JPWO2018016527A1 - 有機絶縁体、金属張積層板および配線基板 - Google Patents
有機絶縁体、金属張積層板および配線基板 Download PDFInfo
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- JPWO2018016527A1 JPWO2018016527A1 JP2018528832A JP2018528832A JPWO2018016527A1 JP WO2018016527 A1 JPWO2018016527 A1 JP WO2018016527A1 JP 2018528832 A JP2018528832 A JP 2018528832A JP 2018528832 A JP2018528832 A JP 2018528832A JP WO2018016527 A1 JPWO2018016527 A1 JP WO2018016527A1
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- Prior art keywords
- organic insulator
- cyclic olefin
- olefin copolymer
- metal
- organic
- Prior art date
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- 239000012212 insulator Substances 0.000 title claims abstract description 106
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 86
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims abstract description 83
- 150000002978 peroxides Chemical class 0.000 claims abstract description 36
- 238000005259 measurement Methods 0.000 claims abstract description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 39
- 239000011888 foil Substances 0.000 claims description 35
- 239000011889 copper foil Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 23
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- 239000000758 substrate Substances 0.000 claims description 13
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 claims description 11
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 claims description 11
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- 239000011342 resin composition Substances 0.000 description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- -1 cyclic olefin Chemical class 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 239000003063 flame retardant Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
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- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 4
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- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
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- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本開示の金属張積層板は、上記の有機絶縁体と、有機絶縁体の少なくとも一方の面に積層された金属箔とを備えている。
本開示の配線基板は、複数の絶縁層と該絶縁層間に配置された導体層とを具備し、前記絶縁層が上記の有機絶縁体により構成されている。
Rw=(W1/(W1+W2))×100 (I)
(環状オレフィンコポリマー)
熱硬化COC:架橋可能な官能基を有する環状オレフィンコポリマー(三井化学(株)製)
熱可塑COC:架橋可能な官能基を有さない環状オレフィンコポリマー(三井化学(株)製)
(ベンゼン環を有する過酸化物)
パーブチルD:ジ−t−ブチルペルオキシド(日油(株)製、ベンゼン環無し)
(その他の添加剤)
平均粒径が1μmシリカ粒子、
難燃剤(臭素系)
表1に示す成分を表1に示す割合で混合し、室温(25℃)で撹拌して樹脂組成物を得た。環状オレフィンコポリマー100質量部に対して、ベンゼン環を有する過酸化物を1.8質量部の割合で添加した。難燃剤としては「SAYTEX8010(アルベマール社製)」を使用した。難燃剤は、環状オレフィンコポリマーとベンゼン環を有する過酸化物との合計量100質量部に対して、30質量部の割合で使用した。次に、得られた樹脂組成物をキシレンに溶解させて樹脂ワニスを得た。樹脂組成物とキシレンとの質量比は40:60とした。次に、得られた樹脂ワニスを、バーコーターを用いてシート状に成形し、150℃にて4分間乾燥させて15μmの厚みを有するシート状成形体を得た。
表1に示す成分を表1に示す割合で混合し、室温(25℃)で撹拌して樹脂組成物を得た。環状オレフィンコポリマー100質量部に対して、ベンゼン環を有する過酸化物を1.8質量部の割合で添加した。難燃剤としては「SAYTEX8010(アルベマール社製)」を使用した。難燃剤は、環状オレフィンコポリマーとベンゼン環を有する過酸化物との合計量100質量部に対して、30質量部の割合で使用した。シリカ粒子は、環状オレフィンコポリマーとベンゼン環を有する過酸化物との合計量100質量部に対して、20質量部の割合で使用した。次に、得られた樹脂組成物をキシレンに溶解させて樹脂ワニスを得た。樹脂組成物とキシレンとの質量比は40:60とした。次に、得られた樹脂ワニスを、バーコーターを用いてシート状に成形し、150℃にて4分間乾燥させて15μmの厚みを有するシート状成形体を得た。
熱可塑COCをキシレンに溶解させて樹脂ワニスを得た。樹脂組成物とキシレンとの質量比は40:60とした。次に、得られた樹脂ワニスを、バーコーターを用いてシート状に成形し、150℃にて4分間乾燥させて15μmの厚みを有するシート状成形体を得た。
実施例5で得られたシート状成形体(実施例9)または実施例7で得られたシート状成形体(実施例10〜13)を小片に切断して8枚重ね合わせて積層し、表2に示す表面粗さ(Sa)を有する銅箔(いずれも厚みは18μm)を積層した。4MPaの加下にて200℃で120分間加熱し、0.8mmの厚みを有する銅張積層板を得た。銅箔は、表2に示す表面処理に供した。得られた銅張積層板の銅箔を、シート状成形体(有機絶縁体)に対して垂直に引っ張り、銅箔を引き剥がすときのピール強度をオートグラフで測定した。結果を表2に示す。
(環状オレフィンコポリマー)
LCOC−4:架橋可能な官能基を有する環状オレフィンコポリマー(三井化学(株)製)
LCOC−3:架橋可能な官能基を有さない環状オレフィンコポリマー(三井化学(株)製)
(過酸化物)
パーキュアーVS:t−ブチルペルオキシベンゾエート(日油(株)製、ベンゼン環有り)
パーブチルP:α,α’−ジ−(t−ブチルパーオキシ)ジイソプロピルベンゼン(日油(株)製、ベンゼン環有り)
パーブチルC:t−ブチルクミルパーオキサイド(日油(株)製、ベンゼン環有り)
パークミルD:ジクミルパーオキシド(日油(株)製、ベンゼン環有り)
パーヘキシン25B:2,5−ジメチル−2,5−ジ(t−ブチルパーオキサイド)ヘキシン−3(日油(株)製、ベンゼン環無し)
パーヘキサV:n−ブチル−4,4−ジ(t−ブチルパーオキシ)バレレート(日油(株)製、ベンゼン環無し)
パーブチルD:ジ−t−ブチルペルオキシド(日油(株)製、ベンゼン環無し)
表3に示す成分を表3に示す割合で混合し、さらに難燃剤として「SAYTEX8010(アルベマール社製)」を、環状オレフィンコポリマーと過酸化物との合計量100質量部に対して30質量部の割合で添加し、室温(25℃)で撹拌して樹脂組成物を得た。次に、得られた樹脂組成物をキシレンに溶解させて樹脂ワニスを得た。樹脂組成物とキシレンとの質量比は40:60であった。次に、得られた樹脂ワニスを、バーコーターを用いてシート状に成形し、150℃にて4分間乾燥させて15μmの厚みを有するシート状成形体(有機絶縁体)を得た。得られたシート状成形体のガラス転移点(Tg)を表1に示す。Tgは動的粘弾性測定(DMA)によって求めた。
表4に示す成分を表4に示す割合で混合し、さらに難燃剤として「SAYTEX8010」を添加した。実施例22〜29および比較例7〜11のいずれも、環状オレフィンコポリマーと過酸化物との合計量100質量部に対して、難燃剤を30質量部の割合で添加した。さらに実施例22〜29および比較例7〜11のいずれも、メタクリル処理された球状シリカ(SFP−30M、平均粒径:0.5μm、デンカ(株)製)を、環状オレフィンコポリマーと過酸化物との合計量100質量部に対して、21質量部の割合で添加した。
3 銅箔
7 絶縁層
8 配線層
A1、A10 損失正接
B1、B10 貯蔵弾性率
C1、C10 損失弾性率
Claims (8)
- 環状オレフィンコポリマーを主成分とし、ベンゼン環を有する過酸化物を含み、動的粘弾性測定において、損失正接のピークが120℃以上に存在する、有機絶縁体。
- 前記環状オレフィンコポリマーが熱硬化性の環状オレフィンコポリマーと熱可塑性の環状オレフィンコポリマーとを含み、前記損失正接のピークが80〜100℃に存在する、請求項1に記載の有機絶縁体。
- 前記動的粘弾性測定によって求められる貯蔵弾性率が8×106Pa以上である、請求項1または2に記載の有機絶縁体。
- 請求項1〜3のいずれかに記載の有機絶縁体と、該有機絶縁体の少なくとも一方の面に積層された金属箔とを備えている、金属張積層板。
- 前記有機絶縁体は、前記金属箔側の表面を、飛行時間型二次イオン質量分析により分析した場合に、分子量340〜350の有機物のピークが存在する、請求項4に記載の金属張積層板。
- 前記ピークは、分子量207の有機物のピークのカウント数を1とした場合のカウント比が1.5以上である、請求項5に記載の金属張積層板。
- 前記銅箔の表面粗さSaが、0.5μm以下である、請求項5または6に記載の金属張積層板。
- 複数の絶縁層と該絶縁層間に配置された導体層とを具備し、前記絶縁層が請求項1〜3のいずれかに記載の有機絶縁体により構成されている、配線基板。
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