 2-phenylimidazole or benzimidazole as compared with 1,2-dimethylimidazole, 1-methylimidazole and 2-methylimidazole. It has been shown that the permeability is reduced.
- the polyimide precursor composition used in the present invention may contain at least one polyimide precursor, a solvent, and optionally at least one of the above imidazole compounds.
- the solvent the above-mentioned solvent described as the solvent used when preparing the polyimide precursor can be used.
- the solvent used in preparing the polyimide precursor can be used as it is, that is, as the polyimide precursor solution, but it may be diluted or concentrated as necessary.
- the imidazole compound is dissolved and present in the polyimide precursor composition.
- the concentration of the polyimide precursor is not particularly limited, but is usually 5 to 45% by mass in terms of polyimide-equivalent mass concentration (solid content concentration).
- the polyimide reduced mass is the mass when all of the repeating units are completely imidized.
- the viscosity (rotational viscosity) of the polyimide precursor of the present invention is not particularly limited, but the rotational viscosity measured at a temperature of 25 ° C. and a shear rate of 20 sec -1 using an E-type rotational viscometer is 0.01 to 1000 Pa ⁇ sec. Is preferable, and 0.1 to 100 Pa ⁇ sec is more preferable. In addition, thixotropic properties can be imparted as needed. When the viscosity is in the above range, it is easy to handle when coating or forming a film, repelling is suppressed, and the leveling property is excellent, so that a good film can be obtained.
- the polyimide precursor composition of the present invention is, if necessary, an antioxidant, an ultraviolet absorber, a filler (inorganic particles such as silica), a dye, a pigment, a coupling agent such as a silane coupling agent, a primer, and a difficulty. It can contain a fuel material, a defoaming agent, a leveling agent, a rheology control agent (fluid auxiliary agent), and the like.
- the polyimide precursor composition of the present invention preferably does not contain a chemical imidizing agent.
- the warp of the produced polyimide film / glass base material laminate is reduced by using the polyimide precursor composition to which a specific siloxane compound is added.
- a siloxane compound of a type that does not impair transparency can be added to the polyimide precursor composition in an appropriate amount, or the siloxane compound may not be contained at all.
- the polyimide precursor composition can be prepared by adding a solution of an imidazole compound or a solution of an imidazole compound to the polyimide precursor solution obtained by the method as described above and mixing them.
- the tetracarboxylic acid component and the diamine component may be reacted in the presence of the imidazole compound.
- a polyimide By further advancing the imidization of the polyimide precursor of the present invention, a polyimide can be produced.
- the present invention is not particularly limited, and any known imidization method can be suitably applied.
- Suitable examples of the form of the obtained polyimide include a film, a laminate of a polyimide film and another substrate, a coating film, a powder, beads, a molded body, and a foam.
- the thickness of the polyimide film is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 5 ⁇ m or more, for example, 250 ⁇ m or less, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably. Is 50 ⁇ m or less.
- the 400 nm light transmittance of the polyimide film is preferably 79% or more, more preferably 80% or more when measured with a film having a thickness of 10 ⁇ m. Further, when measured with a film having a thickness of 10 ⁇ m, the yellowness (YI) of the polyimide film is preferably 3.2 or less, more preferably 3.0 or less, and most preferably 2.7 or less.
- the polyfilm of the present invention has an extremely low coefficient of linear thermal expansion.
- the coefficient of linear thermal expansion (CTE) of the polyimide film from 150 ° C. to 250 ° C. is preferably 20 ppm / K or less, more preferably less than 20 ppm, when measured with a film having a thickness of 10 ⁇ m. Most preferably, it is 15 ppm / K or less.
- the poly film of the present invention has extremely high heat resistance.
- the 5% weight loss temperature of the polyimide is preferably 500 ° C. or higher, more preferably 505 ° C. or higher, and even more preferably 510 ° C. or higher.
- a gas barrier film or the like is formed on a polyimide by forming a transistor on the polyimide, if the heat resistance is low, swelling may occur between the polyimide and the barrier membrane due to outgas caused by decomposition of the polyimide. ..
- the heat resistance is high, but depending on the application, characteristics other than the heat resistance are required, and the 5% weight loss temperature may be 500 ° C. or lower.
- the polyimide film has a breaking elongation of a film having a thickness of 10 ⁇ m, preferably 10% or more.
- the breaking strength of the polyimide film is preferably 150 MPa or more, more preferably 170 MPa or more, still more preferably 180 MPa or more, still more preferably 200 MPa or more, still more preferably 210 MPa or more.
- the breaking strength a value obtained from a film having a film thickness of, for example, about 5 to 100 ⁇ m can be used.
- the polyimide film can be manufactured by a known method.
- a typical method is a method in which a polyimide precursor composition is cast-coated on a substrate and then heated imidized on the substrate to obtain a polyimide film. This method will be described later in relation to the production of the polyimide film / base material laminate. Further, after the polyimide precursor composition is cast-coated on the substrate and dried by heating to produce a self-supporting film, the self-supporting film is peeled off from the substrate, and the film is held by a tenter, for example, from both sides of the film.
- a polyimide film can also be obtained by heating imidization in a degassable state.
- ⁇ Manufacture of polyimide film / substrate laminate and flexible electronic device
- (a) a step of applying a polyimide precursor composition onto a base material (b) the polyimide precursor is heat-treated on the base material, and the base material is used. It can be manufactured by a step of manufacturing a laminate (polyimide film / base material laminate) in which a polyimide film is laminated on top.
- the method for manufacturing a flexible electronic device of the present invention uses the polyimide film / base material laminate produced in the steps (a) and (b), and further steps, that is, (c) on the polyimide film of the laminate. It also has a step of forming at least one layer selected from a conductor layer and a semiconductor layer, and (d) a step of peeling the base material and the polyimide film.
- the polyimide precursor composition that can be used in the method of the present invention contains a polyimide precursor and a solvent.
- the polyimide precursor those described in the section of the polyimide precursor composition can be used.
- the polyimide precursor described as preferable in the section of the polyimide precursor composition is also preferable in the method of the present invention, but is not particularly limited.
- a polyimide film is formed by casting a polyimide precursor composition on a substrate, imidizing and dessolving it by heat treatment, and a laminate (polyimide) of the substrate and the polyimide film. Film / substrate laminate) is obtained.
- a heat-resistant material is used, for example, a plate-like material such as a ceramic material (glass, alumina, etc.), a metal material (iron, stainless steel, copper, aluminum, etc.), a semiconductor material (silicon, compound semiconductor, etc.) or the like.
- a sheet-like base material, or a film such as a heat-resistant plastic material (polyimide, etc.) or a sheet-like base material is used.
- a flat and smooth plate shape is preferable, and generally, a glass substrate such as soda lime glass, borosilicate glass, non-alkali glass, and sapphire glass; a semiconductor (including compound semiconductor) substrate such as silicon, GaAs, InP, and GaN; Metallic substrates such as iron, stainless steel, copper and aluminum are used.
- a glass substrate such as soda lime glass, borosilicate glass, non-alkali glass, and sapphire glass
- a semiconductor (including compound semiconductor) substrate such as silicon, GaAs, InP, and GaN
- Metallic substrates such as iron, stainless steel, copper and aluminum are used.
- a glass substrate is particularly preferable in the present invention.
- Glass substrates that are flat, smooth, and have a large area have been developed and are easily available.
- the problem of warpage becomes apparent especially as the area of the substrate becomes larger, and the glass substrate is relatively prone to warp in terms of rigidity. Therefore, by applying the present invention, it is possible to solve the problem when the glass substrate is used.
- the thickness of the plate-shaped base material such as a glass substrate is not limited, but is, for example, 20 ⁇ m to 4 mm, preferably 100 ⁇ m to 2 mm from the viewpoint of ease of handling.
- the size of the plate-shaped base material is not particularly limited, but one side (long side in the case of a rectangle) is, for example, about 100 mm to 4000 mm, preferably about 200 mm to 3000 mm, and more preferably about 300 mm to 2500 mm. Is.
- the base material such as these glass substrates may have an inorganic thin film (for example, a silicon oxide film) or a resin thin film formed on the surface thereof.
- an inorganic thin film for example, a silicon oxide film
- a resin thin film formed on the surface thereof.
- the method of casting the polyimide precursor composition onto the substrate is not particularly limited, but for example, a slit coating method, a die coating method, a blade coating method, a spray coating method, an inkjet coating method, a nozzle coating method, a spin coating method, and screen printing. Examples thereof include conventionally known methods such as a method, a bar coater method, and an electrodeposition method.
- step (b) the polyimide precursor composition is heat-treated on the substrate and converted into a polyimide film to obtain a polyimide film / substrate laminate.
- the heat treatment conditions are not particularly limited, but are, for example, after drying in a temperature range of 50 ° C. to 150 ° C., the maximum heating temperature is, for example, 150 ° C. to 600 ° C., preferably 200 ° C. to 550 ° C., and more preferably 250 ° C. It is preferable to treat at ⁇ 500 ° C.
- the heat treatment conditions when the polyimide solution is used are not particularly limited, but the maximum heating temperature is, for example, 100 ° C to 600 ° C, preferably 150 ° C or higher, more preferably 200 ° C or higher, and preferably 500 ° C. Below, it is more preferably 450 ° C. or lower.
- the thickness of the polyimide film is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and further preferably 5 ⁇ m or more. If the thickness is less than 1 ⁇ m, the polyimide film cannot maintain sufficient mechanical strength and may not be able to withstand stress and may be broken when used as a flexible electronic device substrate, for example.
- the thickness of the polyimide film is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and further preferably 20 ⁇ m or less. If the thickness of the polyimide film is increased, it may be difficult to reduce the thickness of the flexible device.
- the thickness of the polyimide film is preferably 2 to 50 ⁇ m in order to make the film thinner while maintaining sufficient resistance as a flexible device.
- the polyimide film has a breaking elongation of a film having a thickness of 10 ⁇ m, preferably 10% or more.
- the breaking strength of the polyimide film is preferably 150 MPa or more, more preferably 170 MPa or more, still more preferably 180 MPa or more, still more preferably 200 MPa or more, still more preferably 210 MPa or more.
- the breaking strength a value obtained from a film having a film thickness of, for example, about 5 to 100 ⁇ m can be used.
- the polyimide film in the polyimide film / base material laminate may have a second layer such as a resin film or an inorganic film on the surface. That is, after forming a polyimide film on a substrate, a second layer may be laminated to form a flexible electronic device substrate. It is preferable to have at least an inorganic film, and particularly preferably one that functions as a barrier layer for water vapor, oxygen (air), or the like.
- the water vapor barrier layer include silicon nitride (SiN x ), silicon oxide (SiO x ), silicon oxynitride (SiO x Ny ), aluminum oxide (Al 2 O 3 ), titanium oxide (TIO 2 ), and zirconium oxide.
- Examples thereof include an inorganic film containing an inorganic substance selected from the group consisting of metal oxides such as (ZrO 2 ), metal nitrides and metal oxynitrides.
- a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method and an ion plating method, and a chemical vapor deposition method such as a plasma CVD method and a catalytic chemical vapor deposition method (Cat-CVD method) are used.
- the method (chemical vapor deposition method) is known.
- the second layer may be a plurality of layers.
- the barrier layer / polyimide layer / barrier layer is formed on the polyimide film in the polyimide film / base material laminate. Examples include forming a three-layer structure.
- the polyimide / base material laminate obtained in the step (b) is used on a polyimide film (including a polyimide film on which a second layer such as an inorganic film is laminated on the surface). It forms at least one layer selected from the conductor layer and the semiconductor layer. These layers may be formed directly on a polyimide film (including a laminate of a second layer) or on a laminate of other layers required for the device, i.e. indirectly. good.
- an appropriate conductor layer and (inorganic, organic) semiconductor layer are selected according to the elements and circuits required by the target electronic device.
- the conductor layer and the semiconductor layer include both those formed on the entire surface of the polyimide film and those formed on a part of the polyimide film.
- the present invention may immediately shift to the step (d) after the step (c), or after forming at least one layer selected from the conductor layer and the semiconductor layer in the step (c), further device structure is formed. After forming, the process may proceed to step (d).
- a metal wiring, a TFT made of amorphous silicon or polysilicon, and a transparent pixel electrode are formed on a polyimide film having an inorganic film formed on the entire surface, if necessary.
- the TFT includes, for example, a gate metal layer, a semiconductor layer such as an amorphous silicon film, a gate insulating layer, wiring connected to a pixel electrode, and the like.
- a structure required for a liquid crystal display can also be formed by a known method.
- a transparent electrode and a color filter may be formed on the polyimide film.
- a TFT is formed on a polyimide film having an inorganic film formed on the entire surface, for example, in addition to a transparent electrode, a light emitting layer, a hole transport layer, an electron transport layer, etc. can do.
- the method for forming the circuit, element, and other structures required for the device is not particularly limited.
- the peeling method may be a mechanical peeling method in which physical peeling is performed by applying an external force, or a so-called laser peeling method in which laser light is irradiated from the substrate surface to peel.
- the device is completed by forming or incorporating the structure or parts required for the device into the (semi) product that uses the polyimide film after peeling off the base material as the substrate.
- Imidization rate (%) ⁇ X- (Y / Z) x A ⁇ / 2 x 100 (I) X: Integrated value of amide proton peak when imidization rate is 0% Y: 1 Integrated value of amide proton peak obtained from 1 H-NMR measurement Z: 1 Obtained from 1 H-NMR measurement Integrated value of aromatic proton peak A: Integrated value of aromatic proton peak obtained from the amount of monomer charged
- ⁇ Evaluation of polyimide film> [400 nm light transmittance] Using an ultraviolet-visible spectrophotometer / V-650DS (manufactured by JASCO Corporation), the light transmittance of a polyimide film having a film thickness of about 10 ⁇ m at 400 nm was measured. [Yellowness (YI)] The YI of the polyimide film was measured using an ultraviolet-visible spectrophotometer / V-650DS (manufactured by JASCO Corporation) in accordance with the ASTEM E313 standard. The light source was D65 and the viewing angle was 2 °.
- CTE Coefficient of linear thermal expansion
- DABAN 4,4'-diaminobenzanilide
- PPD p-phenylenediamine
- BABP 4,4'-bis (4-aminophenoxy) biphenyl
- TPE-Q 1,4-bis (4-aminophenoxy) benzene
- TFMB 2 , 2'-bis (trifluoromethyl) benzidine
- CpODA Norbornan-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2 "-norbornan-5,5", 6,6 "-tetracarboxylic acid dianhydride DNDAxx: (4arH, 8acH) -decahydro- 1t, 4t: 5c, 8c-dimethanonaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid dianhydride PMDA-H: cyclohexanetetracarboxylic acid dianhydride CBDA: cyclobutanetetracarboxylic acid dianhydride
- Table 1-1 shows the tetracarboxylic acid component and the diamine component used in Examples and Comparative Examples
- Table 1-2 shows the structural formulas of the imidazole compounds used in Examples and Comparative Examples.
- Example 1 [Preparation of polyimide precursor composition] 2.27 g (0.010 mol) of DABAN was placed in a reaction vessel replaced with nitrogen gas, and N-methyl-2-pyrrolidone was added, and the total mass of the charged monomers (total of diamine component and carboxylic acid component) was 16% by mass. A certain amount of 32.11 g was added, and the mixture was stirred at 50 ° C. for 1 hour. 3.84 g (0.010 mol) of CpODA was gradually added to this solution. The mixture was stirred at 70 ° C. for 4 hours to obtain a uniform and viscous polyimide precursor solution.
- 2-Phenylimidazole as an imidazole compound was dissolved in 4-fold mass of N-methyl-2-pyrrolidone to obtain a uniform solution having a solid content concentration of 2-phenylimidazole of 20% by mass.
- the solution of the imidazole compound and the polyimide precursor solution synthesized above were mixed so that the amount of the imidazole compound was 0.025 mol per 1 mol of the repeating unit of the polyimide precursor, and the mixture was stirred at room temperature for 3 hours. A uniform and viscous polyimide precursor composition was obtained.
- the result of measuring the imidization ratio of the polyimide precursor in the obtained polyimide precursor composition was 18%.
- polyimide film As the glass substrate, a 6-inch Corning Eagle-XG® (registered trademark) (500 ⁇ m thickness) was used.
- the polyimide precursor composition is applied onto a glass substrate with a spin coater, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), the polyimide film is thermally imidized by heating from room temperature to 415 ° C. on the glass substrate as it is. / A substrate laminate was obtained.
- the laminate was immersed in water at 40 ° C. (for example, in the temperature range of 20 ° C. to 100 ° C.) to peel off the polyimide film from the glass substrate, dried, and then the characteristics of the polyimide film were evaluated.
- the film thickness of the polyimide film is about 10 ⁇ m. The evaluation results are shown in Table 2.
- Examples 2 to 10 Polyimide containing a polyimide precursor having an imidization ratio shown in Table 2 in the same manner as in Example 1 except that the imidazole compound was changed to the compound shown in Table 2 (the blank indicates no addition) in Example 1. A precursor composition was obtained. Then, a polyimide film was produced in the same manner as in Example 1 and the physical characteristics of the film were evaluated. The results are shown in Table 2. In Examples 1 to 10, the polyimide precursor compositions of Examples 1 to 5 and 8 to 10 were also very excellent in long-term stability. Examples 1 to 5 are excellent in all physical characteristics.
- Example 11 ⁇ Examples 11 to 17, Comparative Examples 1 to 3>
- the imidazole compound was changed to the compound shown in Table 3. Further, by changing the temperature and time after adding CpODA in Example 1, a polyimide precursor composition containing a polyimide precursor having an imidization ratio shown in Table 3 was obtained. Then, a polyimide film was produced in the same manner as in Example 1 and the physical characteristics of the film were evaluated. The results are shown in Table 3.
- Example 4 ⁇ Examples 18 to 22, Comparative Example 4>
- the diamine component and the imidazole compound were changed to the compounds shown in Table 4. Further, by changing the temperature and time after adding CpODA in Example 1, a polyimide precursor composition containing a polyimide precursor having an imidization ratio shown in Table 4 was obtained. Then, a polyimide film was produced in the same manner as in Example 1 and the physical characteristics of the film were evaluated. The results are shown in Table 4.
- Example 2 ⁇ Examples 23 to 29, Comparative Examples 5 and 6>
- the tetracarboxylic acid component, the diamine component, and the imidazole compound were changed to the compounds shown in Table 5. Further, by changing the temperature and time after adding CpODA in Example 1, a polyimide precursor composition containing a polyimide precursor having an imidization ratio shown in Table 5 was obtained. Then, a polyimide film was produced in the same manner as in Example 1 and the physical characteristics of the film were evaluated. The results are shown in Table 5.
- Example 1 ⁇ Comparative Examples 7 to 10>
- the tetracarboxylic acid component, the diamine component, and the imidazole compound were changed to the compounds shown in Table 6. Further, by changing the temperature and time after adding CpODA in Example 1, a polyimide precursor composition containing a polyimide precursor having an imidization ratio shown in Table 6 was obtained. Then, a polyimide film was produced in the same manner as in Example 1 and the physical characteristics of the film were evaluated. The results are shown in Table 6.
- a polyimide precursor having a CpODA ratio of 70 mol% or more in the tetracarboxylic acid component, a DABAN ratio of 70 mol% or more in the diamine component, and an imidization ratio of less than 50%. It was found that the polyimide film obtained from the composition had a large 400 nm light transmittance, a small coefficient of linear thermal expansion, and a high 5% weight loss temperature.
- the present invention can be suitably applied to the manufacture of flexible electronic devices such as liquid crystal displays, organic EL displays, display devices such as electronic paper, solar cells and light receiving devices such as CMOS.
- flexible electronic devices such as liquid crystal displays, organic EL displays, display devices such as electronic paper, solar cells and light receiving devices such as CMOS.
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Abstract
Description
溶媒
を含有することを特徴とするポリイミド前駆体組成物。
基材と
を有することを特徴とするポリイミドフィルム/基材積層体。
(b)前記基材上で前記ポリイミド前駆体を加熱処理し、前記基材上にポリイミドフィルムを積層する工程
を有するポリイミドフィルム/基材積層体の製造方法。
(b)前記基材上で前記ポリイミド前駆体を加熱処理し、前記基材上にポリイミドフィルムが積層されたポリイミドフィルム/基材積層体を製造する工程、
(c)前記積層体のポリイミドフィルム上に、導電体層および半導体層から選ばれる少なくとも1つの層を形成する工程、および
(d)前記基材と前記ポリイミドフィルムとを剥離する工程
を有するフレキシブル電子デバイスの製造方法。
ポリイミドフィルムを形成するためのポリイミド前駆体組成物は、ポリイミド前駆体および溶媒を含有する。ポリイミド前駆体は溶媒に溶解している。
前述のとおり、ポリイミド前駆体中の全繰り返し単位中、X1は、好ましくは70モル%以上が式(1-1)で示される構造であり、より好ましくは80モル%以上、さらにより好ましくは90モル%以上、最も好ましくは95モル%以上(100モル%も非常に好ましい)が式(1-1)で示される構造である。X1として式(1-1)の構造を与えるテトラカルボン酸二無水物はCpODAである。
で表される構造が好ましい。
前述のとおり、ポリイミド前駆体中の全繰り返し単位中、Y1は、好ましくは70モル%以上が式(D-1)および/または(D-2)で示される構造であり、より好ましくは80モル%以上、さらにより好ましくは90モル%以上(100モル%も好ましい)が、式(D-1)および/または(D-2)で示される構造である。Y1として式(D-1)、式(D-2)の構造を与えるジアミン化合物は、4,4’-ジアミノベンズアニリド(略称:DABAN)である。
で表される構造が好ましい。
1)ポリアミック酸(R1及びR2が水素;別名ポリアミド酸)、
2)ポリアミック酸エステル(R1及びR2の少なくとも一部がアルキル基;別名ポリアミド酸エステル)、
3)4)ポリアミック酸シリルエステル(R1及びR2の少なくとも一部がアルキルシリル基;別名ポリアミド酸シリルエステル)、
に分類することができる。そして、ポリイミド前駆体は、この分類ごとに、以下の製造方法により容易に製造することができる。ただし、本発明で使用されるポリイミド前駆体の製造方法は、以下の製造方法に限定されるものではない。
式(I)で表される繰り返し単位がポリアミック酸である場合、イミド化反応を分子内で平均的に(またはランダムに)進行させる1段供給法および、テトラカルボン酸成分とジアミン成分のそれぞれを分割して供給し、イミド化反応の一部のテトラカルボン酸成分と一部のジアミン成分の間でのみ(またはブロック的に)進行させる多段供給法のどちらも採用し得る。
テトラカルボン酸成分とジアミン成分の反応を比較的高い温度で行う場合、例えば80℃以上、90℃以上、100℃以上の場合、過度のイミド化反応を抑制しながら目的のイミド化率を比較的短時間で達成することも可能であるので、そのまま「本発明のポリイミド前駆体組成物」とすることができる。
式(I)で表される繰り返し単位がポリアミック酸エステルは次の反応によって得られる。まず、テトラカルボン酸二無水物を任意のアルコールと反応させ、ジエステルジカルボン酸を得た後、塩素化試薬(チオニルクロライド、オキサリルクロライドなど)と反応させ、ジエステルジカルボン酸クロライドを得る。このジエステルジカルボン酸クロライドとジアミンを-20~120℃、好ましくは-5~80℃の範囲で1~72時間攪拌することで、ポリイミド前駆体(ポリアミック酸エステル)が得られる。80℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。また、ジエステルジカルボン酸とジアミンを、リン系縮合剤や、カルボジイミド縮合剤などを用いて脱水縮合することでも、簡便にポリイミド前駆体が得られる。
式(I)で表される繰り返し単位がポリアミック酸シリルエステルは、この項で説明する間接法または次項で説明する直接法の反応によって得られる。まず間接法では、あらかじめ、ジアミンとシリル化剤を反応させ、シリル化されたジアミンを得る。必要に応じて、蒸留等により、シリル化されたジアミンの精製を行う。そして、脱水された溶剤中にシリル化されたジアミンを溶解させておき、攪拌しながら、テトラカルボン酸二無水物を徐々に添加し、0~120℃、好ましくは5~80℃の範囲で1~72時間攪拌することで、ポリイミド前駆体が得られる。80℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。
1)の方法で得られた所定のイミド化率を有するポリアミック酸溶液とシリル化剤を混合し、0~120℃、好ましくは5~80℃の範囲で1~72時間攪拌することで、所定のイミド化率を有するポリアミック酸シリルエステルが得られる。
ポリイミド前駆体組成物は、イミダゾール化合物を含有してもよい。イミダゾール化合物の添加は、光透過率の向上および/または線熱膨張係数の低下に効果がある場合もあるが、化合物の選択によってはイミド化率が高くなり易い場合もある。従って、イミダゾール化合物を添加する場合は、化合物を適切に選択し、および/またはイミド化率を適切に調整することが好ましい。
本発明で使用されるポリイミド前駆体組成物は、少なくとも1種のポリイミド前駆体と、溶媒を含み、任意に少なくとも1種の上記のイミダゾール化合物をさらに含んでよい。
本発明のポリイミド前駆体のイミド化をさらに進めることで、ポリイミドを製造することができる。本発明においては、特に限定されず、公知のイミド化の方法いずれも好適に適用することができる。得られるポリイミドの形態は、フィルム、ポリイミドフィルムと他の基材との積層体、コーティング膜、粉末、ビーズ、成型体、発泡体などを好適に挙げることができる。
本発明のポリイミドフィルム/基材積層体は、(a)ポリイミド前駆体組成物を、基材上に塗布する工程、(b)前記基材上で前記ポリイミド前駆体を加熱処理し、前記基材上にポリイミドフィルムが積層された積層体(ポリイミドフィルム/基材積層体)を製造する工程により製造することができる。本発明のフレキシブル電子デバイスの製造方法は、前記工程(a)および工程(b)で製造されたポリイミドフィルム/基材積層体を使用し、さらなる工程、即ち(c)前記積層体のポリイミドフィルム上に、導電体層および半導体層から選ばれる少なくとも1つの層を形成する工程、および(d)前記基材と前記ポリイミドフィルムとを剥離する工程を有する。
[イミド化率]
溶媒にジメチルスルホキシド-d6を用い、日本電子製M-AL400でポリイミド前駆体溶液の1H-NMR測定を行い、芳香族プロトンのピークの積分値とカルボン酸プロトンのピークの積分値の比から、下記式(I)によってイミド化率[全繰り返し単位に対する化学式(2)で表される繰り返し単位の含有量]を算出した。
X:モノマーの仕込み量から求められる、イミド化率0%の場合のアミドプロトンピークの積分値
Y:1H-NMR測定から得られるアミドプロトンピークの積分値
Z:1H-NMR測定から得られる芳香族プロトンピークの積分値
A:モノマーの仕込み量から求められる、芳香族プロトンピークの積分値
[400nm光透過率]
紫外可視分光光度計/V-650DS(日本分光製)を用いて、膜厚約10μmのポリイミド膜の400nmにおける光透過率を測定した。
[黄色度(YI)]
紫外可視分光光度計/V-650DS(日本分光製)を用いて、ASTEM E313の規格に準拠して、ポリイミドフィルムのYIを測定した。光源はD65、視野角は2°とした。
膜厚約10μmのポリイミドフィルムをIEC450規格のダンベル形状に打ち抜いて試験片とし、ORIENTEC社製TENSILONを用いて、チャック間長30mm、引張速度2mm/分で、初期の弾性率、破断伸度、破断強度を測定した。
膜厚約10μmのポリイミドフィルムを幅4mmの短冊状に切り取って試験片とし、TMA/SS6100 (エスアイアイ・ナノテクノロジー株式会社製)を用い、チャック間長15mm、荷重2g、昇温速度20℃/分で500℃まで昇温した。得られたTMA曲線から、150℃から250℃までの線熱膨張係数を求めた。
膜厚約10μmのポリイミドフィルムを試験片とし、TAインスツルメント社製 熱量計測定装置(Q5000IR)を用い、窒素気流中、昇温速度10℃/分で25℃から600℃まで昇温した。得られた重量曲線から、5%重量減少温度を求めた。
以下の各例で使用した原材料の略称、純度等は、次のとおりである。
DABAN: 4,4’-ジアミノベンズアニリド
PPD: p-フェニレンジアミン
BAPB: 4,4’-ビス(4-アミノフェノキシ)ビフェニル
TPE-Q: 1,4-ビス(4-アミノフェノキシ)ベンゼン
TFMB: 2,2’-ビス(トリフルオロメチル)ベンジジン
CpODA: ノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2”-ノルボルナン-5,5”,6,6”-テトラカルボン酸二無水物
DNDAxx:(4arH,8acH)-デカヒドロ-1t,4t:5c,8c-ジメタノナフタレン-2t,3t,6c,7c-テトラカルボン酸二無水物
PMDA-H: シクロヘキサンテトラカルボン酸二無水物
CBDA:シクロブタンテトラカルボン酸二無水物
2-Pz: 2-フェニルイミダゾール
Bz:ベンゾイミダゾール
2-Mz:2-メチルイミダゾール
NMP: N-メチル-2-ピロリドン
DMAc: ジメチルアセトアミド
[ポリイミド前駆体組成物の調製]
窒素ガスで置換した反応容器中にDABAN 2.27g(0.010モル)を入れ、N-メチル-2-ピロリドンを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が16質量%となる量の32.11gを加え、50℃で1時間攪拌した。この溶液にCpODA 3.84g(0.010モル)を徐々に加えた。70℃で4時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。
ガラス基板として、6インチのコーニング社製のEagle-XG(登録商標)(500μm厚)を使用した。ガラス基板上にポリイミド前駆体組成物をスピンコーターにより塗布し、窒素雰囲気下(酸素濃度200ppm以下)で、そのままガラス基板上で室温から415℃まで加熱して熱的にイミド化を行い、ポリイミドフィルム/基材積層体を得た。積層体を40℃の水(例えば温度20℃~100℃の範囲)につけてガラス基板からポリイミドフィルムを剥離し、乾燥後、ポリイミドフィルムの特性を評価した。ポリイミドフィルムの膜厚は約10μmである。評価結果を表2に示す。
実施例1において、イミダゾール化合物を表2に示す化合物(空欄は不添加を示す)に変更した以外は、実施例1と同様にして表2に示すイミド化率を有するポリイミド前駆体を含有するポリイミド前駆体組成物を得た。その後、実施例1と同様にしてポリイミドフィルムを製造してフィルム物性を評価した。結果を表2に示す。尚、実施例1~10の中で、実施例1~5、8~10のポリイミド前駆体組成物は、長期安定性にも非常に優れていた。実施例1~5はすべての物性が優れている。
実施例1において、イミダゾール化合物を表3に示す化合物に変更した。また実施例1においてCpODAを添加した後の温度および時間を変更することで、表3に示すイミド化率を有するポリイミド前駆体を含有するポリイミド前駆体組成物を得た。その後、実施例1と同様にしてポリイミドフィルムを製造してフィルム物性を評価した。結果を表3に示す。
実施例1において、ジアミン成分、およびイミダゾール化合物を表4に示す化合物に変更した。また実施例1においてCpODAを添加した後の温度および時間を変更することで、表4に示すイミド化率を有するポリイミド前駆体を含有するポリイミド前駆体組成物を得た。その後、実施例1と同様にしてポリイミドフィルムを製造してフィルム物性を評価した。結果を表4に示す。
実施例1において、テトラカルボン酸成分、ジアミン成分、およびイミダゾール化合物を表5に示す化合物に変更した。また実施例1においてCpODAを添加した後の温度および時間を変更することで、表5に示すイミド化率を有するポリイミド前駆体を含有するポリイミド前駆体組成物を得た。その後、実施例1と同様にしてポリイミドフィルムを製造してフィルム物性を評価した。結果を表5に示す。
実施例1において、テトラカルボン酸成分、ジアミン成分、およびイミダゾール化合物を表6に示す化合物に変更した。また実施例1においてCpODAを添加した後の温度および時間を変更することで、表6に示すイミド化率を有するポリイミド前駆体を含有するポリイミド前駆体組成物を得た。その後、実施例1と同様にしてポリイミドフィルムを製造してフィルム物性を評価した。結果を表6に示す。
窒素ガスで置換した反応容器中にDABAN 0.713g(3.136ミリモル)とTFMB 1.004g(3.136ミリモル)を入れ、DMAcを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 20質量%となる量の16.5gを加え、室温で1時間攪拌した。この溶液にCpODA 2.411g(6.272ミリモル)を徐々に加え、室温で24時間攪拌した。その後、160℃へ昇温し、トルエンを25mL添加し、10分間トルエンを還流させた後、トルエンを抜き出し、室温まで冷却し、均一で粘稠なポリイミド前駆体溶液(イミド化率:44%)を得た。その後、実施例1と同様にしてポリイミドフィルムを製造してフィルム物性を評価した。結果を表6に示す。
Claims (13)
- 繰り返し単位が、下記一般式(I)で表される繰り返し単位、および一般式(I)がさらにイミド化された繰り返し単位からなり、イミド化率が0%超かつ50%未満であるポリイミド前駆体、および
溶媒
を含有することを特徴とするポリイミド前駆体組成物。
- このポリイミド前駆体組成物から得られるポリイミドフィルムが、厚さ10μmのフィルムでの波長400nmの光透過率79%以上を有することを特徴とする請求項1に記載のポリイミド前駆体組成物。
- このポリイミド前駆体組成物から得られるポリイミドフィルムが、厚さ10μmのフィルムで、150℃から250℃の間で20ppm/K以下の線熱膨張係数を有することを特徴とする請求項1または2に記載のポリイミド前駆体組成物。
- このポリイミド前駆体組成物から得られるポリイミドが、500℃以上の5%重量減少温度を有することを特徴とする請求項1~3のいずれか1項に記載のポリイミド前駆体組成物。
- このポリイミド前駆体組成物から得られるポリイミドフィルムが、厚さ10μmのフィルムでの破断伸度が10%以上であることを特徴とする請求項1~4のいずれか1項に記載のポリイミド前駆体組成物。
- X1の90モル%以上が、前記式(1-1)で表される構造であることを特徴とする請求項1~5のいずれか1項に記載のポリイミド前駆体組成物。
- 請求項1~6のいずれか1項に記載のポリイミド前駆体組成物から得られるポリイミドフィルム。
- 請求項1~6のいずれか1項に記載のポリイミド前駆体組成物から得られるポリイミドフィルムと、
基材と
を有することを特徴とするポリイミドフィルム/基材積層体。 - 前記基材が、ガラス基板である請求項8に記載の積層体。
- (a)請求項1~6のいずれか1項に記載のポリイミド前駆体組成物を、基材上に塗布する工程、および
(b)前記基材上で前記ポリイミド前駆体を加熱処理し、前記基材上にポリイミドフィルムを積層する工程
を有するポリイミドフィルム/基材積層体の製造方法。 - 前記基材が、ガラス基板である請求項10に記載の製造方法。
- (a)請求項1~6のいずれか1項に記載のポリイミド前駆体組成物を、基材上に塗布する工程、
(b)前記基材上で前記ポリイミド前駆体を加熱処理し、前記基材上にポリイミドフィルムが積層されたポリイミドフィルム/基材積層体を製造する工程、
(c)前記積層体のポリイミドフィルム上に、導電体層および半導体層から選ばれる少なくとも1つの層を形成する工程、および
(d)前記基材と前記ポリイミドフィルムとを剥離する工程
を有するフレキシブル電子デバイスの製造方法。 - 前記基材が、ガラス基板である請求項12に記載の製造方法。
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WO2015080158A1 (ja) * | 2013-11-27 | 2015-06-04 | 宇部興産株式会社 | ポリイミド前駆体組成物、ポリイミドの製造方法、ポリイミド、ポリイミドフィルム、及び基板 |
JP2016030760A (ja) * | 2014-07-25 | 2016-03-07 | 富士ゼロックス株式会社 | ポリイミド前駆体組成物、ポリイミド前駆体の製造方法、ポリイミド成形体、及びポリイミド成形体の製造方法 |
JP2017160360A (ja) * | 2016-03-10 | 2017-09-14 | Jxtgエネルギー株式会社 | レーザ剥離用樹脂フィルム、レーザ剥離用ワニス組成物、レーザ剥離用積層体及びレーザ剥離方法 |
JP2017197645A (ja) * | 2016-04-27 | 2017-11-02 | 株式会社カネカ | アルコキシシラン変性ポリイミド前駆体溶液、および、前駆体溶液、積層体並びにフレキシブルデバイスの製造方法。 |
WO2018143314A1 (ja) * | 2017-02-03 | 2018-08-09 | 東京応化工業株式会社 | ポリイミド前駆体組成物 |
WO2019163703A1 (ja) * | 2018-02-21 | 2019-08-29 | Jxtgエネルギー株式会社 | ポリイミド前駆体樹脂組成物 |
JP2019059959A (ja) * | 2018-08-03 | 2019-04-18 | Jxtgエネルギー株式会社 | テトラカルボン酸二無水物、ポリイミド前駆体樹脂、ポリイミド、ポリイミド前駆体樹脂溶液、ポリイミド溶液及びポリイミドフィルム |
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