JP5536202B2 - フレキシブル金属箔積層体及びその製造方法 - Google Patents
フレキシブル金属箔積層体及びその製造方法 Download PDFInfo
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- JP5536202B2 JP5536202B2 JP2012511769A JP2012511769A JP5536202B2 JP 5536202 B2 JP5536202 B2 JP 5536202B2 JP 2012511769 A JP2012511769 A JP 2012511769A JP 2012511769 A JP2012511769 A JP 2012511769A JP 5536202 B2 JP5536202 B2 JP 5536202B2
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- metal foil
- polyimide
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- heat treatment
- flexible metal
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- 229910052751 metal Inorganic materials 0.000 title claims description 78
- 239000002184 metal Substances 0.000 title claims description 78
- 239000011888 foil Substances 0.000 title claims description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229920001721 polyimide Polymers 0.000 claims description 151
- 239000004642 Polyimide Substances 0.000 claims description 89
- 238000010438 heat treatment Methods 0.000 claims description 83
- 239000009719 polyimide resin Substances 0.000 claims description 54
- 239000002243 precursor Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- 229920005575 poly(amic acid) Polymers 0.000 claims description 22
- 230000008859 change Effects 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 76
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 238000005530 etching Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- -1 tetracarboxylic anhydride Chemical class 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- BZIVKXRNXXPVJD-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=C(OC2=CC(=CC=C2)OC2=CC=C(C=C2)N)C=C1.NC1=CC=C(OC2=CC(=CC=C2)OC2=CC=C(C=C2)N)C=C1 BZIVKXRNXXPVJD-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ZKGNPQKYVKXMGJ-UHFFFAOYSA-N N,N-dimethylacetamide Chemical compound CN(C)C(C)=O.CN(C)C(C)=O ZKGNPQKYVKXMGJ-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
- H05K2203/0759—Forming a polymer layer by liquid coating, e.g. a non-metallic protective coating or an organic bonding layer
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/14—Related to the order of processing steps
- H05K2203/1476—Same or similar kind of process performed in phases, e.g. coarse patterning followed by fine patterning
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Moulding By Coating Moulds (AREA)
Description
前記化学式1中、Ar及びAr2は芳香族環構造体で、互いに独立して(C6−C20)アリール基であり、Iは1〜10,000,000から選択された整数であり、用いられる単量体の組成に応じて多様な構造が存在することができるということは勿論である。
m、nは0.6≦m≦1.0、0≦n≦0.4及びm+n=1を満たす実数であり、X及びYは、互いに独立して、下記の構造から選択され、これらを単独あるいは共重合して用いることができる。
t:ポリイミド樹脂層の厚さ(μm)
T:80〜180℃の温度範囲での平均昇温速度(K/min)
t:ポリイミド樹脂層の厚さ(μm)
T:80℃〜180℃の温度範囲での平均昇温速度(K/min)
BPDA:3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(3,3´,4,4´−biphenyltetracarboxylic acid dianhydride)
PDA:パラ−フェニレンジアミン(p−phenylenediamine)
ODA:4,4’−ジアミノジフェニルエーテル(4,4’−diaminodiphenylether)
BAPP:2,2’−ビス(4−アミノフェノキシフェニル)プロパン(2,2’−bis(4−aminophenoxyphenyl))
TPE−R:1,3−ビス(4−アミノフェノキシ)ベンゼン(1,3−bis(4−aminophenoxy)benzene)
線熱膨張係数は、TMA(Thermomechanical Analysis)を利用して5℃/分の速度で400℃まで昇温しながら測定された熱膨張値のうち100℃〜250℃の膨張量を平均して求めた。また、この過程により測定した熱膨張曲線の変曲点をガラス転移温度(Tg)にした。
エッチング前後の積層体をMD(Machine Direction)及びTD(Transverse Direction)方向の長さがそれぞれ20cm及び30cmの正方形に切断した後、四つの角での底面からの高さを測定し、その高さが1cmを超えない場合を平坦であると判断した。
イミド化終了後の積層体の表面形状を観察して、表面の気泡生成、膨張、ポリイミド樹脂の層間またはポリイミド樹脂と金属箔との界面での層間剥離現象(delamination)がない場合を外観が良好であると判断した。
IPC−TM−650,2.2.4の「Method C」に従って、金属箔のエッチング及び150℃、30分熱処理後の寸法変化率を測定した。
Instron社の万能試験機を利用して、IPC−TM−650,2.4.19に準拠して測定した。
25,983gのDMAc溶液に、PDA1,809g及びODA591gのジアミンを窒素雰囲気下で撹拌して完全に溶かした後、二無水物としてBPDA6,000gを数回に分けて添加した。その後、約24時間撹拌を続けてポリアミック酸溶液を製造した。このように製造したポリアミック酸溶液を20μmの厚さのフィルム状にキャスティングした後、60分間350℃まで昇温した後、350℃で30分間維持して完全に硬化した。測定されたガラス転移温度と線熱膨張係数は、それぞれ314℃及び9.9ppm/Kであった。
合成例1と同様の方法により、[表1]の組成及び含量を用いて製造した。
厚さ15μmの銅箔上に、合成例1により製造されたポリアミック酸溶液を最終硬化後の厚さが25μmになるように塗布した後、引き続いて150℃で乾燥して第1ポリイミド前駆体層を形成した。その後、前記第1ポリイミド前駆体層の一面に、合成例2により製造したポリアミック酸溶液を最終硬化後の厚さが15μmになるように塗布した後、引き続いて150℃で乾燥して第2ポリイミド前駆体層を形成した。第1ポリイミド層及び第2ポリイミド層の塗布時の総加熱時間は15.4分であった。上述の積層体を赤外線加熱装置を利用して150℃〜395℃まで昇温して完全にイミド化し、その結果を表2に記載した。
厚さ15μmの銅箔上に、合成例4により製造されたポリアミック酸溶液を最終硬化後の厚さが25μmになるように塗布した後、引き続いて140℃で乾燥して第1ポリイミド前駆体層を形成した。その後、前記第1ポリイミド前駆体層の一面に、合成例2により製造されたポリアミック酸溶液を最終硬化後の厚さが15μmになるように塗布した後、引き続いて140℃で乾燥して第2ポリイミド前駆体層を形成した。第1ポリイミド層及び第2ポリイミド層の塗布時の総加熱時間は11.5分であった。上述の積層体を赤外線加熱装置を利用して150℃〜390℃まで昇温して完全にイミド化し、その結果を表2に記載した。
厚さ12μmの銅箔上に、合成例5により製造されたポリアミック酸溶液を最終硬化後の厚さが2.5μmになるように塗布した後、引き続いて150℃で乾燥して第1ポリイミド前駆体層を形成した。その後、前記第1ポリイミド前駆体層の一面に、合成例6により製造されたポリアミック酸溶液を最終硬化後の厚さが20μmになるように塗布した後、引き続いて150℃で乾燥して第2ポリイミド前駆体層を形成した。その後、前記第2ポリイミド前駆体層の一面に、合成例7により製造されたポリアミック酸溶液を最終硬化後の厚さが3μmになるように塗布した後、引き続いて150℃で乾燥して第3ポリイミド前駆体層を形成した。第1ポリイミド層、第2ポリイミド層及び第3ポリイミド層の塗布時の総加熱時間は15.3分であった。上述の積層体を赤外線加熱装置を利用して150℃〜395℃まで昇温して完全にイミド化し、その結果を表2に記載した。
Claims (10)
- 金属箔と、
前記金属箔上にポリイミド樹脂に変換可能なポリイミド前駆体樹脂を複数回塗布して乾燥した後、赤外線加熱装置を利用して、80℃以上での総加熱時間が5〜60分の範囲であり、このうち80〜180℃の温度区間での熱処理条件が式2を満たし、最高熱処理温度が300〜400℃の範囲で追加乾燥及び硬化して製造されたポリイミド樹脂層と、を含み、
[式2]
t:ポリイミド樹脂層の厚さ(μm)
T:80℃〜180℃の温度範囲での平均昇温速度(K/min)
IPC−TM−650,2.2.4の「Method C」規格に準拠して、150℃で30分間熱処理した後の寸法変化率が±0.05%以下である
フレキシブル金属箔積層体。 - ポリイミド樹脂層は、全体線熱膨張係数が20ppm/K以下である請求項1に記載のフレキシブル金属箔積層体。
- 金属箔と直接接するポリイミド樹脂層のガラス転移温度が300℃以上である請求項1又は2に記載のフレキシブル金属箔積層体。
- 金属箔と直接接するポリイミド樹脂層の組成が下記化学式2を含む請求項1〜3のいずれかに記載のフレキシブル金属箔積層体。
[化学式2]
前記化学式2中、m、nは0.6≦m≦1.0、0≦n≦0.4及びm+n=1を満たす実数であり、X及びYは、互いに独立して、下記の構造から選択され、これらを単独あるいは共重合して用いることができる。
- ポリイミド樹脂層全体の引張弾性率が4〜7GPaの範囲である請求項1〜4のいずれかに記載のフレキシブル金属箔積層体。
- ポリイミド樹脂層と金属箔との界面での引きはがし強さ(Peel Strength)が0.5Kgf/cm以上である請求項1〜5のいずれかに記載のフレキシブル金属箔積層体。
- 金属箔と接するポリイミド層の他面に存在するポリイミド層の線熱膨張係数が20ppm/K以下であり、金属箔と接するポリイミド層の他面に存在するポリイミド層と、金属箔と接するポリイミド層との線熱膨張係数差が5ppm/K以下である請求項1〜6のいずれかに記載のフレキシブル金属箔積層体。
- ポリイミド樹脂に変換可能なポリイミド前駆体樹脂を金属箔上に複数回塗布して乾燥した後、赤外線加熱装置を利用して追加乾燥及び硬化して製造したフレキシブル金属箔積層体の製造方法であって、
金属箔の一面に、最終イミド化後のガラス転移温度が300℃以上であるポリアミック酸溶液を塗布した後、80〜180℃で乾燥して第1ポリイミド層を形成する段階と、
前記形成された第1ポリイミド層上に、最終イミド化後の線熱膨張係数が20ppm/K以下であるポリアミック酸溶液を塗布した後、80〜180℃で乾燥して第2ポリイミド層を形成して積層体を製造する段階を含み、
ポリイミド前駆体樹脂を塗布及び乾燥した後、赤外線加熱装置を利用して追加乾燥及び硬化する工程中の80℃以上での総加熱時間が5〜60分の範囲であり、このうち80〜180℃の温度区間での熱処理条件が式2を満たし、
最高熱処理温度が300〜400℃の範囲であり、300℃以上の総熱処理時間が80℃以上の総加熱時間に対して10〜40%である、
IPC−TM−650,2.2.4の「Method C」規格に準拠して、150℃で30分間熱処理した後の寸法変化率が±0.05%以下であるフレキシブル金属箔積層体の製造方法。
[式2]
t:ポリイミド樹脂層の厚さ(μm)
T:80℃〜180℃の温度範囲での平均昇温速度(K/min) - 第2ポリイミド層を形成する段階と、乾燥及び熱処理する段階との間に、前記第2ポリイミド層上にポリアミック酸溶液を塗布した後、80〜180℃で乾燥して第3ポリイミド層を形成する段階をさらに含む請求項8に記載のフレキシブル金属箔積層体の製造方法。
- ポリイミド前駆体樹脂を塗布して乾燥した後、これを加熱炉内で一定時間静置させるバッチ式であるか、ポリイミド前駆体樹脂で覆われた金属箔を、一定時間で連続的に加熱炉の内部を移動させる連続式である請求項8又は9に記載のフレキシブル金属箔積層体の製造方法。
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2007245525A (ja) * | 2006-03-16 | 2007-09-27 | Nippon Steel Chem Co Ltd | フレキシブル積層板 |
JPWO2007132529A1 (ja) * | 2006-05-17 | 2009-09-17 | 株式会社ピーアイ技術研究所 | 金属複合フィルム及びその製造方法 |
JP2008068406A (ja) * | 2006-09-12 | 2008-03-27 | Tomoegawa Paper Co Ltd | フレキシブル金属積層体およびフレキシブルプリント基板 |
JP2008188893A (ja) * | 2007-02-06 | 2008-08-21 | Toray Ind Inc | 金属層付き積層フィルム、これを用いたフレキシブル回路基板および半導体装置 |
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