JP2021091814A - 樹脂組成物 - Google Patents
樹脂組成物 Download PDFInfo
- Publication number
- JP2021091814A JP2021091814A JP2019223905A JP2019223905A JP2021091814A JP 2021091814 A JP2021091814 A JP 2021091814A JP 2019223905 A JP2019223905 A JP 2019223905A JP 2019223905 A JP2019223905 A JP 2019223905A JP 2021091814 A JP2021091814 A JP 2021091814A
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- Prior art keywords
- resin composition
- mass
- component
- epoxy resin
- semiconductor chip
- Prior art date
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 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
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- XMQSELBBYSAURN-UHFFFAOYSA-M triphenyl(propyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 XMQSELBBYSAURN-UHFFFAOYSA-M 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- IDXDWPWXHTXJMZ-UHFFFAOYSA-N tris(2,4,6-trimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(C)=C1P(C=1C(=CC(C)=CC=1C)C)C1=C(C)C=C(C)C=C1C IDXDWPWXHTXJMZ-UHFFFAOYSA-N 0.000 description 1
- XDHRVAHAGMMFMC-UHFFFAOYSA-N tris(2,4-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC=C1P(C=1C(=CC(C)=CC=1)C)C1=CC=C(C)C=C1C XDHRVAHAGMMFMC-UHFFFAOYSA-N 0.000 description 1
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 description 1
- XRALRSQLQXKXKP-UHFFFAOYSA-N tris(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 XRALRSQLQXKXKP-UHFFFAOYSA-N 0.000 description 1
- RYXYUARTMQUYKV-UHFFFAOYSA-N tris(4-butylphenyl)phosphane Chemical compound C1=CC(CCCC)=CC=C1P(C=1C=CC(CCCC)=CC=1)C1=CC=C(CCCC)C=C1 RYXYUARTMQUYKV-UHFFFAOYSA-N 0.000 description 1
- LQEKTSMTEYLBLJ-UHFFFAOYSA-N tris(4-ethoxyphenyl)phosphane Chemical compound C1=CC(OCC)=CC=C1P(C=1C=CC(OCC)=CC=1)C1=CC=C(OCC)C=C1 LQEKTSMTEYLBLJ-UHFFFAOYSA-N 0.000 description 1
- PCCAGZSOGFNURV-UHFFFAOYSA-N tris(4-ethylphenyl)phosphane Chemical compound C1=CC(CC)=CC=C1P(C=1C=CC(CC)=CC=1)C1=CC=C(CC)C=C1 PCCAGZSOGFNURV-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- NTUMNRFLAZXNBW-UHFFFAOYSA-N tris(4-propan-2-ylphenyl)phosphane Chemical compound C1=CC(C(C)C)=CC=C1P(C=1C=CC(=CC=1)C(C)C)C1=CC=C(C(C)C)C=C1 NTUMNRFLAZXNBW-UHFFFAOYSA-N 0.000 description 1
- JTOQWGJGVSYTTN-UHFFFAOYSA-N tris(4-propylphenyl)phosphane Chemical compound C1=CC(CCC)=CC=C1P(C=1C=CC(CCC)=CC=1)C1=CC=C(CCC)C=C1 JTOQWGJGVSYTTN-UHFFFAOYSA-N 0.000 description 1
- UQHFPPSBVOIUFM-UHFFFAOYSA-N tris(4-tert-butylphenyl)phosphane Chemical compound C1=CC(C(C)(C)C)=CC=C1P(C=1C=CC(=CC=1)C(C)(C)C)C1=CC=C(C(C)(C)C)C=C1 UQHFPPSBVOIUFM-UHFFFAOYSA-N 0.000 description 1
- UGNAOCDIZFIEQK-UHFFFAOYSA-N tris[4-[(2-methylpropan-2-yl)oxy]phenyl]phosphane Chemical compound C1=CC(OC(C)(C)C)=CC=C1P(C=1C=CC(OC(C)(C)C)=CC=1)C1=CC=C(OC(C)(C)C)C=C1 UGNAOCDIZFIEQK-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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Abstract
Description
[1] (A)硬化剤、及び(B)無機充填剤を含む樹脂組成物であって、
(A)成分が、(A−1)水酸基含有シロキサン化合物を含み、
(A−1)成分の含有量が、樹脂組成物中の(B)成分以外の不揮発成分を100質量%とした場合、0.5質量%以上5質量%未満であり、
(B)成分の含有量が、樹脂組成物中の全ての不揮発成分を100質量%とした場合、60質量%以上である、樹脂組成物。
[2] (A−1)成分が、フェノール性水酸基含有シロキサン化合物である、上記[1]に記載の樹脂組成物。
[3] (A−1)成分が、鎖状シロキサン骨格を有する、上記[1]又は[2]に記載の樹脂組成物。
[4] (A−1)成分の水酸基価が、120mgKOH/g以下である、上記[1]〜[3]の何れかに記載の樹脂組成物。
[5] (A)成分が、フェノール系硬化剤、ナフトール系硬化剤、アミン系硬化剤、活性エステル系硬化剤、及び酸無水物系硬化剤から選ばれる硬化剤をさらに含む、上記[1]〜[4]の何れかに記載の樹脂組成物。
[6] (A−1)成分の含有量が、(A)成分全てを100質量%とした場合、3質量%〜20質量%である、上記[1]〜[5]の何れかに記載の樹脂組成物。
[7] (B)成分が、シリカである、上記[1]〜[6]の何れかに記載の樹脂組成物。
[8] (B)成分の含有量が、樹脂組成物中の全ての不揮発成分を100質量%とした場合、70質量%以上である、上記[1]〜[7]の何れかに記載の樹脂組成物。
[9] (B)成分の含有量が、樹脂組成物中の全ての不揮発成分を100質量%とした場合、80質量%以上である、上記[8]に記載の樹脂組成物。
[10] (A−1)成分に対する(B)成分の含有質量比((B)成分/(A−1)成分)が、50〜1,000である、上記[1]〜[9]の何れかに記載の樹脂組成物。
[11] さらに(C)エポキシ樹脂を含む、上記[1]〜[10]の何れかに記載の樹脂組成物。
[12] 半導体チップパッケージの絶縁層を形成するための上記[1]〜[11]の何れかに記載の樹脂組成物。
[13] 回路基板の絶縁層を形成するための上記[1]〜[11]の何れかに記載の樹脂組成物。
[14] 半導体チップパッケージの半導体チップを封止するための上記[1]〜[11]の何れかに記載の樹脂組成物。
[15] 上記[1]〜[14]の何れかに記載の樹脂組成物から得られる硬化物。
[16] 支持体と、上記支持体上に設けられた上記[1]〜[14]の何れかに記載の樹脂組成物を含む樹脂組成物層と、を有する樹脂シート。
[17] 上記[1]〜[14]の何れかに記載の樹脂組成物から得られる硬化物により形成された絶縁層を含む回路基板。
[18] 上記[17]に記載の回路基板と、当該回路基板に搭載された半導体チップと、を含む半導体チップパッケージ。
[19] 半導体チップと、当該半導体チップを封止する上記[1]〜[14]の何れかに記載の樹脂組成物から得られる硬化物と、を含む半導体チップパッケージ。
[20] 上記[18]又は[19]に記載の半導体チップパッケージを備える半導体装置。
本発明の樹脂組成物は、(A)硬化剤、及び(B)無機充填剤を含み、(A)成分が、(A−1)水酸基含有シロキサン化合物を含み、(A−1)成分の含有量が、樹脂組成物中の(B)成分以外の不揮発成分を100質量%とした場合、0.5質量%以上5質量%未満であり、(B)成分の含有量が、樹脂組成物中の全ての不揮発成分を100質量%とした場合、60質量%以上である。このような樹脂組成物を用いることにより、モールド成形後のフローマークの発生、及び反りを抑制でき、且つ優れた熱剥離テープ密着性を備える硬化物を得ることができる。
本発明の樹脂組成物は、(A)硬化剤を含む。(A)硬化剤は、(C)エポキシ樹脂を硬化する機能を有する。(A)硬化剤が硬化対象とする(C)エポキシ樹脂は、本発明の樹脂組成物に含まれていてもよいし、硬化前に別途本発明の樹脂組成物と混合してもよい。
(A)硬化剤は、(A−1)水酸基含有シロキサン化合物を含む。(A−1)水酸基含有シロキサン化合物とは、1個以上(好ましくは2個以上)の水酸基を有し且つ1個以上(好ましくは2個以上、特に好ましくは2個以上が繰り返し連続する)のシロキサン(Si−O−Si)結合を有する化合物をいう。
で表されるシロキサン化合物である。
本発明の樹脂組成物は、さらに(A−1)成分以外の任意の硬化剤を含む場合がある。
本発明の樹脂組成物は、さらに(B)無機充填材を含有する。
本発明の樹脂組成物は、さらに任意成分として(C)エポキシ樹脂を含む場合がある。(C)エポキシ樹脂とは、エポキシ基を有する樹脂を意味する。(C)エポキシ樹脂は、(A)硬化剤により硬化させられる成分であり得る。
本発明の樹脂組成物は、さらに任意成分として(D)硬化促進剤を含む場合がある。(D)硬化促進剤は、(C)エポキシ樹脂の硬化を促進させる機能を有する。
本発明の樹脂組成物は、不揮発性成分として、さらに任意の添加剤を含んでいてもよい。このような添加剤としては、例えば、ゴム粒子、ポリアミド微粒子、シリコーン粒子等の有機充填材;ポリカーボネート樹脂、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリオレフィン樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレンエーテル樹脂、ポリエーテルエーテルケトン樹脂、ポリエステル樹脂等の熱可塑性樹脂;有機銅化合物、有機亜鉛化合物、有機コバルト化合物等の有機金属化合物;フタロシアニンブルー、フタロシアニングリーン、アイオディングリーン、ジアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック等の着色剤;ハイドロキノン、カテコール、ピロガロール、フェノチアジン等の重合禁止剤;シリコーン系レベリング剤、アクリルポリマー系レベリング剤等のレベリング剤;ベントン、モンモリロナイト等の増粘剤;シリコーン系消泡剤、アクリル系消泡剤、フッ素系消泡剤、ビニル樹脂系消泡剤等の消泡剤;ベンゾトリアゾール系紫外線吸収剤等の紫外線吸収剤;尿素シラン等の接着性向上剤;トリアゾール系密着性付与剤、テトラゾール系密着性付与剤、トリアジン系密着性付与剤等の密着性付与剤;ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤等の酸化防止剤;スチルベン誘導体等の蛍光増白剤;フッ素系界面活性剤、シリコーン系界面活性剤等の界面活性剤;リン系難燃剤(例えばリン酸エステル化合物、ホスファゼン化合物、ホスフィン酸化合物、赤リン)、窒素系難燃剤(例えば硫酸メラミン)、ハロゲン系難燃剤、無機系難燃剤(例えば三酸化アンチモン)等の難燃剤等が挙げられる。添加剤は、1種を単独で用いてもよく、2種以上を任意の比率で組み合わせて用いてもよい。(E)その他の添加剤の含有量は当業者であれば適宜設定できる。
本発明の樹脂組成物は、上述した不揮発性成分以外に、揮発性成分として、さらに任意の有機溶剤を含有する場合がある。(F)有機溶剤としては、公知のものを適宜用いることができ、その種類は特に限定されるものではない。(F)有機溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤;酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸イソアミル、プロピオン酸メチル、プロピオン酸エチル、γ-ブチロラクトン等のエステル系溶剤;テトラヒドロピラン、テトラヒドロフラン、1,4−ジオキサン、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジフェニルエーテル等のエーテル系溶剤;メタノール、エタノール、プロパノール、ブタノール、エチレングリコール等のアルコール系溶剤;酢酸2−エトキシエチル、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセタート、エチルジグリコールアセテート、γ−ブチロラクトン、メトキシプロピオン酸メチル等のエーテルエステル系溶剤;乳酸メチル、乳酸エチル、2−ヒドロキシイソ酪酸メチル等のエステルアルコール系溶剤;2−メトキシプロパノール、2−メトキシエタノール、2−エトキシエタノール、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル(ブチルカルビトール)等のエーテルアルコール系溶剤;N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチル−2−ピロリドン等のアミド系溶剤;ジメチルスルホキシド等のスルホキシド系溶剤;アセトニトリル、プロピオニトリル等のニトリル系溶剤;ヘキサン、シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素系溶剤;ベンゼン、トルエン、キシレン、エチルベンゼン、トリメチルベンゼン等の芳香族炭化水素系溶剤等を挙げることができる。(F)有機溶剤は、1種単独で用いてもよく、2種以上を任意の比率で組み合わせて用いてもよい。一実施形態においては、(F)有機溶剤は、量が少ないほど好ましく(例えば樹脂組成物中の不揮発成分を100質量%とした場合0.5質量%以下、0.1質量%以下、0.01質量%以下)、含まないことが特に好ましい。
本発明の樹脂組成物は、例えば、任意の反応容器に(A)硬化剤、(B)無機充填剤、必要に応じて(C)エポキシ樹脂、必要に応じて(D)硬化促進剤、必要に応じて(E)その他の添加剤、及び必要に応じて(F)有機溶剤を、任意の順で及び/又は一部若しくは全部同時に加えて混合することによって、製造することができる。また、各成分を加えて混合する過程で、温度を適宜設定することができ、一時的に又は終始にわたって、加熱及び/又は冷却してもよい。また、各成分を加えて混合する過程において、撹拌又は振盪を行ってもよい。また、各成分を加えて混合する際に又はその後に、樹脂組成物を、例えば、ミキサーなどの撹拌装置を用いて撹拌し、均一に分散させてもよい。
本発明の樹脂組成物は、(A)硬化剤、及び(B)無機充填剤を含む樹脂組成物であって、(A)成分が、(A−1)水酸基含有シロキサン化合物を含み、(A−1)成分の含有量が、樹脂組成物中の(B)成分以外の不揮発成分を100質量%とした場合、5質量%未満であり、(B)成分の含有量が、樹脂組成物中の全ての不揮発成分を100質量%とした場合、60質量%以上であることから、モールド成形後のフローマークの発生、及び反りを抑制でき、且つ優れた熱剥離テープ密着性を備える硬化物を得ることができる。
本発明の樹脂組成物は、(C)エポキシ樹脂を含んでいてもよいし、使用前に(C)エポキシ樹脂と混合させて使用してもよい。以下、(C)エポキシ樹脂を含む本発明の樹脂組成物或いは本発明の樹脂組成物に(C)エポキシ樹脂を混合させて得られる樹脂組成物を「エポキシ樹脂組成物」という。したがって、本発明の樹脂組成物は、そのまま或いは(C)エポキシ樹脂と混合させることにより、下記で説明するエポキシ樹脂組成物と同様の用途で使用することができる。
本発明の樹脂シートは、支持体と、該支持体上に設けられた樹脂組成物層と、を有する。樹脂組成物層は、本発明の樹脂組成物をエポキシ樹脂組成物として含む層である。すなわち、樹脂組成物層を形成する際には、(C)エポキシ樹脂を含む本発明の樹脂組成物或いは本発明の樹脂組成物に(C)エポキシ樹脂を混合させて得られた樹脂組成物を使用する。
本発明の回路基板は、本発明の樹脂組成物から得られるエポキシ樹脂組成物の硬化物により形成された絶縁層を含む。この回路基板は、例えば、下記の工程(1)及び工程(2)を含む製造方法によって、製造できる。
(1)基材上に、本発明の樹脂組成物を用いてエポキシ樹脂組成物の樹脂組成物層を形成する工程。
(2)樹脂組成物層を熱硬化して、絶縁層を形成する工程。
例えば、樹脂シートを用いて回路基板を製造した場合、回路基板の製造方法は、樹脂シートの支持体を剥離する工程を含んでいてもよい。支持体は、樹脂組成物層の熱硬化の前に剥離してもよく、樹脂組成物層の熱硬化の後に剥離してもよい。
本発明の第一実施形態に係る半導体チップパッケージは、上述した回路基板と、この回路基板に搭載された半導体チップとを含む。この半導体チップパッケージは、回路基板に半導体チップを接合することにより、製造することができる。
(A)基材に仮固定フィルムを積層する工程、
(B)半導体チップを、仮固定フィルム上に仮固定する工程、
(C)半導体チップ上に封止層を形成する工程、
(D)基材及び仮固定フィルムを半導体チップから剥離する工程、
(E)半導体チップの基材及び仮固定フィルムを剥離した面に、絶縁層としての再配線形成層を形成する工程、
(F)再配線形成層上に、導体層としての再配線層を形成する工程、並びに、
(G)再配線層上にソルダーレジスト層を形成する工程、
を含む。また、前記の半導体チップパッケージの製造方法は、
(H)複数の半導体チップパッケージを、個々の半導体チップパッケージにダイシングし、個片化する工程
を含んでいてもよい。
工程(A)は、基材に仮固定フィルムを積層する工程である。基材と仮固定フィルムとの積層条件は、回路基板の製造方法における基材と樹脂シートとの積層条件と同様でありうる。
工程(B)は、半導体チップを、仮固定フィルム上に仮固定する工程である。半導体チップの仮固定は、例えば、フリップチップボンダー、ダイボンダー等の装置を用いて行うことができる。半導体チップの配置のレイアウト及び配置数は、仮固定フィルムの形状、大きさ、目的とする半導体チップパッケージの生産数等に応じて適切に設定できる。例えば、複数行で、かつ複数列のマトリックス状に半導体チップを整列させて、仮固定してもよい。
工程(C)は、半導体チップ上に封止層を形成する工程である。封止層は、上述した樹脂組成物の硬化物によって形成する。封止層は、通常、半導体チップ上に樹脂組成物層を形成する工程と、この樹脂組成物層を熱硬化させて封止層を形成する工程とを含む方法で形成する。
工程(D)は、基材及び仮固定フィルムを半導体チップから剥離する工程である。剥離方法は、仮固定フィルムの材質に応じた適切な方法を採用することが望ましい。剥離方法としては、例えば、仮固定フィルムを加熱、発泡又は膨張させて剥離する方法が挙げられる。また、剥離方法としては、例えば、基材を通して仮固定フィルムに紫外線を照射して、仮固定フィルムの粘着力を低下させて剥離する方法が挙げられる。
工程(E)は、半導体チップの基材及び仮固定フィルムを剥離した面に、絶縁層としての再配線形成層を形成する工程である。
工程(F)は、再配線形成層上に、導体層としての再配線層を形成する工程である。再配線形成層上に再配線層を形成する方法は、回路基板の製造方法における絶縁層上への導体層の形成方法と同様でありうる。また、工程(E)及び工程(F)を繰り返し行い、再配線層及び再配線形成層を交互に積み上げて(ビルドアップ)もよい。
工程(G)は、再配線層上にソルダーレジスト層を形成する工程である。ソルダーレジスト層の材料は、絶縁性を有する任意の材料を用いることができる。中でも、半導体チップパッケージの製造のしやすさの観点から、感光性樹脂及び熱硬化性樹脂が好ましい。また、熱硬化性樹脂として、本発明の樹脂組成物を用いてもよい。
半導体チップパッケージの製造方法は、工程(A)〜(G)以外に、工程(H)を含んでいてもよい。工程(H)は、複数の半導体チップパッケージを個々の半導体チップパッケージにダイシングし、個片化する工程である。半導体チップパッケージを個々の半導体チップパッケージにダイシングする方法は特に限定されない。
半導体装置は、半導体チップパッケージを備える。半導体装置としては、例えば、電気製品(例えば、コンピューター、携帯電話、スマートフォン、タブレット型デバイス、ウェラブルデバイス、デジタルカメラ、医療機器、及びテレビ等)及び乗物(例えば、自動二輪車、自動車、電車、船舶及び航空機等)等に供される各種半導体装置が挙げられる。
フェノール性水酸基含有シロキサン化合物(信越化学工業社製「KF−2201」、水酸基価38mgKOH/g)1部、酸無水物硬化剤(新日本理化社製「HNA−100」、酸無水物当量179g/eq.)8部、シリカ(平均粒径6.9μm、比表面積3.4m2/g、信越化学工業社製「KBM5783」で表面処理したもの)120部、ビスフェノール型エポキシ樹脂(日鉄ケミカル&マテリアル社製「ZX1059」、エポキシ当量約165g/eq.、ビスフェノールA型エポキシ樹脂とビスフェノールF型エポキシ樹脂の1:1混合物)7部、グリシジルアミン型エポキシ樹脂(三菱ケミカル社製「630」、エポキシ当量約95g/eq.)5部、ジシクロペンタジエン型エポキシ樹脂(DIC社製「HP−7200L」、エポキシ当量約250g/eq.)2部、イミダゾール系硬化促進剤(四国化成工業社製「1B2PZ」、1−ベンジル−2−フェニルイミダゾール)0.1部を、ミキサーを用いて均一に分散して、樹脂組成物を調製した。
フェノール性水酸基含有シロキサン化合物(信越化学工業社製「KF−2201」、水酸基価38mgKOH/g)の使用量を1部から0.5部に変更したこと以外は、実施例1と同様にして樹脂組成物を得た。
シリカ(平均粒径6.9μm、比表面積3.4m2/g、信越化学工業社製「KBM5783」で表面処理したもの)120部の代わりにアルミナ(平均粒径6.0μm、比表面積1.7m2/g、信越化学工業社製「KBM573」で表面処理をしたもの)165部を用いたこと以外は、実施例1と同様にして樹脂組成物を得た。
シリカ(平均粒径6.9μm、比表面積3.4m2/g、信越化学工業社製「KBM5783」で表面処理したもの)120部の代わりにアルミナ(平均粒径6.0μm、比表面積1.7m2/g、信越化学工業社製「KBM573」で表面処理をしたもの)165部を用いたこと以外は、実施例2と同様にして樹脂組成物を得た。
フェノール性水酸基含有シロキサン化合物(信越化学工業社製「KF−2201」、水酸基価38mgKOH/g)1部の代わりに、カルビノール型水酸基含有シロキサン化合物(信越化学工業社製「KF−6002」、水酸基価35mgKOH/g)0.5部を用いたこと以外は、実施例1と同様にして樹脂組成物を得た。
フェノール性水酸基含有シロキサン化合物(信越化学工業社製「KF−2201」、水酸基価38mgKOH/g)1部の代わりに、カルビノール型水酸基含有シロキサン化合物(信越化学工業社製「X−22−4039」、水酸基価58mgKOH/g)0.5部を用いたこと以外は、実施例1と同様にして樹脂組成物を得た。
フェノール性水酸基含有シロキサン化合物(信越化学工業社製「KF−2201」、水酸基価38mgKOH/g)の使用量を1部から3部に変更したこと以外は、実施例1と同様にして樹脂組成物を得た。
フェノール性水酸基含有シロキサン化合物(信越化学工業社製「KF−2201」、水酸基価38mgKOH/g)を使用しなかったこと以外は、実施例1と同様にして樹脂組成物を得た。
12インチシリコンウエハ上に、実施例及び比較例で調製した樹脂組成物を、コンプレッションモールド装置(金型温度:130℃、圧力:6MPa、キュアタイム:10分)を用いて圧縮成型して、厚さ300μmの樹脂組成物層を形成した。その後、180℃で90分加熱して、樹脂組成物層を熱硬化させた。これにより、シリコンウエハと樹脂組成物の硬化物層とを含む試料基板を得た。シャドウモアレ測定装置(Akorometrix社製「ThermoireAXP」)を用いて、前記の試料基板について25℃での反り量を測定した。測定は、電子情報技術産業協会規格のJEITA EDX−7311−24に準拠して行った。具体的には、測定領域の基板面の全データの最小二乗法によって算出した仮想平面を基準面として、その基準面から垂直方向の最小値と最大値との差を反り量として求め、以下の基準で評価した。
「○」:反り量が3mm未満
「×」:反り量が3mm以上
12インチシリコンウエハに、常温時に粘着性を有し且つ加熱時に容易に剥離できる熱剥離テープ(Thermal release tape;日東電工社製「リバアルファNo.3195V」)を貼り付けた。実施例及び比較例で調製した樹脂組成物をコンプレッションモールド装置(金型温度:130℃、圧力:6MPa、キュアタイム:10分)を用いて圧縮成型して、厚さ300μmの樹脂組成物層を形成した。これにより、シリコンウエハと樹脂組成物とを含む試料基板を得た。
「○」:試料基板を23℃で30分放置し熱剥離テープと樹脂組成物の間で剥離が生じない場合
「×」:試料基板を23℃で30分放置し熱剥離テープと樹脂組成物の間で剥離が生じた場合
12インチシリコンウエハ上に、実施例及び比較例で調製した樹脂組成物を、コンプレッションモールド装置(金型温度:130℃、圧力:6MPa、キュアタイム:10分)を用いて圧縮成型して、厚さ300μmの樹脂組成物層を形成し、サンプルとした。その後、サンプルの樹脂組成物層の外観を観察し、以下の基準で評価した。
「○」:樹脂組成物層表面全体のうち、フローマークの占める面積が20%未満
「×」:樹脂組成物層表面全体のうち、フローマークの占める面積が20%以上
Claims (20)
- (A)硬化剤、及び(B)無機充填剤を含む樹脂組成物であって、
(A)成分が、(A−1)水酸基含有シロキサン化合物を含み、
(A−1)成分の含有量が、樹脂組成物中の(B)成分以外の不揮発成分を100質量%とした場合、0.5質量%以上5質量%未満であり、
(B)成分の含有量が、樹脂組成物中の全ての不揮発成分を100質量%とした場合、60質量%以上である、樹脂組成物。 - (A−1)成分が、フェノール性水酸基含有シロキサン化合物である、請求項1に記載の樹脂組成物。
- (A−1)成分が、鎖状シロキサン骨格を有する、請求項1又は2に記載の樹脂組成物。
- (A−1)成分の水酸基価が、120mgKOH/g以下である、請求項1〜3の何れか1項に記載の樹脂組成物。
- (A)成分が、フェノール系硬化剤、ナフトール系硬化剤、アミン系硬化剤、活性エステル系硬化剤、及び酸無水物系硬化剤から選ばれる硬化剤をさらに含む、請求項1〜4の何れか1項に記載の樹脂組成物。
- (A−1)成分の含有量が、(A)成分全てを100質量%とした場合、3質量%〜20質量%である、請求項1〜5の何れか1項に記載の樹脂組成物。
- (B)成分が、シリカである、請求項1〜6の何れか1項に記載の樹脂組成物。
- (B)成分の含有量が、樹脂組成物中の全ての不揮発成分を100質量%とした場合、70質量%以上である、請求項1〜7の何れか1項に記載の樹脂組成物。
- (B)成分の含有量が、樹脂組成物中の全ての不揮発成分を100質量%とした場合、80質量%以上である、請求項8に記載の樹脂組成物。
- (A−1)成分に対する(B)成分の含有質量比((B)成分/(A−1)成分)が、50〜1,000である、請求項1〜9の何れか1項に記載の樹脂組成物。
- さらに(C)エポキシ樹脂を含む、請求項1〜10の何れか1項に記載の樹脂組成物。
- 半導体チップパッケージの絶縁層を形成するための請求項1〜11の何れか1項に記載の樹脂組成物。
- 回路基板の絶縁層を形成するための請求項1〜11の何れか1項に記載の樹脂組成物。
- 半導体チップパッケージの半導体チップを封止するための請求項1〜11の何れか1項に記載の樹脂組成物。
- 請求項1〜14の何れか1項に記載の樹脂組成物から得られる硬化物。
- 支持体と、上記支持体上に設けられた請求項1〜14の何れか1項に記載の樹脂組成物を含む樹脂組成物層と、を有する樹脂シート。
- 請求項1〜14の何れか1項に記載の樹脂組成物から得られる硬化物により形成された絶縁層を含む回路基板。
- 請求項17に記載の回路基板と、当該回路基板に搭載された半導体チップと、を含む半導体チップパッケージ。
- 半導体チップと、当該半導体チップを封止する請求項1〜14の何れか1項に記載の樹脂組成物から得られる硬化物と、を含む半導体チップパッケージ。
- 請求項18又は19に記載の半導体チップパッケージを備える半導体装置。
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