JP6106082B2 - 補強板一体型フレキシブルプリント基板 - Google Patents
補強板一体型フレキシブルプリント基板 Download PDFInfo
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- JP6106082B2 JP6106082B2 JP2013512431A JP2013512431A JP6106082B2 JP 6106082 B2 JP6106082 B2 JP 6106082B2 JP 2013512431 A JP2013512431 A JP 2013512431A JP 2013512431 A JP2013512431 A JP 2013512431A JP 6106082 B2 JP6106082 B2 JP 6106082B2
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- Prior art keywords
- insulating film
- film
- reinforcing plate
- bis
- resin
- Prior art date
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- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
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- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 5
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- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 5
- JRRDISHSXWGFRF-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOC JRRDISHSXWGFRF-UHFFFAOYSA-N 0.000 description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 4
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
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- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
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- 239000001257 hydrogen Substances 0.000 description 4
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
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- 238000000790 scattering method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray 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
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- PLCFYBDYBCOLSP-UHFFFAOYSA-N tris(prop-2-enyl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound C=CCOC(=O)CC(O)(CC(=O)OCC=C)C(=O)OCC=C PLCFYBDYBCOLSP-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
- PJEUXMXPJGWZOZ-UHFFFAOYSA-L zinc;diphenylphosphinate Chemical compound [Zn+2].C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 PJEUXMXPJGWZOZ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- 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
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
- H05K1/0281—Reinforcement details thereof
-
- 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
- H05K1/18—Printed circuits structurally associated with non-printed electric components
- H05K1/189—Printed circuits structurally associated with non-printed electric components characterised by the use of a flexible or folded printed circuit
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- 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
- H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
- H05K2201/2009—Reinforced areas, e.g. for a specific part of a flexible printed circuit
-
- 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
- H05K3/0058—Laminating printed circuit boards onto other substrates, e.g. metallic substrates
- H05K3/0064—Laminating printed circuit boards onto other substrates, e.g. metallic substrates onto a polymeric substrate
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Materials For Photolithography (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Structure Of Printed Boards (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本願発明の補強板一体型FPCの構成図を図1に示すが、これに限定されるものではない。先ず、配線パターン(2)およびベースフィルム(1)からなる(D)配線パターン付きフィルム(3)上に(C)絶縁膜(4)を形成し、FPC(5)を得る。続いて、(A)補強板(6)を(B)熱硬化性接着剤(7)を介して、(C)絶縁膜(4)上に形成する事で本願発明の補強板一体型FPCを得ることができる。
本願発明における(A)補強板とは、フレキシブルプリント基板を補強する目的で用いられる材料であれば限定されるものではない。例えば、厚手の補強板材料としては、紙フェノール、ガラス・エポキシ板等が挙げられる。また、薄型の補強板材料としては、ポリイミドフィルム、ポリエステルフィルム、金属板(銅板、アルミ板)等が挙げられる。
本願発明における(B)熱硬化性接着剤とは、一般的な熱硬化性接着剤であれば適宜選択することができるが、例えば、エポキシ系またはアクリル系の熱硬化性接着剤が挙げられる。エポキシ系の熱硬化性接着剤としては、例えば、ソニーケミカル&インフォメーションデバイス株式会社製の商品名D3410、D3411等が挙げられる。また、アクリル系の熱硬化性接着剤としては、例えば、デュポン社製の商品名パイララックスLF0100、パイララックスFR0100等が挙げられる。また、アクリル/エポキシ系熱硬化性接着剤としては、例えば、ソニーケミカル&インフォメーションデバイス株式会社製の商品名D3450、D3451等が挙げられる。
本願発明における(C)絶縁膜とは、絶縁性を有する厚さ5〜100μmの膜である。
本願発明における(a)バインダーポリマーとは、有機溶媒に対して可溶性であり、重量平均分子量が、ポリエチレングリコール換算で1,000以上、1,000,000以下のポリマーである。
使用装置:東ソーHLC−8220GPC相当品
カラム :東ソー TSK gel Super AWM−H(6.0mmI.D.×15cm)×2本
ガードカラム:東ソー TSK guard column Super AW−H
溶離液:30mM LiBr+20mM H3PO4 in DMF
流速:0.6mL/min
カラム温度:40℃
検出条件:RI:ポラリティ(+)、レスポンス(0.5sec)
試料濃度:約5mg/mL
標準品:PEG(ポリエチレングリコール)。
で示されるジオール化合物と、下記一般式(2)
で示されるジイソシアネート化合物を反応させることにより、下記一般式(3)
で示されるウレタン結合を含有する繰り返し単位を含有する構造として得られる。
で示される水酸基及び少なくとも1つの(メタ)アクリロイル基を含有する化合物及び/又は下記一般式(5)
で示されるイソシアネート基及び少なくとも1つの(メタ)アクリロイル基を含有する化合物を反応させることにより得られる。
で示される2つの水酸基及び1つのカルボキシル基を含有する化合物を反応させることにより得られる。
で示されるテトラカルボン酸二無水物を反応させることにより得られる。
本願発明における(b)球状有機ビーズとは、炭素を含む球状ポリマーで、楕円状のものも含まれる。
装置 :株式会社堀場製作所製 LA−950V2相当品
測定方式:レーザー回折/散乱式。
補強板一体型FPCにおいて、5mm×3mmの範囲をカッターナイフで切り出し、エポキシ系包埋樹脂及びカバーガラスを使用して切り出した補強板一体型FPCの両面に保護膜層及びカバーガラス層を形成した後、絶縁膜の厚み方向の断面をイオンビームによるクロスセクションポリッシャ加工を行った。
使用装置:日本電子株式会社製 SM−09020CP相当品
加工条件:加速電圧 6kV
(絶縁膜の断面観察)
上記得られた絶縁膜の厚み方向の断面について、走査型電子顕微鏡により観察を行った。
使用装置:株式会社日立ハイテクノロジーズ製 S−3000N相当品
観察条件:加速電圧 15kV
検出器 :反射電子検出(組成モード)
倍率 :1000倍。
本願発明の(c)リン、アルミニウム及びマグネシウムからなる群から選ばれる少なくとも1種の元素を含有する微粒子とは、構造中に少なくとも1つのリン、アルミニウム及びマグネシウムからなる群から選ばれる少なくとも1種の元素を有している微粒子である。
使用装置:株式会社堀場製作所製 EMAX−7000相当品
分析条件:加速電圧 15kV 積算時間900秒。
本願発明の(d)熱硬化性樹脂は、(C)絶縁膜の樹脂組成物を構成する要素の一つであり、加熱により架橋構造を形成し、熱硬化剤として機能する化合物である。本発明においては、(C)絶縁膜が、(d)熱硬化性樹脂を含有している樹脂組成物から得られることが好ましい。(d)熱硬化性樹脂としては、例えば、エポキシ樹脂、ビスマレイミド樹脂、ビスアリルナジイミド樹脂、アクリル樹脂、メタクリル樹脂、ヒドロシリル硬化樹脂、アリル硬化樹脂、不飽和ポリエステル樹脂等の熱硬化性樹脂;高分子鎖の側鎖または末端にアリル基、ビニル基、アルコキシシリル基、ヒドロシリル基、等の反応性基を有する側鎖反応性基型熱硬化性高分子等を用いることができる。上記熱硬化性成分の1種又は2種以上を適宜組み合わせて用いればよい。(d)成分としては、この中でも、エポキシ樹脂を用いることがより好ましい。エポキシ樹脂成分を含有することにより、絶縁膜に対して耐熱性を付与できると共に、(D)配線パターン付きフィルムに対する接着性、更には(B)熱硬化性接着剤との密着性を付与することができるため好ましい。上記エポキシ樹脂とは、分子内に少なくとも1個のエポキシ基を含む化合物であり、例えば、ビスフェノールA型エポキシ樹脂としては、ジャパンエポキシレジン株式会社製の商品名jER828、jER1001、jER1002、株式会社ADEKA製の商品名アデカレジンEP−4100E、アデカレジンEP−4300E、日本化薬株式会社製の商品名RE−310S、RE−410S、大日本インキ株式会社製の商品名エピクロン840S、エピクロン850S、エピクロン1050、エピクロン7050、東都化成株式会社製の商品名エポトートYD−115、エポトートYD−127、エポトートYD−128、ビスフェノールF型エポキシ樹脂としては、ジャパンエポキシレジン株式会社製の商品名jER806、jER807、株式会社ADEKA製の商品名アデカレジンEP−4901E、アデカレジンEP−4930、アデカレジンEP−4950、日本化薬株式会社製の商品名RE−303S、RE−304S、RE−403S、RE−404S、DIC株式会社製の商品名エピクロン830、エピクロン835、東都化成株式会社製の商品名エポトートYDF−170、エポトートYDF−175S、エポトートYDF−2001、ビスフェノールS型エポキシ樹脂としては、DIC株式会社製の商品名エピクロンEXA−1514、水添ビスフェノールA型エポキシ樹脂としては、ジャパンエポキシレジン株式会社製の商品名jERYX8000、jERYX8034、jERYL7170、株式会社ADEKA製の商品名アデカレジンEP−4080E、DIC株式会社製の商品名エピクロンEXA−7015、東都化成株式会社製の商品名エポトートYD−3000、エポトートYD−4000D、ビフェニル型エポキシ樹脂としては、ジャパンエポキシレジン株式会社製の商品名jERYX4000、jERYL6121H、jERYL6640、jERYL6677、日本化薬株式会社製の商品名NC−3000、NC−3000H、フェノキシ型エポキシ樹脂としては、ジャパンエポキシレジン株式会社製の商品名jER1256、jER4250、jER4275、ナフタレン型エポキシ樹脂としては、DIC株式会社製の商品名エピクロンHP−4032、エピクロンHP−4700、エピクロンHP−4200、日本化薬株式会社製の商品名NC−7000L、フェノールノボラック型エポキシ樹脂としては、ジャパンエポキシレジン株式会社製の商品名jER152、jER154、日本化薬株式会社製の商品名EPPN−201−L、DIC株式会社製の商品名エピクロンN−740、エピクロンN−770、東都化成株式会社製の商品名エポトートYDPN−638、クレゾールノボラック型エポキシ樹脂としては、日本化薬株式会社製の商品名EOCN−1020、EOCN−102S、EOCN−103S、EOCN−104S、DIC株式会社製の商品名エピクロンN−660、エピクロンN−670、エピクロンN−680、エピクロンN−695、トリスフェノールメタン型エポキシ樹脂としては、日本化薬株式会社製の商品名EPPN−501H、EPPN−501HY、EPPN−502H、ジシクロペンタジエン型エポキシ樹脂としては、日本化薬株式会社製の商品名XD−1000、DIC株式会社製の商品名エピクロンHP−7200、アミン型エポキシ樹脂としては、東都化成株式会社の商品名エポトートYH−434、エポトートYH−434L、可とう性エポキシ樹脂としては、ジャパンエポキシレジン株式会社製の商品名jER871、jER872、jERYL7175、jERYL7217、DIC株式会社製の商品名エピクロンEXA−4850、ウレタン変性エポキシ樹脂としては、株式会社ADEKA製の商品名アデカレジンEPU−6、アデカレジンEPU−73、アデカレジンEPU−78−11、ゴム変性エポキシ樹脂としては、株式会社ADEKA製の商品名アデカレジンEPR−4023、アデカレジンEPR−4026、アデカレジンEPR−1309、キレート変性エポキシ樹脂としては、株式会社ADEKA製の商品名アデカレジンEP−49−10、アデカレジンEP−49−20等が挙げられる。
本願発明の(e)光重合開始剤とは、(C)絶縁膜の樹脂組成物を構成する要素の一つであり、UVなどのエネルギーによって活性化し、ラジカル重合性基含有樹脂の反応を開始・促進させる化合物である。したがって、本願発明の(e)光重合開始剤を含有する樹脂組成物は、感光性樹脂組成物となる。本願発明は、(C)絶縁膜が(e)光重合開始剤を含有している感光性樹脂組成物から得られることが好ましい。本願発明の(e)成分としては、例えば、ミヒラ−ズケトン、4,4’−ビス(ジエチルアミノ)ベンゾフェノン、4,4’,4’’−トリス(ジメチルアミノ)トリフェニルメタン、2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ジイミダゾール、アセトフェノン、ベンゾイン、2−メチルベンゾイン、ベンゾインメチルエ−テル、ベンゾインエチルエ−テル、ベンゾインイソプロピルエ−テル、ベンゾインイソブチルエ−テル、2−t−ブチルアントラキノン、1,2−ベンゾ−9,10−アントラキノン、メチルアントラキノン、チオキサントン、2,4−ジエチルチオキサントン、2−イソプロピルチオキサントン、1−ヒドロキシシクロヘキシルフェニルケトン、ジアセチルベンジル、ベンジルジメチルケタ−ル、ベンジルジエチルケタ−ル、2(2’−フリルエチリデン)−4,6−ビス(トリクロロメチル)−S−トリアジン、2[2’(5’’−メチルフリル)エチリデン]−4,6−ビス(トリクロロメチル)−S−トリアジン、2(p−メトキシフェニル)−4,6−ビス(トリクロロメチル)−S−トリアジン、2,6−ジ(p−アジドベンザル)−4−メチルシクロヘキサノン、4,4’−ジアジドカルコン、ジ(テトラアルキルアンモニウム)−4,4’−ジアジドスチルベン−2,2’−ジスルフォネ−ト、2,2−ジメトキシ−1,2−ジフェニルエタン−1−オン、1−ヒドロキシ−シクロヘキシル−フェニル−ケトン、2−ヒドロキシ−2−メチル−1−フェニル−プロパン−1−オン、1−[4−(2−ヒドロキシエトキシ)−フェニル]−2−ヒドロキシ−2−メチル−1−プロパン−1−オン、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)−ブタン−1、ビス(2,4,6−トリメチルベンゾイル)−フェニルフォスフィンオキサイド、ビス(2,6−ジメトキシベンゾイル)−2,4,4−トリメチル−ペンチルフォスフィンオキサイド、2,4,6−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、2−ヒドロキシ−2−メチル−1−フェニル−プロパン−1−ケトン、ビス(n5−2,4−シクロペンタジエン−1−イル)−ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)−フェニル)チタニウム、1,2−オクタンジオン,1−[4−(フェニルチオ)−,2−(O−ベンゾイルオキシム)]、ヨード二ウム,(4−メチルフェニル)[4−(2−メチルプロピル)フェニル]−ヘキサフルオロフォスフェート(1−)、エチル−4−ジメチルアミノベンゾエート、2−エチルヘキシル−4−ジメチルアミノベンゾエート、エタノン,1−[9−エチル−6−(2−メチルベンゾイル)−9H−カルバゾール−3−イル]−,1−(O−アセチルオキシオム)などが挙げられる。上記(e)光重合開始剤は適宜選択することが望ましく、1種以上を混合させて用いることが望ましい。
本願発明の(C)絶縁膜の樹脂組成物には、更に必要に応じて、ラジカル重合性樹脂、着色剤、密着性付与剤、重合禁止剤、溶媒等の添加剤を用いることができる。
本願発明の配線パターン付きフィルムとは、厚さ5〜100μmのベースフィルムの片面又は両面に配線パターンを有するフィルムである。本願発明における配線パターン付きフィルムの作製方法は、特に限定されないが、例えば、ベースフィルムに導体層を形成することにより、フレキシブル金属張積層板を作製し、導体層をパターンエッチングする事によって作製することができる。
〔合成例1〕
攪拌機、温度計、滴下漏斗、および窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2−ビス(2−メトキシエトキシ)エタン)100.0gを仕込み、窒素気流下で攪拌しながら80℃まで昇温した。これに、室温で予め混合しておいた、メタクリル酸12.0g(0.14モル)、メタクリル酸ベンジル28.0g(0.16モル)、メタクリル酸ブチル60.0g(0.42モル)、ラジカル重合開始剤としてアゾビスイソブチロニトリル0.5gを80℃に保温した状態で3時間かけて滴下漏斗から滴下した。滴下終了後、反応溶液を攪拌しながら90℃まで昇温し、反応溶液の温度を90℃に保ちながら更に2時間攪拌し、本願発明のポリ(メタ)アクリル系樹脂溶液を得た(a−1)。得られたポリ(メタ)アクリル系樹脂溶液の固形分濃度は48%、重量平均分子量は48,000、酸価は78mgKOH/gであった。尚、固形分濃度、重量平均分子量、酸価は下記の方法で測定した。
JIS K 5601−1−2に従って測定を行った。尚、乾燥条件は150℃×1時間の条件を選択した。
合成したポリ(メタ)アクリル系樹脂((a)バインダーポリマーに対応)の重量平均分子量を下記条件にて測定した。
使用装置 :東ソーHLC−8220GPC相当品
カラム :東ソー TSK gel Super AWM-H(6.0mmI.D.×15cm)×2本
ガードカラム:東ソー TSK guard column Super AW-H
溶離液 :30mM LiBr+20mM H3PO4 in DMF
流速 :0.6mL/min
カラム温度:40℃
検出条件 :RI:ポラリティ(+)、レスポンス(0.5sec)
試料濃度 :約5mg/mL
標準品 :PEG(ポリエチレングリコール)
<酸価>
JIS K 5601−2−1に従って、合成したポリ(メタ)アクリル系樹脂((a)バインダーポリマーに対応)の酸価の測定を行った。
攪拌機、温度計、及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2−ビス(2−メトキシエトキシ)エタン)30.00gを仕込み、これに、ノルボルネンジイソシアネート10.31g(0.050モル)を仕込み、窒素気流下で攪拌しながら80℃に加温して溶解させた。この溶液に、ポリカーボネートジオール50.00g(0.025モル)(旭化成株式会社製:商品名PCDL T5652、重量平均分子量2000)及び2,2−ビス(ヒドロキシメチル)ブタン酸3.70g(0.025モル)をメチルトリグライム30.00gに溶解した溶液を1時間かけて添加した。この溶液を5時間80℃で加熱攪拌を行い反応させた。上記反応を行うことで分子内にウレタン結合を有する樹脂溶液を得た(a−2)。得られた樹脂溶液の固形分濃度は52%、重量平均分子量は5,600、固形分の酸価は22mgKOH/gであった。尚、固形分濃度、重量平均分子量、酸価は合成例1と同様の方法で測定した。
攪拌機、温度計、及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2−ビス(2−メトキシエトキシ)エタン)130.60gを仕込み、これに、3,3’,4,4’−オキシジフタル酸二無水物31.02g(0.100モル)、ビス[4−(3−アミノフェノキシ)フェニル]スルホン34.45g(0.080モル)、ポリ(テトラメチレン/3−メチルテトラメチレンエーテル)グリコールビス(4−アミノベンゾエート)24.76g(0.020モル)を仕込み、窒素気流下で30分攪拌してポリアミド酸溶液を得た。
<樹脂組成物の調製>
合成例で得られた(a)バインダーポリマー、(b)球状有機ビーズ、(c)リン、アルミニウム及びマグネシウムからなる群から選ばれる少なくとも1種の元素を含有する微粒子、(d)熱硬化性樹脂、及びその他の成分を添加して樹脂組成物を作製した。それぞれの構成原料の樹脂固形分での配合量及び原料の種類を表1に記載する。なお、表中の溶媒である1,2−ビス(2-メトキシエトキシ)エタンは上記合成例で合成した樹脂溶液等に含まれる溶剤等も含めた全溶剤量である。混合溶液を脱泡装置で溶液中の泡を完全に脱泡して下記評価を実施した。
<2>大日精化工業株式会社製 架橋ウレタン系球状有機フィラーの製品名、平均粒子径7μm
<3>クラリアントジャパン株式会社製 リン及びアルミニウム元素を含有する微粒子(ジエチルホスフィン酸アルミニウム塩)の製品名、平均粒子径2.5μm
<4>DIC株式会社製 グリシジルアミン型の多官能エポキシ樹脂の製品名
<5>日本アエロジル株式会社製 シリカ粒子の製品名。
上記で調整した樹脂組成物を、ベーカー式アプリケーターを用いて、片面配線パターン付きフィルム(電解銅箔の厚み12μm、ポリイミドフィルムは株式会社カネカ製アピカル25NPI、エポキシ系接着剤で銅箔を接着している)の銅箔面上に、最終乾燥厚みが25μmになるように100mm×100mmの面積に流延・塗布し、80℃で20分乾燥した。次いで、150℃のオーブン中で30分加熱硬化させて樹脂組成物の絶縁膜を片面配線パターン付きフィルム上に形成し、FPCを作製した。次いで、補強板であるポリイミドフィルム(株式会社カネカ製、商品名アピカル125NPI)上に熱硬化性接着剤(Dupont社製、商品名パイララックスLF0100)を185℃の熱ロールラミで仮圧着し、積層体1を作製した。その後、上記で作製したFPCの絶縁膜表面と上記積層体1の熱硬化性接着剤面とを熱プレスにて165℃/90minで圧着し、補強板一体型FPC評価試験片を作製した。
得られた補強板一体型FPCについて、以下の項目につき評価を行った。評価結果を表2に記載する。
上記<補強板一体型FPC評価試験片の作製>で得られた試験片を用いて、JIS K5400に従って碁盤目テープ法で評価した。
○:碁盤目テープ法で剥がれの無いもの
△:升目の95%以上が残存しているもの
×:升目の残存量が80%未満のもの。
上記<補強板一体型FPC評価試験片の作製>で得られた試験片を用いて、260℃で完全に溶解してある半田浴に補強板一体型FPCの補強板面が接する様に浮かべて10秒後に引き上げた。その操作を3回行い、熱硬化性接着剤と絶縁膜との接着強度をJIS K5400に従って碁盤目テープ法で評価した。
○:碁盤目テープ法で剥がれの無いもの
△:升目の95%以上が残存しているもの
×:升目の残存量が80%未満のもの。
上記<補強板一体型FPC評価試験片の作製>で得られた試験片を用いて、260℃:ピークトップ260℃×20secのリフロー条件でリフロー処理した後の試験片の外観を観察する。
○:試験前後で外観に変化の無いもの
×:試験後、試験片の何れかの積層界面で膨れが発生するもの。
上記<補強板一体型FPC評価試験片の作製>の項目と同様の方法で、25μm厚みのポリイミドフィルム(株式会社カネカ製、商品名アピカル25NPI)表面に樹脂組成物の絶縁膜を形成し、積層体2を作製した。次いで、補強板であるポリイミドフィルム(株式会社カネカ製、商品名アピカル125NPI)上に熱硬化性接着剤(Dupont社製、商品名パイララックスLF0100)を185℃の熱ロールラミで仮圧着し、積層体1を作製した。その後、上記で作製した積層体2の絶縁膜表面と積層体1の熱硬化性接着剤面とを熱プレスにて165℃/90minで圧着し、補強板一体型FPC評価試験片を作製した。上記で得られた試験片を50mm×50mmの面積に切り出して平滑な台の上に補強板面が上面になるように置き、試験片端部の反り高さを測定した。測定部位の模式図を図2に示す。反り量が少ない程、補強板一体型FPCにした場合も反り量が低下することになる。反り量は5mm以下であることが好ましい。
<感光性樹脂組成物の調製>
合成例で得られた(a)バインダーポリマー、(b)球状有機ビーズ、(c)リン、アルミニウム及びマグネシウムからなる群から選ばれる少なくとも1種の元素を含有する微粒子、(d)熱硬化性樹脂、(e)光重合開始剤、及びその他の成分を添加して感光性樹脂組成物を作製した。それぞれの構成原料の樹脂固形分での配合量及び原料の種類を表3に記載する。なお、表中の溶媒である1,2−ビス(2−メトキシエトキシ)エタンは上記合成例で合成した樹脂溶液等に含まれる溶剤等も含めた全溶剤量である。混合溶液を脱泡装置で溶液中の泡を完全に脱泡して下記評価を実施した。
<2>大日精化工業株式会社製 架橋ウレタン系球状有機フィラーの製品名、平均粒子径7μm
<3>クラリアントジャパン株式会社製 リン及びアルミニウム元素を含有する微粒子(ジエチルホスフィン酸アルミニウム塩)の製品名、平均粒子径2.5μm
<4>DIC株式会社製 グリシジルアミン型の多官能エポキシ樹脂の製品名
<5>日本アエロジル株式会社製 シリカ粒子の製品名
<6>日本化薬株式会社製 ウレタン変性エポキシアクリレート樹脂の製品
<7>BASF ジャパン株式会社製 光重合開始剤の製品名
<8>新中村化学社製 製品名NKエステルA−9300(エトキシ化イソシアヌル酸トリアクリレート)。
上記で調整した感光性樹脂組成物を、ベーカー式アプリケーターを用いて、片面配線パターン付きフィルム(電解銅箔の厚み12μm、ポリイミドフィルムは株式会社カネカ製アピカル25NPI、エポキシ系接着剤で銅箔を接着している)上の銅箔面上に、最終乾燥厚みが25μmになるように100mm×100mmの面積に流延・塗布し、80℃で20分乾燥した。次いで、300mJ/cm2の積算露光量の紫外線を照射して露光した。次いで、1.0重量%の炭酸ナトリウム水溶液を30℃に加熱した溶液を用いて、1.0kgf/mm2の吐出圧で90秒スプレー現像を行った。現像後、純水で十分洗浄した後、150℃のオーブン中で30分加熱硬化させて感光性樹脂組成物の絶縁膜を片面配線パターン付きフィルム上に形成し、FPCを作製した。次いで、補強板であるポリイミドフィルム(株式会社カネカ製、商品名アピカル125NPI)上に熱硬化性接着剤(Dupont社製、商品名パイララックス LF0100)を185℃の熱ロールラミで仮圧着し、積層体1を作製した。その後、上記で作製したFPCの絶縁膜表面と積層体1の熱硬化性接着剤面とを熱プレスにて165℃/90minで圧着し、補強板一体型FPC評価試験片を作製した。
得られた補強板一体型FPCについて、以下の項目につき評価を行った。評価結果を表4に記載する。
上記<補強板一体型FPC評価試験片の作製>で得られた試験片を用いて、JIS K5400に従って碁盤目テープ法で評価した。
○:碁盤目テープ法で剥がれの無いもの
△:升目の95%以上が残存しているもの
×:升目の残存量が80%未満のもの。
上記<補強板一体型FPC評価試験片の作製>で得られた試験片を用いて、260℃で完全に溶解してある半田浴に補強板一体型FPCの補強板面が接する様に浮かべて10秒後に引き上げた。その操作を3回行い、熱硬化性接着剤と絶縁膜との接着強度をJIS K5400に従って碁盤目テープ法で評価した。
○:碁盤目テープ法で剥がれの無いもの
△:升目の95%以上が残存しているもの
×:升目の残存量が80%未満のもの。
上記<補強板一体型FPC評価試験片の作製>で得られた試験片を用いて、260℃:ピークトップ260℃×20secのリフロー条件でリフロー処理した後の試験片の外観を観察する。
○:試験前後で外観に変化の無いもの
×:試験後、試験片の何れかの積層界面で膨れが発生するもの。
上記<補強板一体型FPC評価試験片の作製>の項目と同様の方法で、25μm厚みのポリイミドフィルム(株式会社カネカ製、商品名アピカル25NPI)表面に感光性樹脂組成物の絶縁膜を形成し、積層体2を作製した。次いで、補強板であるポリイミドフィルム(株式会社カネカ製、商品名アピカル125NPI)上に熱硬化性接着剤(Dupont社製、商品名パイララックス LF0100)を185℃の熱ロールラミで仮圧着し、積層体1を作製した。その後、上記で積層体2の絶縁膜表面と積層体1の熱硬化性接着剤面とを熱プレスにて165℃/90minで圧着し、補強板一体型FPC評価試験片を作製した。上記で得られた試験片を50mm×50mmの面積に切り出して平滑な台の上に補強板面が上面になるように置き、試験片端部の反り高さを測定した。測定部位の模式図を図2に示す。反り量が少ない程、補強板一体型FPCにした場合も反り量が低下することになる。反り量は5mm以下であることが好ましい。
2.配線パターン
3.配線パターン付きフィルム
4.絶縁膜
5.FPC
6.補強板
7.熱硬化性接着剤
8.平滑な台
9.反り量
10.絶縁膜積層フィルム
Claims (4)
- (A)補強板、(B)熱硬化性接着剤、(C)絶縁膜、(D)配線パターン付きフィルムの順で構成された補強板一体型フレキシブルプリント基板であって、
該(C)絶縁膜が、少なくとも(a)バインダーポリマー及び(b)球状有機ビーズを含有し、
該(b)球状有機ビーズは、架橋ウレタン系球状有機ビーズであることを特徴とする補強板一体型フレキシブルプリント基板。 - 更に上記(C)絶縁膜が、(c)リン、アルミニウム、及びマグネシウムからなる群から選ばれる少なくとも1種の元素を含有する微粒子を含有していることを特徴とする請求項1に記載の補強板一体型フレキシブルプリント基板。
- 更に上記(C)絶縁膜が、(d)熱硬化性樹脂を含有している樹脂組成物から得られることを特徴とする請求項1または2に記載の補強板一体型フレキシブルプリント基板。
- 更に上記(C)絶縁膜が、(e)光重合開始剤を含有している感光性樹脂組成物から得られることを特徴とする請求項1〜3のいずれか1項に記載の補強板一体型フレキシブルプリント基板。
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-
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WO2012147855A1 (ja) | 2012-11-01 |
US9204528B2 (en) | 2015-12-01 |
KR102021845B1 (ko) | 2019-09-18 |
JPWO2012147855A1 (ja) | 2014-07-28 |
TWI525172B (zh) | 2016-03-11 |
TW201302970A (zh) | 2013-01-16 |
KR20140018951A (ko) | 2014-02-13 |
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CN103503582B (zh) | 2017-07-18 |
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