JP2001315256A - Flexible metal foil-clad laminate - Google Patents
Flexible metal foil-clad laminateInfo
- Publication number
- JP2001315256A JP2001315256A JP2000133945A JP2000133945A JP2001315256A JP 2001315256 A JP2001315256 A JP 2001315256A JP 2000133945 A JP2000133945 A JP 2000133945A JP 2000133945 A JP2000133945 A JP 2000133945A JP 2001315256 A JP2001315256 A JP 2001315256A
- Authority
- JP
- Japan
- Prior art keywords
- metal foil
- clad laminate
- flexible metal
- thermoplastic polyimide
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 64
- 239000002184 metal Substances 0.000 title claims abstract description 64
- 229920006259 thermoplastic polyimide Polymers 0.000 claims abstract description 41
- 229920001721 polyimide Polymers 0.000 claims abstract description 36
- 238000010521 absorption reaction Methods 0.000 claims abstract description 27
- 239000011888 foil Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 230000009477 glass transition Effects 0.000 claims abstract description 13
- 229910000679 solder Inorganic materials 0.000 claims abstract description 11
- 229920005575 poly(amic acid) Polymers 0.000 claims description 21
- 239000012790 adhesive layer Substances 0.000 claims description 15
- 125000000962 organic group Chemical group 0.000 claims description 12
- 239000009719 polyimide resin Substances 0.000 claims description 10
- 229920001169 thermoplastic Polymers 0.000 claims description 10
- 239000004416 thermosoftening plastic Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 6
- 230000002159 abnormal effect Effects 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 5
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 30
- 239000010410 layer Substances 0.000 description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- -1 dianhydride compound Chemical class 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000006798 ring closing metathesis reaction Methods 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- RKFCDGOVCBYSEW-AUUKWEANSA-N tmeg Chemical compound COC=1C(OC)=CC(C(OC(C=2OC)=C34)=O)=C3C=1OC(=O)C4=CC=2O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O RKFCDGOVCBYSEW-AUUKWEANSA-N 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 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 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 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
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 101150051106 SWEET11 gene Proteins 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Moving Of Heads (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、電気配線板材料と
して用いられ得るフレキシブル金属箔張積層板に関す
る。さらに詳しくは、40℃/90%/96時間吸湿処
理後の半田浴ディップ試験(280℃10秒間)におい
て外観異常のない、すなわち、各層間の膨れや、剥がれ
が発生しないという優れた耐熱性を有するフレキシブル
金属箔張積層板、特には、ハードディスクドライブサス
ペンションに用いられるフレキシブル金属箔張積層板に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible metal foil-clad laminate that can be used as an electric wiring board material. More specifically, in a solder bath dip test (280 ° C. for 10 seconds) after a moisture absorption treatment at 40 ° C./90%/96 hours, there is no abnormal appearance, that is, excellent heat resistance such that no swelling or peeling between layers occurs. More particularly, the present invention relates to a flexible metal foil-clad laminate used for a hard disk drive suspension.
【0002】[0002]
【従来の技術】電子機器の高性能化、高機能化、小型化
が急速に進む中、フレキシブル配線板(以下、FPC)
の材料であるフレキシブル金属箔張積層板の需要は益々
拡大してきており、耐熱性、機械的強度、電気特性等の
諸物性に関わる市場要求はさらに高度化している。2. Description of the Related Art Flexible electronic circuit boards (hereinafter, referred to as FPCs) have been rapidly advancing as electronic devices have become more sophisticated, functional and smaller.
The demand for flexible metal foil-clad laminates, which is a material of the above, has been expanding more and more, and the market requirements for various physical properties such as heat resistance, mechanical strength, and electrical properties have been further enhanced.
【0003】耐熱性が良好なフレキシブル金属箔張積層
板として、ベースフィルムにポリイミドが用いられた積
層板が従来より使用されているが、金属箔とポリイミド
フィルムとの接着にエポキシ樹脂系やアクリル樹脂系と
いったポリイミドと比較すると耐熱性の劣る接着剤が用
いられているため、ポリイミドフィルムの耐熱性が十分
に活かされているとは言えなかった。この問題解決のた
めに、ベースフィルム及び接着剤もポリイミドである、
いわゆるオールポリイミドの金属箔張積層板の開発が行
われている。As a flexible metal foil-clad laminate having good heat resistance, a laminate using polyimide as a base film has been conventionally used. However, an epoxy resin or an acrylic resin is used to bond the metal foil to the polyimide film. Since an adhesive having lower heat resistance was used as compared with polyimide such as a system, it could not be said that the heat resistance of the polyimide film was fully utilized. To solve this problem, the base film and the adhesive are also polyimide,
A so-called all-polyimide metal foil-clad laminate has been developed.
【0004】また、最近注目されているオールポリイミ
ドの金属箔張積層板の一つに、接着剤層を有しない2層
タイプの積層板があり、その作製方法としてポリイミド
フィルム上に直接金属導体層を形成する方法及び金属箔
上に直接ポリイミド層を形成する方法が知られている。[0004] One of the all-polyimide metal foil-clad laminates that has recently attracted attention is a two-layer type laminate having no adhesive layer. And a method of forming a polyimide layer directly on a metal foil are known.
【0005】ところが、ポリイミドフィルム上に直接導
体層を形成する方法では、蒸着法やスパッタリング法で
金属導体の薄層を先ず形成し、その後メッキ法で金属導
体の厚層を形成するが、薄層形成時にピンホールが発生
しやすかったり、絶縁層と金属導体層の充分な接着力を
得られないという問題があった。However, in the method of forming a conductor layer directly on a polyimide film, a thin layer of a metal conductor is first formed by a vapor deposition method or a sputtering method, and then a thick layer of a metal conductor is formed by a plating method. There are problems that pinholes are easily generated during formation and that sufficient adhesion between the insulating layer and the metal conductor layer cannot be obtained.
【0006】一方、金属箔上に直接ポリイミド層を形成
する方法では、ポリイミドの溶液もしくはポリアミド酸
の溶液を金属箔上に流延塗布・乾燥しポリイミド層を形
成する方法を採用する。しかし、流延に用いる溶剤によ
っては導体層の腐食が起こりやすく、また両面板を作製
する際には、2枚の片面板を作製した後にこれら片面板
を張りあわすことが必要であり、煩雑な工程が必要とな
る問題があった。On the other hand, in the method of forming a polyimide layer directly on a metal foil, a method of casting and drying a solution of a polyimide or a solution of a polyamic acid on a metal foil and forming the polyimide layer is employed. However, depending on the solvent used for casting, corrosion of the conductor layer is likely to occur, and when preparing a double-sided board, it is necessary to make two single-sided boards and then to peel off these single-sided boards, which is complicated. There was a problem that required a process.
【0007】上記のような問題を解決するオールポリイ
ミドの金属箔張積層板として、熱融着性を有する熱可塑
性ポリイミドを介してベースポリイミドフィルムと金属
箔とを張り合わせる積層板が、特開平2−138789
号、特開平5−279224号、特開平5−22376
8号で提案されている。As an all-polyimide metal-foil-clad laminate that solves the above-mentioned problems, a laminate in which a base polyimide film and a metal foil are adhered to each other via a thermoplastic polyimide having a heat-fusing property is disclosed in Japanese Unexamined Patent Publication No. Hei. 138789
JP-A-5-279224, JP-A-5-22376
No. 8 is proposed.
【0008】ところで、プリント配線板のうち、ハード
ディスクドライブの磁気ヘッド用サスペンション配線板
等においては、ディスクの回転に伴って受ける空気浮上
力とプリント配線板の剛性反力とを釣り合わせて、でき
るだけ磁気ヘッドをディスクに近接するために、ヘッド
からの配線をステンレス製の超小型支持バネに直接パタ
ーン形成する方が都合がよく、上記のような方法で製造
された基板が好適に用いられている。Meanwhile, among printed wiring boards, a suspension wiring board for a magnetic head of a hard disk drive or the like is used to balance the air levitation force received with the rotation of the disk and the rigid reaction force of the printed wiring board so that the magnetic flux can be reduced as much as possible. In order to bring the head close to the disk, it is more convenient to pattern the wiring from the head directly onto a microminiature support spring made of stainless steel, and a substrate manufactured by the above method is suitably used.
【0009】[0009]
【発明が解決しようとする課題】しかし、近年、機器の
コンパクト化に伴ない、ハードディスク用基板も精密加
工が求められ、高い耐熱性が求められるようになってき
たため、ハードディスクドライブの磁気ヘッド用サスペ
ンション用配線基材においては、同サスペンションの動
作中に種々の外力によって基板が反ってしまうなどの問
題が生じることが指摘されていた。However, in recent years, with the miniaturization of the equipment, the precision of the substrate for the hard disk has been required and the heat resistance has been required. Therefore, the suspension for the magnetic head of the hard disk drive has been required. It has been pointed out that a problem arises in the wiring substrate for use that the substrate is warped by various external forces during the operation of the suspension.
【0010】このような問題を解決するために、ハード
ディスクサスペンション配線基板として良好な可とう性
を具備するような絶縁材料の採用が望まれていた。しか
し、良好な可とう性に加えて、耐熱性をも両有するよう
な材料は、世の中には知られていなかった。In order to solve such a problem, it has been desired to employ an insulating material having good flexibility as a hard disk suspension wiring board. However, a material that has both heat resistance and good flexibility has not been known in the world.
【0011】[0011]
【課題を解決するための手段】本発明者らは、上述した
熱融着性を有する熱可塑性ポリイミドを接着剤層とする
金属箔張積層板において、フレキシビリティと良好な耐
熱性を示す材料、特にオールポリイミドのハードディス
クサスペンション用に好適に用いることができる材料を
提供することを目的として、鋭意研究を重ねた結果、本
発明に想到した。Means for Solving the Problems The present inventors have developed a metal foil-clad laminate using the above-mentioned thermoplastic polyimide having heat-fusibility as an adhesive layer, a material showing flexibility and good heat resistance, In particular, the inventors of the present invention have made intensive studies for the purpose of providing a material that can be suitably used for an all-polyimide hard disk suspension, and as a result, have arrived at the present invention.
【0012】すなわち、本発明に係るフレキシブル金属
箔張積層板は、少なくとも1種以上の金属箔と熱可塑性
ポリイミド層と耐熱性ベースフィルムとを包含するフレ
キシブル金属箔張積層板において、該熱可塑性ポリイミ
ド層が150℃以上300℃以下のガラス転移温度と1
%以下の吸水率を有する熱可塑性ポリイミドであり、お
よび/または、耐熱性ベースフィルムが、2%以下の吸
水率の非熱可塑性ポリイミドフィルム、または、350
℃以上のガラス転移温度と2%以下の吸水率とを併せ有
する熱可塑性ポリイミドフィルムがそれぞれ用いられ
る。これにより、本発明は、良好な加とう性と耐熱性を
両有するフレキシブル金属箔張積層板、特には、ハード
ディスクドライブサスペンション用フレキシブル金属箔
張積層板を実現し得る。That is, a flexible metal foil-clad laminate according to the present invention is a flexible metal foil-clad laminate comprising at least one or more metal foils, a thermoplastic polyimide layer and a heat-resistant base film. The layer has a glass transition temperature of 150 ° C or more and 300 ° C or less and 1
% Of a thermoplastic polyimide film having a water absorption of not more than 2%, and / or a heat-resistant base film having a water absorption of not more than 2%.
Thermoplastic polyimide films having both a glass transition temperature of not less than ° C. and a water absorption of not more than 2% are used. Thus, the present invention can realize a flexible metal foil-clad laminate having both good flexibility and heat resistance, particularly a flexible metal foil-clad laminate for a hard disk drive suspension.
【0013】[0013]
【発明の実施の形態】以下に、本発明の実施の形態につ
いて説明する。本発明のフレキシブル積層板は、少なく
とも1種以上の薄層金属箔と熱可塑性接着層と耐熱性ベ
ースフィルムとを積層して得られる。Embodiments of the present invention will be described below. The flexible laminate of the present invention is obtained by laminating at least one or more thin metal foils, a thermoplastic adhesive layer, and a heat-resistant base film.
【0014】絶縁層を形成する樹脂層、つまり、熱可塑
性接着層および耐熱性ベースフィルムは、当業者がこの
用途を想定する場合に一般的に想定されうるものであれ
ば何ら制限はないが、特には、ポリイミド系樹脂が好適
に用いられ、これを主成分とすることが好ましい。ま
た、ポリイミド系樹脂は引張伸び率が20%以上あるこ
とにより、ハードディスク用ドライブサスペンション用
フレキシブル金属箔張積層板として好適なフレキシビリ
ティーを有するので望ましい。The resin layer forming the insulating layer, that is, the thermoplastic adhesive layer and the heat-resistant base film are not particularly limited as long as those skilled in the art can generally assume this application. In particular, a polyimide-based resin is suitably used, and it is preferable to use this as a main component. Further, a polyimide resin having a tensile elongation of 20% or more has desirable flexibility as a flexible metal foil-clad laminate for a hard disk drive suspension, and is therefore desirable.
【0015】さらに、本発明のフレキシブル金甌箔張積
層板に用いられる熱可塑性接着層を構成する熱可塑性ポ
リイミドは、その前駆体であるポリアミド酸の繰り返し
単位が下記一般式(2)化4、Further, the thermoplastic polyimide constituting the thermoplastic adhesive layer used in the flexible gold pot foil-clad laminate of the present invention has a repeating unit of polyamic acid, which is a precursor thereof, represented by the following general formula (2):
【0016】[0016]
【化4】 Embedded image
【0017】(式中、R1 は、4価、R2 は、2価の有
機基を示す。)で表されるが、好ましく用いられ得る熱
可塑性ポリイミドの前駆体ポリアミド酸は下記一般式
(1)化5、(Wherein, R 1 represents a tetravalent organic group and R 2 represents a divalent organic group). The precursor polyamic acid of a thermoplastic polyimide which can be preferably used is represented by the following general formula ( 1) Chemical 5,
【0018】[0018]
【化5】 Embedded image
【0019】(式中、kは、1以上の整数、m,nは、
m+nが1以上となるそれぞれ0以上の整数である。
A,Bはそれぞれ同一であっても異なっていてもよい4
価の有機基、X,Yはそれぞれ同一であっても異なって
いてもよい2価の有機基を示す。)で表されるポリアミ
ド酸共重合体を脱水閉環して得ることができる。(Where k is an integer of 1 or more, and m and n are
m + n is an integer of 0 or more, each of which is 1 or more.
A and B may be the same or different 4
X and Y each represent a divalent organic group which may be the same or different. ) Can be obtained by dehydration and ring closure of the polyamic acid copolymer represented by the formula (1).
【0020】上記ポリアミド酸共重合体は、下記一般式
(3)、化6、The polyamic acid copolymer is represented by the following general formula (3):
【0021】[0021]
【化6】 Embedded image
【0022】一般式(4)、化7、The general formula (4),
【0023】[0023]
【化7】 Embedded image
【0024】で表される酸二無水物化合物と下記一般式
(5)、及び、 H2 N−X−NH2 一般式(5) 下記一般式(6) H2 N−Y−NH2 一般式(6) で表されるジアミン化合物とを有機溶媒中で反応させる
ことにより得られが、本発明においては、一般式(3)
中の4価の有機基A及び一般式(4)中の4価の有機基
Bは、下記群(I)化8、An acid dianhydride compound represented by the following general formula (5) and H 2 N—X—NH 2 general formula (5) The following general formula (6) H 2 NY—NH 2 general It is obtained by reacting a diamine compound represented by the formula (6) in an organic solvent.
The tetravalent organic group A in the formula (4) and the tetravalent organic group B in the formula (4) are represented by the following group (I) 8,
【0025】[0025]
【化8】 Embedded image
【0026】から選択される4価の有機基であることが
好ましい。It is preferably a tetravalent organic group selected from
【0027】また、一般式(5)中の2価の有機基X及
び一般式(6)中の2価の有機基Yは、下記群(II)、
化9、The divalent organic group X in the general formula (5) and the divalent organic group Y in the general formula (6) are represented by the following group (II):
Chemical formula 9,
【0028】[0028]
【化9】 Embedded image
【0029】から選択される2価の有機基であることが
好ましい。It is preferably a divalent organic group selected from the group consisting of:
【0030】ポリアミド酸重合反応の手順は公知の方法
を適用できるが、一実施態様を説明すると次の通りであ
る。アルゴン、窒素などの不活性ガス雰囲気中におい
て、一般式(3)の酸二無水物化合物を有機溶媒中に溶
解、又は拡散させ、一般式(5)で表されるジアミン化
合物及び一般式(6)で表されるジアミン化合物を、固
体の状態または有機溶媒溶液の状態で添加する。さら
に、一般式(3)で表される酸二無水物化合物と一般式
(4)で表される酸二無水物化合物の混合物を固体の状
態または有機溶媒溶液の状態で添加し、ポリアミド酸共
重合体溶液を得る。また、この反応において、上記添加
手順とは逆に、まずジアミン化合物の溶液を調製し、こ
の溶液中に固体状の酸二無水物化合物または酸二無水物
化合物の有機溶媒溶液を添加してもよい。このときの反
応温度は−10℃〜0℃が好ましい。反応時間は30分
間〜3時間である。かかる反応により熱可塑性ポリイミ
ドの前駆体であるポリアミド酸溶液が調製される。Known procedures can be applied to the procedure of the polyamic acid polymerization reaction. One embodiment will be described below. In an atmosphere of an inert gas such as argon or nitrogen, the acid dianhydride compound of the general formula (3) is dissolved or diffused in an organic solvent, and the diamine compound represented by the general formula (5) and the general formula (6) ) Is added in a solid state or an organic solvent solution state. Further, a mixture of the acid dianhydride compound represented by the general formula (3) and the acid dianhydride compound represented by the general formula (4) is added in a solid state or an organic solvent solution, and the polyamic acid copolymer is added. Obtain a polymer solution. In this reaction, contrary to the above-described addition procedure, first, a solution of a diamine compound is prepared, and a solid acid dianhydride compound or an organic solvent solution of an acid dianhydride compound is added to the solution. Good. The reaction temperature at this time is preferably from -10C to 0C. The reaction time is 30 minutes to 3 hours. By this reaction, a polyamic acid solution which is a precursor of the thermoplastic polyimide is prepared.
【0031】また、酸二無水物全モル量と、ジアミン全
モル量の割合は、実質的に等モルであることが好まし
い。The ratio of the total molar amount of the acid dianhydride to the total molar amount of the diamine is preferably substantially equimolar.
【0032】ポリアミド酸の合成反応に使用される有機
溶媒としては、例えばジメチルスルホキシド、ジエチル
スルホキシド等のスルホキシド系溶媒、N,N−ジメチ
ルホルムアミド、N,N−ジエチルホルムアミド等のホ
ルムアミド系溶媒、N,N−ジメチルアセトアミド、
N,N−ジエチルアセトアミド等のアセトアミド系溶媒
を挙げることができる。これらを1種類のみで用いるこ
とも、2種あるいは3種以上からなる混合溶媒も用いる
こともできる。また、これらの極性溶媒とポリアミド酸
の非溶媒とからなる混合溶媒も用いることもできる。ポ
リアミド酸の非溶媒としては、アセトン、メタノール、
エタノール、イソプロパノール、ベンゼン、メチルセロ
ソルブ等を挙げることができる。Examples of the organic solvent used in the synthesis reaction of the polyamic acid include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; N-dimethylacetamide,
Acetamide solvents such as N, N-diethylacetamide can be mentioned. These may be used alone or in combination of two or more. Further, a mixed solvent composed of these polar solvents and a non-solvent of polyamic acid can also be used. Non-solvents for polyamic acid include acetone, methanol,
Ethanol, isopropanol, benzene, methyl cellosolve and the like can be mentioned.
【0033】熱可塑性ポリイミドおよびその前駆体であ
るポリアミド酸の分子量は特に限定されるものではない
が、耐熱性接着剤としての強度を維持するためには、数
平均分子量が5万以上、さらには8万以上、特には10
万以上が好ましい。分子量は、GPC(ゲル浸透クロマ
トグラフィー)により測定が可能である。平均分子量
が、5万未満では、できあがったフィルムが脆くなり、
一方10万を超えるとポリアミド酸ワニスの粘度が高く
なりすぎて、取り扱いが難しくなって好ましくない。The molecular weight of the thermoplastic polyimide and the polyamic acid as a precursor thereof are not particularly limited. However, in order to maintain the strength as a heat-resistant adhesive, the number average molecular weight is 50,000 or more, and 80,000 or more, especially 10
10,000 or more is preferable. The molecular weight can be measured by GPC (gel permeation chromatography). If the average molecular weight is less than 50,000, the resulting film becomes brittle,
On the other hand, if it exceeds 100,000, the viscosity of the polyamic acid varnish becomes too high, and handling becomes difficult, which is not preferable.
【0034】次に、これらポリアミド酸からポリイミド
を得る方法について説明する。ポリアミド酸をイミド化
する方法としては、熱的方法又は化学的方法により脱水
閉環(イミド化)する方法が挙げられる。Next, a method for obtaining polyimide from these polyamic acids will be described. Examples of the method for imidizing the polyamic acid include a method for dehydration ring closure (imidization) by a thermal method or a chemical method.
【0035】熱的方法により脱水閉環(イミド化)する
方法には、常圧下での加熱による方法と、減圧下での加
熱による方法が挙げられる。常圧下で加熱を行う場合、
例えば、まず有機溶媒を蒸発させるために150℃以下
の温度で約5分間〜90分間加熱を行うのが好ましい。
続いて、これを好ましくは150〜400℃の温度範囲
で加熱してイミド化する。イミド化の最終段階の加熱温
度は300〜400℃が好ましい。一方、減圧下で加熱
を行う場合は、溶媒除去とイミド化が同時に進行する。
加熱温度としては、150℃〜200℃の範囲が好まし
い。減圧下で加熱すると、系内から水が除去されやすく
常圧加熱に比べてイミド環の加水分解及びそれに伴う分
子量低下が起こりにくい点で常圧加熱よりも有利であ
る。The method of dehydration ring closure (imidization) by a thermal method includes a method by heating under normal pressure and a method by heating under reduced pressure. When heating under normal pressure,
For example, it is preferable to perform heating at a temperature of 150 ° C. or less for about 5 minutes to 90 minutes to evaporate the organic solvent.
Subsequently, it is preferably imidized by heating in a temperature range of 150 to 400 ° C. The heating temperature in the final stage of imidization is preferably 300 to 400 ° C. On the other hand, when heating is performed under reduced pressure, solvent removal and imidization proceed simultaneously.
The heating temperature is preferably in the range of 150C to 200C. Heating under reduced pressure is more advantageous than normal pressure heating in that hydrolysis of the imide ring and accompanying molecular weight reduction are less likely to occur than in normal pressure heating, since water is easily removed from the system.
【0036】化学的方法によりに脱水閉環(イミド化)
する方法では、上記ポリアミド酸溶液に化学量論以上の
脱水剤と触媒量の第3級アミンとを加え、熱的方法によ
り脱水閉環する場合と同様の方法で処理すると、熱的方
法よりも短時間で所望のポリイミドが得られる。触媒と
して使用される第3級アミンとしては、ピリジン、α-
ピコリン、β- ピコリン、γ- ピコリン、トリメチルア
ミン、トリエチルアミン、イソキノリンなどが好まし
く、脱水剤としては無水酢酸等の脂肪族酸無水物が用い
られる。Dehydration ring closure (imidization) by a chemical method
In the method, a dehydrating agent having a stoichiometric amount or more and a catalytic amount of a tertiary amine are added to the polyamic acid solution, and the resultant is treated in the same manner as in the case of dehydration ring closure by a thermal method. The desired polyimide can be obtained in time. Tertiary amines used as catalysts include pyridine, α-
Picoline, β-picoline, γ-picoline, trimethylamine, triethylamine, isoquinoline and the like are preferable, and an aliphatic acid anhydride such as acetic anhydride is used as a dehydrating agent.
【0037】上記方法で、生成されたポリイミド樹脂
は、有機溶媒を蒸発させることにより、保存性の高い、
固体として得ることもできる。固体として得られる本発
明のフレキシブル金属箔張積層板の接着層に用いられる
ポリイミド樹脂は、有機溶媒に溶解して、ベースフィル
ムに積層する。The polyimide resin produced by the above method has a high preservability by evaporating the organic solvent.
It can also be obtained as a solid. The polyimide resin used for the adhesive layer of the flexible metal foil-clad laminate of the present invention obtained as a solid is dissolved in an organic solvent and laminated on a base film.
【0038】上記得られたポリイミド樹脂を溶解させる
有機溶媒としては、例えばジメチルスルホキシド、ジエ
チルスルホキシド等のスルホキシド系溶媒、N,N−ジ
メチルホルムアミド、N,N−ジエチルホルムアミド等
のホルムアミド系溶媒、N,N−ジメチルアセトアミ
ド、N,N−ジエチルアセトアミド等のアセトアミド系
溶媒、N−メチル−2−ピロリドン等のピロリドン系溶
媒、テトラヒドロフラン、1,4−ジオキサン、ジオキ
ソラン等のエーテル系溶媒を挙げることができる。これ
らを1種類のみで用いることも、2種あるいは3種以上
からなる混合溶媒も用いることもできる。これらの有機
溶媒中、ポリイミド樹脂は、5〜40重量%、好ましく
は10〜30重量%溶解されていることが取り扱いの面
から好ましいが、これに限定されない。以上の手順によ
り、本発明の金属箔張積層板の熱可塑性接着層である熱
可塑性ポリイミド層を構成する熱可塑性ポリイミドの溶
液が得られる。Examples of the organic solvent for dissolving the polyimide resin obtained above include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and N, N-diethylformamide. Acetamide solvents such as N-dimethylacetamide and N, N-diethylacetamide; pyrrolidone solvents such as N-methyl-2-pyrrolidone; ether solvents such as tetrahydrofuran, 1,4-dioxane and dioxolane can be mentioned. These may be used alone or in combination of two or more. In these organic solvents, the polyimide resin is preferably dissolved in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, from the viewpoint of handling, but is not limited thereto. By the above procedure, a solution of the thermoplastic polyimide constituting the thermoplastic polyimide layer which is the thermoplastic adhesive layer of the metal foil clad laminate of the present invention is obtained.
【0039】あるいは、上記ポリイミド樹脂は、反応溶
液に溶解したワニス状態のまま、接着層としてベースフ
ィルムに塗布することもできる。さらに、ポリアミド酸
溶液の状態で、ベースフィルムに塗布し、加熱乾燥させ
て、イミド化させることもできる。Alternatively, the polyimide resin can be applied to a base film as an adhesive layer in a varnish state dissolved in a reaction solution. Further, in the state of a polyamic acid solution, it can be applied to a base film, dried by heating, and imidized.
【0040】上記のようにして得られる本発明の接着層
に用いられる熱可塑性ポリイミドは、ガラス転移温度の
値が150℃以上300℃以下で、かつ、吸水率の値が
1%以下である。このような特性を有する熱可塑性ポリ
イミドを、フレキシブル金属箔張積層板の熱可塑性接着
層に用いると、吸湿処理後にも高い半田耐熱性を示し4
0℃/90%/96時間吸湿処理後の半田ディップ試験
においても外観異常が発生しない特性を有する金属箔張
積層板が得ることができる。The thermoplastic polyimide used for the adhesive layer of the present invention obtained as described above has a glass transition temperature of 150 ° C. or more and 300 ° C. or less, and a water absorption value of 1% or less. When a thermoplastic polyimide having such properties is used for the thermoplastic adhesive layer of a flexible metal foil-clad laminate, it exhibits high solder heat resistance even after moisture absorption.
A metal foil-clad laminate having characteristics in which appearance abnormality does not occur even in a solder dip test after a moisture absorption treatment at 0 ° C./90%/96 hours can be obtained.
【0041】次に、本発明の金属箔張積層板に用いられ
る耐熱性ベースフィルムについて説明する。本発明に用
いられる耐熱性ベースフィルムとしては、ポリイミドフ
ィルム、ポリアミドイミド、ポリベンズイミダゾール、
ポリベンズオキサゾール、ポリフェニレンサルファイ
ド、ポリエーテルエーテルケトン、ポリエーテルスルホ
ン、ポリエーテルイミド等からなる耐熱性ベースフィル
ムが、好ましく用いられ得るが、ポリイミドフィルムが
特に好ましい。ポリイミドフィルムとしては、ピロメリ
ット酸2無水物と4,4´−ジアミノジフェニルエーテ
ルとから得られるポリイミドに代表される非熱可塑性ポ
リイミドが好ましいが、特には、2%以下の吸水率のポ
リイミド系樹脂を用いると、吸湿処理後にも高い半田耐
熱性を示し40℃/90%/96時間吸湿処理後の半田
ディップ試験においても外観異常が発生しない金属箔張
積層板が得られることから、望ましい。また、ガラス転
移温度が350℃以上である熱可塑性ポリイミドフィル
ムも耐熱性ベースフィルムとして好ましく用いることが
できる。このような特性を有するポリイミドフィルム
は、例えば、ポリイミドフィルム商品名アピカルHP
(鐘淵化学工業株式会社製)が用いられる。Next, the heat-resistant base film used for the metal foil-clad laminate of the present invention will be described. As the heat-resistant base film used in the present invention, a polyimide film, polyamide imide, polybenzimidazole,
A heat-resistant base film made of polybenzoxazole, polyphenylene sulfide, polyetheretherketone, polyethersulfone, polyetherimide, or the like can be preferably used, but a polyimide film is particularly preferable. As the polyimide film, a non-thermoplastic polyimide typified by a polyimide obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether is preferable. In particular, a polyimide resin having a water absorption of 2% or less is preferably used. It is desirable to use a metal foil-clad laminate that exhibits high solder heat resistance even after the moisture absorption treatment and does not cause abnormal appearance even in a solder dip test after the moisture absorption treatment at 40 ° C./90%/96 hours. Further, a thermoplastic polyimide film having a glass transition temperature of 350 ° C. or higher can also be preferably used as the heat-resistant base film. A polyimide film having such characteristics is, for example, a polyimide film brand name Apical HP
(Kanebuchi Chemical Industry Co., Ltd.) is used.
【0042】次に、耐熱性ベースフィルムに上述の熱可
塑性ポリイミド溶液を塗布して熱可塑性ポリイミド層を
形成する。あるいは耐熱性ベースフィルムに熱可塑性ポ
リイミドの前駆体であるポリアミド酸を塗布し、ベース
フィルム上で熱的方法または化学的方法によりポリイミ
ドに転化して熱可塑性ポリイミド層を形成する方法も採
りうる。Next, the above-mentioned thermoplastic polyimide solution is applied to the heat-resistant base film to form a thermoplastic polyimide layer. Alternatively, a method in which a polyamic acid, which is a precursor of a thermoplastic polyimide, is applied to a heat-resistant base film and converted into polyimide by a thermal or chemical method on the base film to form a thermoplastic polyimide layer may be employed.
【0043】上記耐熱性ベースフィルム上に熱可塑性ポ
リイミド層形成したものと金属箔とを加熱下で加圧積層
して本発明の金属箔張積層板は完成する。積層方法とし
ては多段プレス機バッチ式で行う方式や、ダブルベルト
プレス機や熱ロール加圧ラミネート機で連続式で行う方
式が挙げられるが、生産性や設備コストの点から熱ロー
ル加圧方式で連続的に製造する方法が好ましく、多段ラ
ミネートすれば生産性は更に向上し得る。The heat-resistant base film having the thermoplastic polyimide layer formed thereon and the metal foil are laminated under pressure under heating to complete the metal foil-clad laminate of the present invention. Examples of the laminating method include a multi-stage press machine using a batch system, and a continuous system using a double belt press machine or a hot roll press laminating machine.From the viewpoint of productivity and equipment costs, the hot roll press method is used. A continuous production method is preferable, and productivity can be further improved by laminating in multiple stages.
【0044】なお、金属箔積層基板に使用される薄層金
属箔は、特に限定されないが、SUS箔、銅合金箔、ア
ルミ箔等を用いうる。The thin metal foil used for the metal foil laminated substrate is not particularly limited, but SUS foil, copper alloy foil, aluminum foil and the like can be used.
【0045】また、本発明にかかるフレキシブル金属箔
張積層板は、可とう性が要求されるフレキシブル基板、
特には、ハードディスクサスペンション用フレキシブル
金属箔張積層板に用いられることから、耐熱性ベースフ
ィルムの厚みは、5μm以上20μm以下、特には、5
μm以上10μm以下が好ましく用いられ、熱可塑性接
着層の厚みは、5μm以上20μm以下が好ましく用い
られ、特には、5μm以上10μm以下が好ましく用い
られる。また、金属箔の厚みは、5μm以上18μm以
下が、特には、5μm以上18μm以下が好ましく用い
られ得る。Further, the flexible metal foil-clad laminate according to the present invention is a flexible substrate requiring flexibility.
In particular, since the heat-resistant base film is used for a flexible metal foil-clad laminate for a hard disk suspension, the thickness of the heat-resistant base film is 5 μm or more and 20 μm or less, particularly 5 μm or less.
The thickness of the thermoplastic adhesive layer is preferably 5 μm or more and 20 μm or less, and particularly preferably 5 μm or more and 10 μm or less. Further, the thickness of the metal foil is preferably 5 μm or more and 18 μm or less, and particularly preferably 5 μm or more and 18 μm or less.
【0046】上記のようにして得られた、本発明にかか
るフレキシブル金属箔張積層板は、150℃以上300
℃以下のガラス転移温度と1%以下の吸水率を有する熱
可塑性ポリイミドを熱可塑性ポリイミド層として用い、
また、耐熱性ベースフィルムが、2%以下の吸水率の非
熱可塑性ポリイミドフィルム、または、350℃以上の
ガラス転移温度と2%以下の吸水率とを併せ有する熱可
塑性ポリイミドフィルムがそれぞれ用いられる。The flexible metal foil-clad laminate of the present invention obtained as described above has a
Using a thermoplastic polyimide having a glass transition temperature of not more than 1 ° C. and a water absorption of not more than 1% as a thermoplastic polyimide layer,
In addition, a non-thermoplastic polyimide film having a water absorption of 2% or less as a heat-resistant base film, or a thermoplastic polyimide film having a glass transition temperature of 350 ° C. or more and a water absorption of 2% or less is used.
【0047】従って、良好な加とう性と耐熱性を両有
し、半田耐熱性に優れたフレキシブル金属箔張積層板を
得ることができ、さらには、所定の厚さを有する金属箔
および、ベースフィルムとの組み合わせにより、特に、
ハードディスクドライブサスペンション用に適するフレ
キシブル金属箔張積層板として有用である。Accordingly, it is possible to obtain a flexible metal foil-clad laminate having both good flexibility and heat resistance and excellent solder heat resistance. Further, a metal foil having a predetermined thickness and a base can be obtained. Especially in combination with film,
It is useful as a flexible metal foil-clad laminate suitable for hard disk drive suspension.
【0048】以上、本発明に係るフレキシブル金属箔張
積層板の実施の形態について説明したが、本発明はこれ
らによって限定されるものではなく、その趣旨を逸脱し
ない範囲で当業者の知識に基づき、改良、変更、修正を
加えた様態で実施しうるものである。Although the embodiments of the flexible metal foil-clad laminate according to the present invention have been described above, the present invention is not limited to these, and based on the knowledge of those skilled in the art without departing from the spirit thereof. It can be implemented with improvements, changes, and modifications.
【0049】[0049]
【実施例】以下、本発明にかかるハードディスクドライ
ブサスペンション用フレキシブル金属箔張積層板の実施
例を詳しく説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a flexible metal foil-clad laminate for a hard disk drive suspension according to the present invention will be described in detail below.
【0050】接着強度(kgf/cm)は、JIS C
6481に従い測定した。The adhesive strength (kgf / cm) is measured according to JIS C
6481.
【0051】半田耐熱性は、JIS C 6471に従
い、40℃、90%RH、96時間調整後、280℃
10秒間浸漬、の条件で測定し、外観上の白化現象と剥
離現象の異常の有無を判定した。According to JIS C 6471, the solder heat resistance is 280 ° C. after adjusting at 40 ° C., 90% RH and 96 hours.
The measurement was performed under the condition of immersion for 10 seconds, and the presence or absence of abnormalities of the whitening phenomenon and the peeling phenomenon on the appearance was determined.
【0052】熱可塑性ポリイミド層のガラス転移温度
(Tg)は、上記得られた熱可塑性ポリイミド溶液を、
キャストし、乾燥して得られる25μmの熱可塑性ポリ
イミド単体のフィルムに加工したサンプルについて粘弾
性測定装置によって測定した。The glass transition temperature (Tg) of the thermoplastic polyimide layer was determined by using the above-obtained thermoplastic polyimide solution as follows:
A sample processed into a 25 μm thermoplastic polyimide simple film obtained by casting and drying was measured by a viscoelasticity measuring device.
【0053】吸水率は、ASTM D570に基づいた
測定により、算出した。上記25μmの熱可塑性ポリイ
ミド単体のフィルムについて、さらに150℃、30分
間乾燥させたものの重量をW1とし、20℃環境下、蒸
留水中に24時間浸漬後、表面をふき取ったものの重量
をW2とし、下記式によりの重量増加率を算出した。 吸水率(%)=(W2−W1)÷W1×100The water absorption was calculated by measurement based on ASTM D570. The above-mentioned 25 μm film of the thermoplastic polyimide alone was further dried at 150 ° C. for 30 minutes, and the weight of the film was W1. Under a 20 ° C. environment, the film was immersed in distilled water for 24 hours. The weight increase rate was calculated by the equation. Water absorption (%) = (W2−W1) ÷ W1 × 100
【0054】また、耐屈曲性評価試験(MIT)は、J
IS C5016に準拠し、R=0.38の屈曲治具を
装着したミツトヨMIT試験機(株式会社ミツトヨ製)
によってCCLが破断するまでの回数を測定した。The flex resistance evaluation test (MIT)
Mitutoyo MIT tester (manufactured by Mitutoyo Corporation) equipped with a bending jig of R = 0.38 based on IS C5016
The number of times until the CCL was broken was measured.
【0055】[0055]
【実施例1】系全体を氷水で冷やし、窒素置換をした2
000mlの三口のセパラブルフラスコに123.1gの
2,2−ビス[4 −(4−アミノフェノキシ)フェニ
ル]プロパン(以下、BAPPという。)を716.2
gのジメチルホルムアミド(以下、DMFという。)に
投入し15分間攪拌した。続いて67.7gの3,3
´,4,4´−ベンゾフェノンテトラカルボン酸二無水
物(以下、BTDAという。)、20gのDMFを用い
て投入した。続いて、33.9gの3,3´,4,4´
−エチレングリコールジベンゾエートテトラカルボン酸
二無水物(以下、TMEGという。) を20gのDMF
を用いて投入し30分間撹拌した。30分間の撹拌の
後、さらに4.1gのTMEGを36.9gのDMFに
溶かした溶液をフラスコ内の溶液の粘度に注意しながら
徐々に投入し、その後1時間撹拌しながら放置し、固形
分濃度23重量%のポリアミド酸溶液を得た。Example 1 The whole system was cooled with ice water and purged with nitrogen.
In a 000 ml three-neck separable flask, 123.1 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as BAPP) was 716.2 g.
g of dimethylformamide (hereinafter referred to as DMF) and stirred for 15 minutes. Then 67.7g of 3,3
', 4,4'-Benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA) and 20 g of DMF were added. Then, 33.9 g of 3,3 ', 4,4'
-Ethylene glycol dibenzoate tetracarboxylic dianhydride (hereinafter referred to as TMEG) in 20 g of DMF
And stirred for 30 minutes. After stirring for 30 minutes, a solution in which 4.1 g of TMEG was dissolved in 36.9 g of DMF was gradually added while paying attention to the viscosity of the solution in the flask. A polyamic acid solution having a concentration of 23% by weight was obtained.
【0056】得られた熱可塑性ポリイミドを、別途サン
プル用に25μm厚さのフィルムとし、のガラス転移温
度(Tg)、吸水率を測定した。結果を表1に示す。The obtained thermoplastic polyimide was separately formed into a film having a thickness of 25 μm for a sample, and the glass transition temperature (Tg) and the water absorption were measured. Table 1 shows the results.
【0057】得られたポリアミド酸溶液を、ポリイミド
フィルム(アピカル12.5HP;鐘淵化学工業株式会
社製、吸水率1.4%)の両面に、熱可塑性ポリイミド
層の最終片面厚みが6μmとなるように塗布した後、1
40℃、220℃で各2分間加熱して溶媒を除去し、熱
可塑性ポリイミド層を形成した。このものの吸水率は、
0.8%であった。このものの両面に18μm厚の圧延
銅箔を重ね、その上に25μm厚ポリイミドフィルムを
離型フィルムとして配設して、ダブルベルトプレス機に
てラミネートしフレキシブル銅張積層板を得た。ラミネ
ート温度は280℃、圧力70kgf/cm2、ラミネ
ート時間約5分間であった。The resulting polyamic acid solution was coated on both sides of a polyimide film (Apical 12.5HP; manufactured by Kaneka Chemical Co., Ltd., water absorption: 1.4%) to a final thickness of one side of a thermoplastic polyimide layer of 6 μm. After application, 1
The solvent was removed by heating at 40 ° C. and 220 ° C. for 2 minutes each to form a thermoplastic polyimide layer. The water absorption of this product is
0.8%. A 18 μm-thick rolled copper foil was overlaid on both sides of this, and a 25 μm-thick polyimide film was provided thereon as a release film, and laminated with a double belt press to obtain a flexible copper-clad laminate. The lamination temperature was 280 ° C., the pressure was 70 kgf / cm 2, and the lamination time was about 5 minutes.
【0058】得られた銅張積層板について、接着強度
(kgf/cm)、半田耐熱性を測定した。また、耐屈
曲性評価試験(MIT)を行った。その結果を表1に示
す。With respect to the obtained copper-clad laminate, the adhesive strength (kgf / cm) and the solder heat resistance were measured. Further, a bending resistance evaluation test (MIT) was performed. Table 1 shows the results.
【0059】[0059]
【実施例2】実施例1のBTDAとTMEGのかわりに
3,3’,4,4’−ビフェニルテトラカルボン酸二無
水物(以下、BPDAという。) 88. 2gを用いた以
外は実施例1と同様にしてフレキシブル銅張積層板を作
製した。結果を表1に示す。Example 2 Example 1 was repeated except that 88.2 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA) was used in place of BTDA and TMEG in Example 1. A flexible copper-clad laminate was produced in the same manner as described above. Table 1 shows the results.
【0060】[0060]
【実施例3】実施例1のBTDAのかわりにオキシフタ
ル酸二無水物(以下、ODPAという。) 65. 1gを
用いた以外は実施例1と同様にしてフレキシブル銅張積
層板を作製した。結果を表1に示す。Example 3 A flexible copper-clad laminate was produced in the same manner as in Example 1, except that 65.1 g of oxyphthalic dianhydride (hereinafter referred to as ODPA) was used instead of BTDA of Example 1. Table 1 shows the results.
【0061】[0061]
【比較例1】実施例1のアピカル12.5HPのかわり
にアピカル12.5NPIを用い、接着剤にピクシオD
ワニス( 鐘淵化学工業株式会社製、Tg140℃、吸水
率0.4%) た以外は実施例1と同様にしてフレキシブ
ル銅張積層板を作製した。結果を表1に示す。Comparative Example 1 Apical 12.5NPI was used in place of Apical 12.5HP of Example 1, and Pixio D was used as an adhesive.
A flexible copper-clad laminate was prepared in the same manner as in Example 1 except that varnish (manufactured by Kanegafuchi Chemical Co., Ltd., Tg 140 ° C, water absorption 0.4%) was used. Table 1 shows the results.
【0062】[0062]
【比較例2】BTDAとベンゾフェノンジアミンから合
成された熱可塑性ポリイミドを接着剤として用いた以外
は実施例1と同様にしてフレキシブル銅張積層板を作製
した。結果を表1に示す。Comparative Example 2 A flexible copper-clad laminate was produced in the same manner as in Example 1 except that a thermoplastic polyimide synthesized from BTDA and benzophenonediamine was used as an adhesive. Table 1 shows the results.
【0063】[0063]
【表1】 [Table 1]
【0064】[0064]
【発明の効果】以上のように、本発明のフレキシブル金
属箔張積層板は、吸水率、ガラス転移温度の特性を有す
るベースフィルムおよび熱可塑性接着層の組み合わせに
より、積層板とした場合に、基板のそりがなく、フレキ
シビリティーと半田耐熱性に優れ、ハードディスクサス
ペンション用基板として、また、他方、FPCやリジッ
ト‐フレックス基板材料、COF及びLOCパッケー
ジ、MCM等の今後の新規高密度実装用途材料としても
好適に用いられる。As described above, the flexible metal foil-clad laminate of the present invention can be used as a substrate when a laminate is obtained by combining a base film having characteristics of water absorption and glass transition temperature and a thermoplastic adhesive layer. No warpage, excellent flexibility and solder heat resistance, and as a substrate for hard disk suspension, and on the other hand, as a new high-density packaging material for FPC, rigid-flex substrate, COF and LOC packages, MCM, etc. Is also preferably used.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) H05K 1/03 610 H05K 1/03 610N 670 670Z // C08L 79:08 C08L 79:08 Fターム(参考) 4F071 AA60 AA86 AF10Y AF21Y AF26 AH12 BA02 BB02 BC01 BC02 4F100 AB01A AB04A AB10A AB31A AB33A AK49B AT00B BA02 GB43 JJ03 JJ03B JK06 JK17 4J043 PA04 QB31 UA121 UA122 UA131 UA132 UA141 UA151 UA152 UB011 UB021 UB022 UB051 UB052 UB121 UB122 UB131 UB132 UB152 UB172 UB301 UB302 VA011 VA021 VA031 VA041 VA042 VA061 VA062 VA081 XA13 XA15 XA16 ZA02 ZA05 ZA33 ZA34 ZB01 ZB47 5D068 AA01 BB01 CC01 EE19 GG03──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H05K 1/03 610 H05K 1/03 610N 670 670Z // C08L 79:08 C08L 79:08 F term (reference) 4F071 AA60 AA86 AF10Y AF21Y AF26 AH12 BA02 BB02 BC01 BC02 4F100 AB01A AB04A AB10A AB31A AB33A AK49B AT00B BA02 GB43 JJ03 JJ03B JK06 JK17 4J043 PA04 QB31 UA121 UA122 UA131 UA132 UA141 UA151 UA152 UB011 UB021 UB022 UB051 UB052 UB121 UB122 UB131 UB132 UB152 UB172 UB301 UB302 VA011 VA021 VA031 VA041 VA042 VA061 VA062 VA081 XA13 XA15 XA16 ZA02 ZA05 ZA33 ZA34 ZB01 ZB47 5D068 AA01 BB01 CC01 EE19 GG03
Claims (10)
塑性接着層と耐熱性ベースフィルムとを包含するフレキ
シブル金属箔張積層板において、該熱可塑性接着層と耐
熱性ベースフィルムが、主成分が、引張伸び率20%以
上を有するポリイミド系樹脂であり、かつ、該熱可塑性
接着層が、150℃以上300℃以下のガラス転移温度
と1%以下の吸水率を有する熱可塑性ポリイミド系樹脂
で構成される、フレキシブル金属箔張積層板。1. A flexible metal foil-clad laminate comprising at least one or more thin metal foils, a thermoplastic adhesive layer, and a heat-resistant base film, wherein the thermoplastic adhesive layer and the heat-resistant base film are mainly composed of Is a polyimide resin having a tensile elongation of 20% or more, and the thermoplastic adhesive layer is a thermoplastic polyimide resin having a glass transition temperature of 150 ° C. or more and 300 ° C. or less and a water absorption of 1% or less. Composed, flexible metal foil clad laminate.
一般式(1) 【化1】 (式中、kは、1以上の整数、m,nは、m+nが1以
上となるそれぞれ0以上の整数である。A,Bはそれぞ
れ同一であっても異なっていてもよい4価の有機基、
X,Yはそれぞれ同一であっても異なっていてもよい2
価の有機基を示す。)で表されるポリアミド酸を脱水閉
環してなる熱可塑性ポリイミドからなる、請求項1に記
載するフレキシブル金属箔張積層板。2. The thermoplastic polyimide resin is represented by the following general formula (1): (In the formula, k is an integer of 1 or more, and m and n are each an integer of 0 or more where m + n is 1 or more. A and B may be the same or different and each may be a tetravalent organic compound. Group,
X and Y may be the same or different 2
It shows a valent organic group. The flexible metal foil-clad laminate according to claim 1, comprising a thermoplastic polyimide obtained by dehydrating and ring-closing the polyamic acid represented by the formula (1).
(I) 【化2】 から選択される少なくとも1種の4価の有機基である、
請求項2に記載するフレキシブル金属箔張積層板。3. A and B in the general formula (1) are represented by the following group (I): Is at least one tetravalent organic group selected from
The flexible metal foil-clad laminate according to claim 2.
群(II)化3 【化3】 から選択される二価の有機基である、請求項2または3
に記載するフレキシブル金属箔張積層板。4. X and Y in the general formula (1) are represented by the following group (II): 4. A divalent organic group selected from the group consisting of:
The flexible metal foil-clad laminate according to the above.
の吸水率の非熱可塑性ポリイミドフィルム、または、3
50℃以上のガラス転移温度及び2%以下の吸水率とを
あわせ持つ熱可塑性ポリイミドフィルムである、請求項
1乃至請求項4のいずれか1項に記載するフレキシブル
金属箔張積層板。5. The non-thermoplastic polyimide film having a water absorption of 2% or less, wherein
The flexible metal foil-clad laminate according to any one of claims 1 to 4, which is a thermoplastic polyimide film having a glass transition temperature of 50 ° C or more and a water absorption of 2% or less.
はアルミ箔のいずれかから選択される、請求項1乃至請
求項5のいずれか1項に記載するフレキシブル金属箔張
積層板。6. The flexible metal foil-clad laminate according to claim 1, wherein the metal foil is selected from one of a copper alloy foil, a SUS foil, and an aluminum foil.
半田浴ディップ試験(280℃10秒間)において外観
異常が発生しないことを特徴する、請求項1乃至請求項
6のいずれか1項に記載するフレキシブル金属箔張積層
板。7. The solder bath dip test (280 ° C. for 10 seconds) after a moisture absorption treatment at 40 ° C./90%/96 hours does not cause any abnormal appearance. The flexible metal foil-clad laminate according to the above.
するフレキシブル金属箔張積層板を用いる、ハードディ
スクドライブサスペンション用フレキシブル金属箔張積
層板。8. A flexible metal foil-clad laminate for a hard disk drive suspension, using the flexible metal foil-clad laminate according to claim 1. Description:
上20μm以下の膜厚を有する薄層フィルムである、請
求項7に記載するハードディスクドライブサスペンショ
ン用フレキシブル金属箔張積層板。9. The flexible metal foil-clad laminate for a hard disk drive suspension according to claim 7, wherein the heat-resistant base film is a thin film having a thickness of 5 μm or more and 20 μm or less.
下の厚みを有する薄層金属箔である、請求項8または9
に記載するハードディスクドライブサスペンション用フ
レキシブル金属箔張積層板。10. The metal foil according to claim 8, wherein the metal foil is a thin metal foil having a thickness of 5 μm or more and 18 μm or less.
The flexible metal foil-clad laminate for a hard disk drive suspension described in the above item.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2000133945A JP2001315256A (en) | 2000-05-02 | 2000-05-02 | Flexible metal foil-clad laminate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000133945A JP2001315256A (en) | 2000-05-02 | 2000-05-02 | Flexible metal foil-clad laminate |
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JP2001315256A true JP2001315256A (en) | 2001-11-13 |
Family
ID=18642325
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JP2000133945A Pending JP2001315256A (en) | 2000-05-02 | 2000-05-02 | Flexible metal foil-clad laminate |
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Cited By (10)
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WO2004073975A1 (en) * | 2003-02-18 | 2004-09-02 | Mitsui Chemicals, Inc. | Layered polyimide/metal product |
JP2004338159A (en) * | 2003-05-14 | 2004-12-02 | Kanegafuchi Chem Ind Co Ltd | Adhesive laminated film for csp and flexible metal clad laminated sheet comprising it |
JP2005096251A (en) * | 2003-09-25 | 2005-04-14 | Kaneka Corp | Adhesive film and flexible metal-clad laminate with improved hygroscopic solder resistance obtained therefrom |
JP2005150728A (en) * | 2003-11-12 | 2005-06-09 | E I Du Pont De Nemours & Co | Multilayer substrate having at least two dissimilar polyamide layers and a conductive layer and useful for electronics-type applications, and compositions related thereto |
WO2006033267A1 (en) * | 2004-09-24 | 2006-03-30 | Kaneka Corporation | Novel polyimide film and adhesive film and flexible metal-clad laminate both obtained with the same |
JP2006124685A (en) * | 2004-09-29 | 2006-05-18 | Ube Ind Ltd | Polyimide film for COF and laminate |
JP2006281458A (en) * | 2005-03-31 | 2006-10-19 | Tomoegawa Paper Co Ltd | Double-sided metal plate |
JP2007291409A (en) * | 2007-07-09 | 2007-11-08 | Kyocera Chemical Corp | Molded article |
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2000
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2004073975A1 (en) * | 2003-02-18 | 2004-09-02 | Mitsui Chemicals, Inc. | Layered polyimide/metal product |
JP2004338159A (en) * | 2003-05-14 | 2004-12-02 | Kanegafuchi Chem Ind Co Ltd | Adhesive laminated film for csp and flexible metal clad laminated sheet comprising it |
JP2005096251A (en) * | 2003-09-25 | 2005-04-14 | Kaneka Corp | Adhesive film and flexible metal-clad laminate with improved hygroscopic solder resistance obtained therefrom |
JP2005150728A (en) * | 2003-11-12 | 2005-06-09 | E I Du Pont De Nemours & Co | Multilayer substrate having at least two dissimilar polyamide layers and a conductive layer and useful for electronics-type applications, and compositions related thereto |
JP2012077302A (en) * | 2004-09-24 | 2012-04-19 | Kaneka Corp | Novel polyimide film and adhesive film and flexible metal-clad laminate both obtained with the same |
WO2006033267A1 (en) * | 2004-09-24 | 2006-03-30 | Kaneka Corporation | Novel polyimide film and adhesive film and flexible metal-clad laminate both obtained with the same |
US8426548B2 (en) | 2004-09-24 | 2013-04-23 | Kaneka Corporation | Polyimide film and adhesive film and flexible metal-clad laminate both obtained with the same |
JP2006124685A (en) * | 2004-09-29 | 2006-05-18 | Ube Ind Ltd | Polyimide film for COF and laminate |
JP2006281458A (en) * | 2005-03-31 | 2006-10-19 | Tomoegawa Paper Co Ltd | Double-sided metal plate |
US8338560B2 (en) | 2005-04-25 | 2012-12-25 | Kaneka Corporation | Polyimide film and use thereof |
JP2007291409A (en) * | 2007-07-09 | 2007-11-08 | Kyocera Chemical Corp | Molded article |
JP2022153664A (en) * | 2015-09-29 | 2022-10-12 | ミネベアミツミ株式会社 | Strain gauge, load sensor, strain gauge manufacturing method, and load sensor manufacturing method |
JP7543349B2 (en) | 2015-09-29 | 2024-09-02 | ミネベアミツミ株式会社 | Strain gauge, load sensor, method for manufacturing strain gauge, and method for manufacturing load sensor |
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