JP4183765B2 - Manufacturing method of flexible printed wiring board - Google Patents
Manufacturing method of flexible printed wiring board Download PDFInfo
- Publication number
- JP4183765B2 JP4183765B2 JP22595795A JP22595795A JP4183765B2 JP 4183765 B2 JP4183765 B2 JP 4183765B2 JP 22595795 A JP22595795 A JP 22595795A JP 22595795 A JP22595795 A JP 22595795A JP 4183765 B2 JP4183765 B2 JP 4183765B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyimide precursor
- solvent
- wiring board
- precursor resin
- 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.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000011347 resin Substances 0.000 claims description 65
- 229920005989 resin Polymers 0.000 claims description 65
- 229920001721 polyimide Polymers 0.000 claims description 33
- 239000004642 Polyimide Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 21
- 239000004020 conductor Substances 0.000 claims description 15
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 15
- 239000002609 medium Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002798 polar solvent Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 125000005462 imide group Chemical group 0.000 claims 1
- 238000007654 immersion Methods 0.000 description 12
- -1 diamine compound Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 2
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 2
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- 241000989747 Maba Species 0.000 description 2
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- UMMYYBOQOTWQTD-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-n,n'-diphenylpropane-1,3-diamine Chemical compound C=1C=CC=CC=1NC(F)(F)C(F)(F)C(F)(F)NC1=CC=CC=C1 UMMYYBOQOTWQTD-UHFFFAOYSA-N 0.000 description 1
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- YUZSJKBFHATJHV-UHFFFAOYSA-N 2-[4-[2-[4-(2-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C(=CC=CC=3)N)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 YUZSJKBFHATJHV-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- PQFRTJPVZSPBFI-UHFFFAOYSA-N 3-(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=CC=CC(C(F)(F)F)=C1N PQFRTJPVZSPBFI-UHFFFAOYSA-N 0.000 description 1
- MFTFTIALAXXIMU-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MFTFTIALAXXIMU-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明はポリイミド前駆体樹脂溶液を導体上に直接塗布してなるフレキシブルプリント配線用基板の製法に関するものである。
【０００２】
【従来の技術】
フレキシブルプリント配線用基板は一般に導体とポリイミド樹脂の絶縁体とを接着剤で接着して製造されている。しかし、この方法では耐熱性、耐薬品性、難燃性、電気特性、あるいは密着性といった特性は接着剤に支配されてしまい、ポリイミドの優れた諸特性を充分に生かすことができず高機能化の点で十分なものでなかった。
【０００３】
接着剤を用いず、銅箔等の導体上にポリイミド前駆体樹脂溶液を直接塗布し、乾燥および硬化してフレキシブルプリント配線用基板を製造することは特開昭５８−１９００９３号公報、特開昭６１−１８２９４１号公報等で知られている。しかし、一般に樹脂の線膨張係数は導体より大きい値であるため、この方法においては、高温で乾燥硬化ののち室温に冷却すると樹脂と導体の線膨張係数の差に起因する熱応力のためカールをしたり、フレキシブルプリント配線用基板の導体をエッチングするとひずみの解除により寸法が大きく変化するという問題があるため、樹脂の線膨張係数を小さくすることがより望まれている。
【０００４】
熱膨張係数を小さくする手段として特開昭６３−２４５９８８号公報に開示されているような低熱膨張性のポリイミド樹脂を用いる方法が提案されている。
【０００５】
一方、ポリイミド前駆体樹脂の合成には極性溶媒が用いられるが、このポリイミド前駆体樹脂中に含まれる残存溶媒が硬化後のポリイミド樹脂の熱膨張係数に影響を及ぼすことが本願発明者等によって明らかになってきた。
【０００６】
溶媒の回収を目的とし、ポリイミドフィルムを水系の媒体中で脱溶媒させることは特公昭６２−４４０９号公報で知られている。
【０００７】
【発明が解決しようとする課題】
本発明の目的は、樹脂の線膨張係数を小さくし、カールがなく、良好な寸法安定性を有するフレキシブル配線用基板の製造方法を提供することにある。
【０００８】
【課題を解決するための手段】
すなわち本発明は、導体上に直接ポリイミド前駆体樹脂溶液を塗布し、形成されたフィルム中の樹脂のイミド閉環率が３０％未満で、樹脂濃度が５０重量％以上となるまで加熱乾燥を行ったのち、導体上にポリイミド前駆体樹脂が保持されている状態のままポリイミド前駆体樹脂溶液を構成している溶媒と親和性があり、ポリイミド前駆体樹脂に対しては貧溶媒である極性溶媒の媒体中に浸漬したのち取り出し、次いで１２０℃以上に加熱してイミド化することを特徴とするフレキシブルプリント配線用基板の製造方法である。
【０００９】
【発明の実施の形態】
本発明に用いる導体は任意の金属箔で可能であり、好ましくは銅、アルミ、および、ＳＵＳ箔であり、さらに好ましくは５〜１５０μｍの厚みの銅箔である。
【００１０】
ポリイミド前駆体樹脂はジアミン化合物と酸無水物化合物とを極性溶媒中０〜２００℃で反応させて合成される。この際イミド化反応が起きると溶解性が低下し、好ましくない。
【００１１】
極性溶媒としてはN-メチルピロリドン（ＮＭＰ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルスルフォキサイド（ＤＭＳＯ）、硫酸ジメチル、スルホラン、ブチロラクトン、クレゾ−ル、フェノール、ハロゲン化フェノール、シクロヘキサノン、ジオキサン、テトラヒドロフラン、ダイグライム、等が挙げられる。
【００１２】
ジアミン化合物としてはｐ−フェニレンジアミン、ｍ−フェニレンジアミン、2'−メトキシ−4,4'−ジアミノベンズアニリド、4,4'−ジアミノジフェニルエ−テル、ジアミノトルエン、4,4'−ジアミノジフェニルメタン、3,3'−ジメチル−4,4'−ジアミノジフェニルメタン、3,3'−ジメチル−4,4'−ジアミノジフェニルメタン、2,2 −ビス〔4-(4−アミノフェノキシ）フェニル〕プロパン、1,2-ビス（アニリノ）エタン、ジアミノジフェニルスルホン、ジアミノベンズアニリド、ジアミノベンゾエード、ジアミノジフェニルスルフィド、2,2-ビス（p-アミノフェニル）プロパン、2,2-ビス（p-アミノフェニル）ヘキサフルオロプロパン、1,5-ジアミノナフタレン、ジアミノトルエン、ジアミノベンゾトリフルオライド、1,4-ビス（p-アミノフェノキシ）ベンゼン、4,4'−（p-アミノフェノキシビフェニル、ジアミノアントラキノン、4,4'−ビス(3−アミノフェノキシフェニル）ジフェニルスルホン、1,3-ビス（アニリノ）ヘキサフルオロプロパン、1,4-ビス（アニリノ）オクタフルオロプロパン、1,5-ビス（アニリノ）デカフルオロプロパン、1,7-ビス（アニリノ）テトラデカフルオロプロパン、
下記一般式
【化１】
【００１３】
またテトラカルボン酸無水物並びにその誘導体としては次の様なものが挙げられる。なお、ここではテトラカルボン酸として例示するが、これらのエステル化物、酸無水物、酸塩化物も勿論使用できる。ピロメリット酸、3,3',4,4' −ビフェニルテトラカルボン酸、3,3',4,4' −ベンゾフェノンテトラカルボン酸、3,3',4,4' −ジフェニルスルホンテトラカルボン酸、3,3',4,4' −ジフェニルエーテルテトラカルボン酸、2,3,3',4'-ベンゾフェノンテトラカルボン酸、2,3,6,7 −ナフタレンテトラカルボン酸、1,2,5,6 −ナフタレンテトラカルボン酸、3,3',4,4' −ジフェニルメタンテトラカルボン酸、2,2-ビス(3,4−ジカルボキシフェニル) プロパン、2,2-ビス(3,4−ジカルボキシフェニル) ヘキサフルオロプロパン、3,4,9,10- テトラカルボキシペリレン、2,2-ビス[4-(3,4-ジカルボキシフェノキシ) フェニル] プロパン、2,2-ビス[4-(3,4-ジカルボキシフェノキシ) フェニル] ヘキサフルオロプロパン、ブタンテトラカルボン酸、シクロペンタンテトラカルボン酸等がある。また、トリメリット酸及びその誘導体も挙げられる。
【００１４】
また、反応性官能基を有する化合物で変成し、架橋構造やラダー構造を導入することもできる。例えば、次のような方法がある。
（１）下記一般式で表される化合物で変成することによって、ピロロン環やイソインドロキナゾリンジオン環等を導入する。
【化２】
（３）フェノール性水酸基あるいはカルボン酸を有する芳香族アミンで変成し、この水酸基又はカルボキシル基と反応しうる橋かけ剤を形成する。
【００１５】
線膨張係数のコントロール、あるいは機械的特性の調整等を目的として、前記化合物等を用いて共重合あるいはブレンドすることも可能である。また種々の特性改良を目的として無機質、有機質、または金属等の粉末、繊維等を混合して使用することもできる。また導体の酸化を防ぐ目的で酸化防止剤等の添加剤あるいは接着性の向上を目的としてシランカップリング剤を加えることも可能である。また、接着性の向上等を目的として異種のポリマーをブレンドすることも可能である。
【００１６】
ポリイミド樹脂層の厚みは２μｍから３００μｍが好ましく、それ未満であると、回路の絶縁に対する信頼性に乏しく、また折り曲げ等の機械的特性が低い。３００μｍを越えると加熱の際、発泡が生じやすく好ましくない。
【００１７】
前記極性溶媒中でジアミン化合物と酸無水物とを反応させて得られたポリイミド前駆体樹脂溶液は任意の塗工装置を用いて導体上に塗布される。塗工装置としては、グラビアコーター、リバースロールコーター、バーリバースロールコーター、バーコーター、ドクターブレードコーター、カーテンフローコーター、ダイコーター及び多層ダイコーター等を用いることができるが、特性の向上等を目的として複数種のポリイミド前駆体樹脂溶液を多層になるように塗布することも可能である。
【００１８】
本発明に使用する媒体は、樹脂に対しては貧溶媒でありポリイミド前駆体樹脂溶液を構成している溶媒とは親和性のある液体のことである。極性溶媒として使用することが可能な液体として、例えば、低級アルコール、アセトニトリル、酢酸、アセトン、炭酸プロピレン等の単独、混合物、およびこれらの極性溶媒とポリイミド前駆体樹脂溶液を構成している溶媒との混合物等が挙げられる。水系の媒体として使用することが可能な液体として、例えば水単独、水とポリイミド前駆体樹脂溶液を構成している溶媒との混合物、水と低級アルコール、酢酸、アセトン等の混合物等が挙げられる。浸漬処理を行うことにより、樹脂中の溶媒を抽出し加熱による閉環前の溶媒含有率を下げることができる。
【００１９】
また、樹脂の加水分解を防止することなどを目的として添加剤を加えることも可能である。
【００２０】
導体上にポリイミド前駆体樹脂溶液を塗布し、形成されたフィルム中の樹脂濃度が５０重量％以上となるまで加熱乾燥を行ったのち、ポリイミド前駆体樹脂溶液を構成している溶媒と親和性のある媒体に浸漬したのち取り出し、次いで１２０℃以上、好ましくは完全に閉環させる温度（通常２２０℃以上）に加熱されるわけであるが、加熱後の樹脂の線膨張係数は、乾燥時間および温度、媒体への浸漬時間および温度、浸漬後の加熱温度、樹脂の厚みなどによって決まる。
【００２１】
乾燥温度および時間は特に限定されないが、乾燥後のフィルム中の樹脂濃度が５０重量％以下であると、媒体への浸漬時にフィルムが不均一になり十分な強度が得られない。また、乾燥後の閉環率が高くなるほど線膨張係数は小さくなりにくいため、線膨張係数を小さくする効果を十分に得るためには、樹脂の閉環率は３０％以下であることが好ましい。本発明においては、媒体に浸漬する際、導体上に樹脂が保持されているため樹脂の自己支持性は必要でなく、媒体中で樹脂が析出せず均質な最終フィルムが得られる範囲で、浸漬前の樹脂の含有溶媒濃度を高く、樹脂の閉環率を低くすることがより好ましい。浸漬前の樹脂の含有溶媒濃度が低いと線膨張係数を十分小さくするためには媒体中への浸漬時間を長くする必要がある。
【００２２】
媒体への浸漬時間は特に限定されないが、線膨張係数を小さくする効果を十分に得るためには浸漬時間は１分以上６０分以下とすることが好ましい。浸漬時間が１分以下であると媒体への浸漬を行わないものと比較し線膨張係数はあまり小さくならず、浸漬時間が６０分以上では浸漬時間がそれより短いものより線膨張係数は小さくならない。
【００２３】
媒体への浸漬処理後は、媒体からフィルムを取り出し、次いで加熱オーブン等による通常の加熱処理によりイミド化を行う。加熱温度は少なくとも１２０℃以上、好ましくは２２０℃以上である。加熱に際しては、一気に高温に晒すのではなく、徐々に昇温するか、または段階的に昇温していくようにするのが好ましい。
【００２４】
【実施例】
以下、本発明を実施例をもって説明する。
なお、例における略語は以下の通りである。
ＭＡＢＡ：２’−メチル−４，４’−ジアミノベンズアニリド
ＤＤＥ：４，４’−ジアミノジフェニルエーテル
ＰＭＤＡ：ピロメリット酸二無水物
ＤＭＡＣ：ジメチルアセトアミド
【００２５】
イミド閉環率は、ポリイミド前駆体のみである場合を０、完全にポリイミドに転化した場合を１００とし、赤外吸収スペクトルにより求めた。
【００２６】
含有溶媒濃度は、熱重量測定により２０℃／分で昇温したときの試料の１００℃と３００℃のときの重量差からイミド化生成水の重量分を除き求めた。
【００２７】
合成例１
ＭＡＢＡ５．２ｋｇとＤＤＥ４．０ｋｇをＤＭＡＣ１０２ｋｇに溶解した後、１０℃に冷却し、ＰＭＤＡ８．８ｋｇを徐々に加えて反応させ、ポリイミド前駆体樹脂溶液を得た。
【００２８】
実施例１
厚み３５μｍの電解銅箔の粗化面にダイコーターを用いて合成例１で調整したポリイミド前駆体樹脂溶液を完全に硬化した後の厚みが１５μｍになるように塗工し、１１０℃にて１．２分間の乾燥を行ったところ、樹脂の含有溶媒濃度４０％、閉環率は０であった。これを極性溶媒であるメタノールに２０℃で１０分間浸漬を行ったのち取り出し、２２０℃、３６０℃にてそれぞれ２分間加熱して、閉環率が１００％のフレキシブル配線用基板が得られた。このフレキシブル配線用基板の樹脂は実用上十分な強度があり、樹脂の線膨張係数は１．０×１０-5／℃と小さく、高品質なものであった。
【００２９】
実施例２
実施例１と同様の塗工、乾燥を行ったものを、極性溶媒であるアセトニトリルに２０℃で６０分間浸漬を行ったのち取り出し、２２０℃、３６０℃にてそれぞれ２分間加熱して閉環率が１００％のフレキシブル配線用基板が得られた。このフレキシブル配線用基板の樹脂は実用上十分な強度があり、樹脂の線膨張係数は１．２×１０-5／℃と小さく、高品質なものであった。
【００３０】
比較例１
実施例１と同様の塗工、乾燥を行ったものを、非極性溶媒であるノルマルヘキサンおよびトルエンに２０℃で１０分間浸漬を行ったのち取り出し、２２０℃、３６０℃にてそれぞれ２分間加熱して閉環率が１００％のフレキシブル配線用基板が得られた。このフレキシブル配線用基板の樹脂の線膨張係数はそれぞれ３．９×10-5／℃、３．８×10-5／℃と大きかった。
【００３１】
比較例２
実施例１と同様の塗工、乾燥を行ったものを、さらに２２０℃、３６０℃にてそれぞれ２分間加熱して閉環率が１００％のフレキシブル配線用基板が得られた。このフレキシブル配線用基板の樹脂の線膨張係数は３．８×10-5／℃と大きかった。
【００３２】
実施例３
実施例１と同様の塗工、乾燥を行ったものを、４０℃の水に４分間浸漬を行ったのち取り出し、２２０℃、３６０℃にてそれぞれ２分間加熱して閉環率が１００％のフレキシブル配線用基板が得られた。このフレキシブル配線用基板の樹脂は実用上十分な強度があり、樹脂の線膨張係数は１．１×１０-5／℃と小さく、高品質なものであった。
【００３３】
実施例４
厚み３５μｍの電解銅箔の粗化面にダイコーターを用いて合成例１で調整したポリイミド前駆体樹脂溶液を完全に硬化した後の厚みが２５μｍになるように塗工し、１１０℃にて２分間の乾燥を行ったところ、樹脂の含有溶媒濃度３８％、閉環率は０であった。これを２０℃の水に６０分間浸漬を行ったのち取り出し、２２０℃、３６０℃にてそれぞれ２分間加熱して、閉環率が１００％のフレキシブル配線用基板が得られた。このフレキシブル配線用基板の樹脂は実用上十分な強度があり、樹脂の線膨張係数は１．０×１０-5／℃と小さく、高品質なものであった。
【００３４】
実施例５
実施例４と同様の塗工を行った後、１４５℃にて３０分間の乾燥行ったところ、樹脂の含有溶媒濃度１８％、閉環率３０％であった。これを２０℃の水に６０分間浸漬を行った後取り出し、１１０℃、２２０℃、３６０℃にてそれぞれ２分間加熱して閉環率が１００％のフレキシブル配線用基板が得られた。このフレキシブル配線用基板の樹脂は実用上十分な強度があり、樹脂の線膨張係数は２．３×１０-5／℃と比較的小さく、高品質なものであった。
【００３５】
比較例３
実施例４と同様の塗工、乾燥を行ったものを、さらに２２０℃、３６０℃にてそれぞれ２分間加熱して閉環率が１００％のフレキシブル配線用基板が得られた。このフレキシブル配線用基板の樹脂の線膨張係数は４．２×10-5／℃と大きかった。
【００３６】
比較例４
実施例５と同様の塗工、乾燥を行ったものを、さらに１１０℃、２２０℃、３６０℃にてそれぞれ２分間加熱して閉環率が１００％のフレキシブル配線用基板が得られた。このフレキシブル配線用基板の樹脂の線膨張係数は３．２×10-5／℃と大きかった。
【００３７】
【発明の効果】
本発明の積層体は加工精度が高くかつ信頼性に優れた絶縁体を導体上で極めて容易に加工しうるものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a substrate for flexible printed wiring formed by directly applying a polyimide precursor resin solution onto a conductor.
[0002]
[Prior art]
A flexible printed wiring board is generally manufactured by adhering a conductor and a polyimide resin insulator with an adhesive. However, with this method, properties such as heat resistance, chemical resistance, flame retardancy, electrical properties, and adhesion are governed by the adhesive, making it impossible to fully utilize the excellent properties of polyimide, resulting in higher functionality. The point was not enough.
[0003]
A flexible printed wiring board can be produced by directly applying a polyimide precursor resin solution onto a conductor such as a copper foil without using an adhesive, and drying and curing. It is known in Japanese Patent No. 61-182941. However, since the linear expansion coefficient of the resin is generally larger than that of the conductor, in this method, when it is dried and cured at a high temperature and then cooled to room temperature, curling occurs due to thermal stress due to the difference in the linear expansion coefficient between the resin and the conductor. However, when the conductor of the flexible printed wiring board is etched, there is a problem that the size is greatly changed by releasing the strain. Therefore, it is more desirable to reduce the linear expansion coefficient of the resin.
[0004]
As a means for reducing the thermal expansion coefficient, a method using a low thermal expansion polyimide resin as disclosed in JP-A-63-245988 has been proposed.
[0005]
On the other hand, a polar solvent is used for the synthesis of the polyimide precursor resin, but it is clear by the inventors of the present application that the residual solvent contained in the polyimide precursor resin affects the thermal expansion coefficient of the cured polyimide resin. It has become.
[0006]
For the purpose of recovering the solvent, it is known in Japanese Patent Publication No. 62-4409 to remove the solvent from the polyimide film in an aqueous medium.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for manufacturing a flexible wiring board having a low linear expansion coefficient of resin, no curling, and good dimensional stability.
[0008]
[Means for Solving the Problems]
That is, in the present invention, the polyimide precursor resin solution was directly applied on the conductor, and the resin in the formed film was heat-dried until the imide ring closure rate of the resin was less than 30% and the resin concentration was 50% by weight or more. Later, it is compatible with the solvent that makes up the polyimide precursor resin solution while the polyimide precursor resin is held on the conductor, and is a poor solvent for the polyimide precursor resin. It is a method for producing a substrate for flexible printed wiring, wherein the substrate is taken out after being immersed therein and then heated to 120 ° C. or higher to imidize.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The conductor used in the present invention can be any metal foil, preferably copper, aluminum, and SUS foil, and more preferably a copper foil having a thickness of 5 to 150 μm.
[0010]
The polyimide precursor resin is synthesized by reacting a diamine compound and an acid anhydride compound in a polar solvent at 0 to 200 ° C. In this case, if an imidization reaction occurs, the solubility is lowered, which is not preferable.
[0011]
Examples of polar solvents include N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), dimethyl sulfate, sulfolane, butyrolactone, cresol, phenol, halogenated phenol, Examples include cyclohexanone, dioxane, tetrahydrofuran, diglyme, and the like.
[0012]
Examples of the diamine compound include p-phenylenediamine, m-phenylenediamine, 2′-methoxy-4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, diaminotoluene, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1, 2-bis (anilino) ethane, diaminodiphenylsulfone, diaminobenzanilide, diaminobenzoate, diaminodiphenyl sulfide, 2,2-bis (p-aminophenyl) propane, 2,2-bis (p-aminophenyl) hexafluoro Propane, 1,5-diaminonaphthalene, diaminotoluene, diaminobenzotrifluoride, 1,4-bis (p-aminophenoxy) benzene, 4,4 '-(P-aminophenoxybiphenyl, diaminoanthraquinone, 4,4'-bis (3-aminophenoxyphenyl) diphenylsulfone, 1,3-bis (anilino) hexafluoropropane, 1,4-bis (anilino) octafluoro Propane, 1,5-bis (anilino) decafluoropropane, 1,7-bis (anilino) tetradecafluoropropane,
The following general formula
[0013]
Examples of tetracarboxylic acid anhydrides and derivatives thereof include the following. In addition, although illustrated here as tetracarboxylic acid, these esterified products, acid anhydrides, and acid chlorides can of course be used. Pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid, 2,3,3', 4'-benzophenone tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6 -Naphthalenetetracarboxylic acid, 3,3 ', 4,4'-Diphenylmethanetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) ) Hexafluoropropane, 3,4,9,10-tetracarboxyperylene, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane, 2,2-bis [4- (3,4 -Dicarboxyphenoxy) phenyl] hexafluoropropane, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and the like. Also included are trimellitic acid and its derivatives.
[0014]
Further, it can be modified with a compound having a reactive functional group to introduce a crosslinked structure or a ladder structure. For example, there are the following methods.
(1) A pyrrolone ring, an isoindoloquinazolinedione ring, or the like is introduced by modification with a compound represented by the following general formula.
[Chemical 2]
(3) Modification with an aromatic amine having a phenolic hydroxyl group or carboxylic acid to form a crosslinking agent capable of reacting with the hydroxyl group or carboxyl group.
[0015]
For the purpose of controlling the linear expansion coefficient or adjusting the mechanical properties, it is possible to copolymerize or blend using the above compounds. In addition, for the purpose of improving various properties, it is also possible to use a mixture of inorganic, organic, or metal powders, fibers and the like. It is also possible to add an additive such as an antioxidant or a silane coupling agent for the purpose of improving adhesiveness in order to prevent the conductor from being oxidized. It is also possible to blend different types of polymers for the purpose of improving adhesiveness.
[0016]
The thickness of the polyimide resin layer is preferably 2 μm to 300 μm, and if it is less than that, the reliability of circuit insulation is poor, and mechanical properties such as bending are low. If it exceeds 300 μm, foaming is likely to occur during heating, which is not preferable.
[0017]
A polyimide precursor resin solution obtained by reacting a diamine compound and an acid anhydride in the polar solvent is applied onto a conductor using an arbitrary coating apparatus. As the coating device, gravure coater, reverse roll coater, bar reverse roll coater, bar coater, doctor blade coater, curtain flow coater, die coater, multilayer die coater, etc. can be used. It is also possible to apply a plurality of types of polyimide precursor resin solutions so as to form a multilayer.
[0018]
The medium used in the present invention is a liquid which is a poor solvent for the resin and has an affinity for the solvent constituting the polyimide precursor resin solution. As a liquid that can be used as a polar solvent, for example, a lower alcohol, acetonitrile, acetic acid, acetone, propylene carbonate and the like alone, a mixture, and these polar solvents and a solvent constituting a polyimide precursor resin solution A mixture etc. are mentioned. Examples of the liquid that can be used as the aqueous medium include water alone, a mixture of water and a solvent constituting the polyimide precursor resin solution, a mixture of water and a lower alcohol, acetic acid, acetone, and the like. By performing the immersion treatment, it is possible to extract the solvent in the resin and reduce the solvent content before ring closure by heating.
[0019]
It is also possible to add an additive for the purpose of preventing hydrolysis of the resin.
[0020]
After applying the polyimide precursor resin solution on the conductor and drying by heating until the resin concentration in the formed film is 50% by weight or more, it has affinity with the solvent constituting the polyimide precursor resin solution. It is taken out after being immersed in a certain medium, and then heated to 120 ° C. or higher, preferably to a temperature for complete ring closure (usually 220 ° C. or higher). The linear expansion coefficient of the resin after heating is determined by the drying time and temperature, It depends on the immersion time and temperature in the medium, the heating temperature after immersion, the thickness of the resin, and the like.
[0021]
The drying temperature and time are not particularly limited, but if the resin concentration in the dried film is 50% by weight or less, the film becomes non-uniform when immersed in the medium and sufficient strength cannot be obtained. Further, since the linear expansion coefficient is less likely to decrease as the ring closing ratio after drying becomes higher, the ring closing ratio of the resin is preferably 30% or less in order to sufficiently obtain the effect of reducing the linear expansion coefficient. In the present invention, when the resin is immersed in the medium, the resin is held on the conductor, so that the resin does not need to be self-supporting. It is more preferable to increase the solvent concentration of the previous resin and lower the ring closure rate of the resin. If the solvent concentration of the resin before immersion is low, it is necessary to lengthen the immersion time in the medium in order to sufficiently reduce the linear expansion coefficient.
[0022]
The immersion time in the medium is not particularly limited, but the immersion time is preferably 1 minute or more and 60 minutes or less in order to sufficiently obtain the effect of reducing the linear expansion coefficient. When the immersion time is 1 minute or less, the linear expansion coefficient is not so small as compared with the case where the immersion in the medium is not performed, and when the immersion time is 60 minutes or more, the linear expansion coefficient is not smaller than that when the immersion time is shorter than that. .
[0023]
After the immersion treatment in the medium, the film is taken out from the medium, and then imidized by a normal heat treatment using a heating oven or the like. The heating temperature is at least 120 ° C or higher, preferably 220 ° C or higher. In heating, it is preferable not to be exposed to a high temperature at once, but to raise the temperature gradually or stepwise.
[0024]
【Example】
Hereinafter, the present invention will be described with reference to examples.
Abbreviations in the examples are as follows.
MABA: 2′-methyl-4,4′-diaminobenzanilide DDE: 4,4′-diaminodiphenyl ether PMDA: pyromellitic dianhydride DMAC: dimethylacetamide
The imide cyclization rate was determined from an infrared absorption spectrum, assuming that the polyimide precursor alone was 0, and the complete polyimide conversion was 100.
[0026]
The solvent concentration was determined by excluding the weight of imidized product water from the weight difference between 100 ° C. and 300 ° C. of the sample when the temperature was raised at 20 ° C./min by thermogravimetry.
[0027]
Synthesis example 1
MABA 5.2 kg and DDE 4.0 kg were dissolved in DMAC 102 kg, cooled to 10 ° C., PMDA 8.8 kg was gradually added and reacted to obtain a polyimide precursor resin solution.
[0028]
Example 1
A 35 μm thick electrolytic copper foil was coated on the roughened surface of the polyimide precursor resin solution prepared in Synthesis Example 1 using a die coater so that the thickness after completely curing was 15 μm. After drying for 2 minutes, the solvent concentration of the resin was 40% and the ring closure rate was 0. This was immersed in methanol as a polar solvent at 20 ° C. for 10 minutes and then taken out and heated at 220 ° C. and 360 ° C. for 2 minutes, respectively, to obtain a flexible wiring substrate with a ring closure rate of 100%. The resin for this flexible wiring board had a sufficient strength for practical use, and the linear expansion coefficient of the resin was as small as 1.0 × 10 −5 / ° C., which was high quality.
[0029]
Example 2
The same coating and drying as in Example 1 were immersed in polar solvent acetonitrile at 20 ° C. for 60 minutes and then taken out and heated at 220 ° C. and 360 ° C. for 2 minutes, respectively. A 100% flexible wiring board was obtained. The resin for this flexible wiring board had a sufficient strength for practical use, and the linear expansion coefficient of the resin was as small as 1.2.times.10.sup.- 5 / .degree.
[0030]
Comparative Example 1
The same coating and drying as in Example 1 were immersed in normal hexane and toluene, which are nonpolar solvents, at 20 ° C. for 10 minutes, then taken out and heated at 220 ° C. and 360 ° C. for 2 minutes, respectively. Thus, a flexible wiring substrate having a ring closure rate of 100% was obtained. Linear expansion coefficient of the resin of the flexible wiring board was as large as 3.9 × 10 -5 /℃,3.8×10 -5 / ℃ respectively.
[0031]
Comparative Example 2
The substrate coated and dried in the same manner as in Example 1 was further heated at 220 ° C. and 360 ° C. for 2 minutes, respectively, to obtain a flexible wiring substrate with a ring closure rate of 100%. The linear expansion coefficient of the resin for this flexible wiring board was as large as 3.8 × 10 −5 / ° C.
[0032]
Example 3
The same coating and drying as in Example 1 were immersed in water at 40 ° C. for 4 minutes and then taken out and heated at 220 ° C. and 360 ° C. for 2 minutes, respectively. A wiring board was obtained. The resin of this flexible wiring board had a sufficient strength for practical use, and the linear expansion coefficient of the resin was as small as 1.1 × 10 −5 / ° C., which was high quality.
[0033]
Example 4
The surface of the 35 μm thick electrolytic copper foil was coated on the roughened surface of the polyimide precursor resin solution prepared in Synthesis Example 1 using a die coater so that the thickness after completely curing was 25 μm. When drying was performed for a minute, the resin-containing solvent concentration was 38% and the ring closure rate was 0. This was immersed in water at 20 ° C. for 60 minutes and then taken out and heated at 220 ° C. and 360 ° C. for 2 minutes, respectively, to obtain a flexible wiring board with a ring closure rate of 100%. The resin for this flexible wiring board had a sufficient strength for practical use, and the linear expansion coefficient of the resin was as small as 1.0 × 10 −5 / ° C., which was high quality.
[0034]
Example 5
When the same coating as in Example 4 was performed and dried at 145 ° C. for 30 minutes, the resin-containing solvent concentration was 18% and the ring closure rate was 30%. This was immersed in water at 20 ° C. for 60 minutes and then taken out and heated at 110 ° C., 220 ° C. and 360 ° C. for 2 minutes, respectively, to obtain a flexible wiring board with a ring closure rate of 100%. The resin for this flexible wiring board had a sufficient strength in practical use, and the linear expansion coefficient of the resin was relatively small, 2.3 × 10 −5 / ° C., and was of high quality.
[0035]
Comparative Example 3
What was coated and dried in the same manner as in Example 4 was further heated at 220 ° C. and 360 ° C. for 2 minutes, respectively, to obtain a flexible wiring substrate with a ring closure rate of 100%. The linear expansion coefficient of the resin for this flexible wiring board was as large as 4.2 × 10 −5 / ° C.
[0036]
Comparative Example 4
What was coated and dried in the same manner as in Example 5 was further heated at 110 ° C., 220 ° C., and 360 ° C. for 2 minutes, respectively, to obtain a flexible wiring substrate with a ring closure rate of 100%. The linear expansion coefficient of the resin for this flexible wiring board was as large as 3.2 × 10 −5 / ° C.
[0037]
【The invention's effect】
The laminated body of the present invention can process an insulator having high processing accuracy and excellent reliability on a conductor very easily.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22595795A JP4183765B2 (en) | 1995-08-10 | 1995-08-10 | Manufacturing method of flexible printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22595795A JP4183765B2 (en) | 1995-08-10 | 1995-08-10 | Manufacturing method of flexible printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0955567A JPH0955567A (en) | 1997-02-25 |
| JP4183765B2 true JP4183765B2 (en) | 2008-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22595795A Expired - Fee Related JP4183765B2 (en) | 1995-08-10 | 1995-08-10 | Manufacturing method of flexible printed wiring board |
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| JP (1) | JP4183765B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3627151B2 (en) | 1996-09-18 | 2005-03-09 | 株式会社 ティーティーティー | Plasma display discharge tube and driving method thereof |
| JP4667675B2 (en) * | 2001-09-11 | 2011-04-13 | 三井化学株式会社 | Polyimide metal foil laminate |
| JP4817165B2 (en) * | 2004-03-25 | 2011-11-16 | 大阪府 | Method for producing porous polyimide membrane |
| JP5998994B2 (en) * | 2012-03-16 | 2016-09-28 | 日本ゼオン株式会社 | Method for producing polyimide laminate |
| JP2014133783A (en) * | 2013-01-08 | 2014-07-24 | Nippon Zeon Co Ltd | Resin composition, insulating film, laminated body and method for manufacturing laminated body |
| JP5994694B2 (en) * | 2013-03-19 | 2016-09-21 | 日本ゼオン株式会社 | Manufacturing method of semiconductor device |
| JP6875252B2 (en) * | 2017-10-26 | 2021-05-19 | 信越化学工業株式会社 | Method of drying polyimide paste and method of manufacturing high photoelectric conversion efficiency solar cell |
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1995
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| JPH0955567A (en) | 1997-02-25 |
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