JP4004004B2 - Polybenzoxazole precursor, resin composition for insulating material, and insulating material using the same - Google Patents
Polybenzoxazole precursor, resin composition for insulating material, and insulating material using the same Download PDFInfo
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- JP4004004B2 JP4004004B2 JP2000017724A JP2000017724A JP4004004B2 JP 4004004 B2 JP4004004 B2 JP 4004004B2 JP 2000017724 A JP2000017724 A JP 2000017724A JP 2000017724 A JP2000017724 A JP 2000017724A JP 4004004 B2 JP4004004 B2 JP 4004004B2
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- Prior art keywords
- polybenzoxazole
- polybenzoxazole precursor
- group
- insulating material
- molecular weight
- Prior art date
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- 229920002577 polybenzoxazole Polymers 0.000 title claims description 87
- 239000002243 precursor Substances 0.000 title claims description 58
- 239000011810 insulating material Substances 0.000 title claims description 15
- 239000011342 resin composition Substances 0.000 title claims description 12
- 125000000962 organic group Chemical group 0.000 claims description 18
- 125000003827 glycol group Chemical group 0.000 claims description 12
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 46
- -1 diamine compound Chemical class 0.000 description 32
- 239000011347 resin Substances 0.000 description 28
- 229920005989 resin Polymers 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- ZXKINMCYCKHYFR-UHFFFAOYSA-N aminooxidanide Chemical compound [O-]N ZXKINMCYCKHYFR-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 5
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
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- 150000002148 esters Chemical class 0.000 description 4
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- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 238000002329 infrared spectrum Methods 0.000 description 3
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 2
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- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- 239000012153 distilled water Substances 0.000 description 2
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
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- 230000004580 weight loss Effects 0.000 description 2
- 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
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- XFFVWQRWVKPHDE-UHFFFAOYSA-N 1-fluorocyclohexa-3,5-diene-1,2-dicarboxylic acid Chemical compound OC(=O)C1C=CC=CC1(F)C(O)=O XFFVWQRWVKPHDE-UHFFFAOYSA-N 0.000 description 1
- SPNKRWLNDSRCFM-UHFFFAOYSA-N 1-fluorocyclohexa-3,5-diene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(F)(C(O)=O)C1 SPNKRWLNDSRCFM-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- PGRIMKUYGUHAKH-UHFFFAOYSA-N 2,4,5,6-tetrafluorobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(C(O)=O)=C1F PGRIMKUYGUHAKH-UHFFFAOYSA-N 0.000 description 1
- CBTRJEXEEWVQHL-UHFFFAOYSA-N 2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound COCCOCCOCCOCC1CO1 CBTRJEXEEWVQHL-UHFFFAOYSA-N 0.000 description 1
- KZLDGFZCFRXUIB-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC(C=2C=C(N)C(O)=CC=2)=C1 KZLDGFZCFRXUIB-UHFFFAOYSA-N 0.000 description 1
- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 1
- CERCNNGWSFHMRS-UHFFFAOYSA-N 2-amino-4-[2-[3-amino-4-hydroxy-5-(trifluoromethyl)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]-6-(trifluoromethyl)phenol Chemical compound FC(F)(F)C1=C(O)C(N)=CC(C(C=2C=C(C(O)=C(N)C=2)C(F)(F)F)(C(F)(F)F)C(F)(F)F)=C1 CERCNNGWSFHMRS-UHFFFAOYSA-N 0.000 description 1
- FNHXGMKHCQZENO-UHFFFAOYSA-N 2-amino-4-[4-(3-amino-4-hydroxyphenyl)-2,3,5,6-tetrafluorophenyl]phenol Chemical compound C1=C(O)C(N)=CC(C=2C(=C(F)C(=C(F)C=2F)C=2C=C(N)C(O)=CC=2)F)=C1 FNHXGMKHCQZENO-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- DWOLBEJAJWCIGK-UHFFFAOYSA-N 2-fluorobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1F DWOLBEJAJWCIGK-UHFFFAOYSA-N 0.000 description 1
- YUWKPDBHJFNMAD-UHFFFAOYSA-N 2-fluoroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(F)=C1 YUWKPDBHJFNMAD-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- YJLVXRPNNDKMMO-UHFFFAOYSA-N 3,4,5,6-tetrafluorophthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1C(O)=O YJLVXRPNNDKMMO-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- BBCQSMSCEJBIRD-UHFFFAOYSA-N 3-fluorophthalic acid Chemical compound OC(=O)C1=CC=CC(F)=C1C(O)=O BBCQSMSCEJBIRD-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- ZYEAKJZYRUSXMV-UHFFFAOYSA-N 5-[2-(3-amino-4-methoxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-methoxyaniline Chemical compound C1=C(N)C(OC)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(OC)C(N)=C1 ZYEAKJZYRUSXMV-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- UVNYQSUCIGWUHW-UHFFFAOYSA-N N=C=O.CCCC Chemical compound N=C=O.CCCC UVNYQSUCIGWUHW-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
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- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Formation Of Insulating Films (AREA)
- Organic Insulating Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は絶縁材に関するものであり、更に詳しくは電気電子機器用、半導体装置用として優れた特性を有するポリベンゾオキサゾール前駆体、絶縁材用樹脂組成物およびこれを用いた絶縁材に関するものである。
【０００２】
【従来の技術】
電気電子機器用、半導体装置用材料に求められている特性のなかで、電気特性と耐熱性は最も重要な特性である。特に近年、回路の微細化と信号の高速化に伴い、誘電率の低い絶縁材料が要求されている。この２つの特性を両立させるために耐熱性の高い有機系の絶縁膜が期待されている。例えば、従来から用いられている二酸化シリコン等の無機の絶縁膜は高耐熱性を示すが誘電率が高く、前述の特性について、両立が困難になりつつある。ポリイミド樹脂に代表される有機系の絶縁膜は、電気特性、耐熱性に優れ２つの特性の両立が可能であり、実際にソルダーレジスト、カバーレイ、液晶配向膜などに用いられている。
【０００３】
しかしながら、近年の半導体の高機能化、高性能化にともない、電気特性、耐熱性について、著しい向上が必要とされているため、更に高性能な樹脂が必要とされるようになっている。特に誘電率について２．５を下回るような低誘電率材料が期待されており、ポリイミド樹脂においても、フッ素及びトリフルオロメチル基を高分子内に導入することにより電気特性と耐熱性を両立することが試みられているが、現時点では必要とされる水準まで達していない。
【０００４】
ポリイミド樹脂以外の樹脂では、ポリベンゾオキサゾール樹脂が期待されている。ポリイミド樹脂は、イミド環にカルボキシル基を２個有していることで、電気特性に悪影響を及ぼしている。従って、一般にポリベンゾオキサゾール樹脂は、ポリイミド樹脂よりも電気特性に優れ、かつ耐熱性も同等であるため、極めて有用な樹脂である。しかし、要求されている電気特性の水準が非常に高く、これまでのポリベンゾオキサゾール樹脂では要求されている水準まで達していない。
【０００５】
【発明が解決しようとする課題】
本発明は、極めて低い誘電率と良好な絶縁性を示すとともに、耐熱性にも優れたポリベンゾオキサゾール前駆体、絶縁材用樹脂組成物及びこれを用いた絶縁材を提供する事を目的とする。
【０００６】
【課題を解決するための手段】
本発明者らは、前記従来の問題点を鑑み、鋭意検討を重ねた結果、一般式（１）で表される繰り返し単位を有するポリベンゾオキサゾール前駆体を見いだし、本発明を完成するに至った。
【０００７】
すなわち、下記（ａ）〜（ｅ）項に記載の通りである。
（ａ） 一般式（１）で表される繰り返し単位を有するポリベンゾオキサゾール前駆体。
【０００８】
【化４】
（式中、ＸおよびＹは２価の有機基または単結合を、Ｚは２価の有機基を表す。Ｒ1〜Ｒ6は、Ｈ、Ｆまたはフルオロアルキル基であり、互いに同じであっても異なってもよい。Ｒ7およびＲ8は、数平均分子量が４０以上１０００００以下でグリコール基を有する１価の有機基であり、互いに同じであっても異なってもよい。ｎは１〜１００００の整数である。）
【００１０】
（ｂ） 前記一般式（１）のＸもしくはＺの一方、またはＸとＺの両方がフッ素基またはフルオロアルキル基を有する２価の有機基である前記（ａ）項に記載のポリベンゾオキサゾール前駆体。
【００１２】
（ｃ） 前記一般式（１）のＹが式（２）もしくは（３）である前記（ａ）項または（ｂ）項に記載のポリベンゾオキサゾール前駆体。
【００１３】
【化５】
【化６】
（ｄ） 前記（ａ）〜（ｃ）項のいずれかに記載のポリベンゾオキサゾール前駆体を脱水閉環した構造を有するポリベンゾオキサゾール樹脂組成物。
【００１６】
（ｅ） 前記（ｄ）項に記載のポリベンゾオキサゾール樹脂組成物を用いて得られた絶縁材。
【００１７】
【発明の実施の形態】
本発明のポリベンゾオキサゾール前駆体は、一般式（４）で表されるジアミン化合物と一般式（５）で表されるジカルボン酸化合物とを、ジシクロヘキシルカルボジイミド等の脱水縮合剤の存在下での縮合反応等の方法や酸クロリド法により重合を行うか、
【００１８】
【化７】
【００１９】
【化８】
【００２０】
一般式（６）で表されるビスアミノフェノール化合物と前記一般式（５）で表されるジカルボン酸化合物とを、活性エステル法や酸クロリド法により重合を行い、ポリ（ヒドロキシアミド）とした後、ポリ（ヒドロキシアミド）の水酸基に、一般式（７），（８）で表されるカルボン酸化合物や一般式（９），（１０）で表されるイソシアネート化合物や一般式（１１），（１２）で表されるグリシジル化合物を反応させることにより、製造することができる。
【００２１】
【化９】
【００２２】
【化１０】
【００２３】
【化１１】
【００２４】
【化１２】
【００２５】
【化１３】
【００２６】
【化１４】
【００２７】
【化１５】
【００２８】
一般式（４）で表されるジアミン化合物の例としては、式（１３）〜式（１７）で表される化合物等が挙げられるが、これらに限定されるものではない。また２種以上を併用することも可能である。これらのうち、式（１４）および式（１５）で表される化合物のように、フルオロアルキル基を有するものやフッ素基を有するものは、特に低い誘電率が得られるので好ましい。さらに、樹脂の溶解性等の諸特性とのバランスをとるために、本発明の効果が得られる範囲内で、各種のビスアミノフェノール化合物と共重合を行うことも可能である。
【００２９】
【化１６】
【化１７】
【化１８】
一般式（５）で表されるジカルボン酸化合物の例を挙げると、イソフタル酸、テレフタル酸、３−フルオロイソフタル酸、２−フルオロイソフタル酸、３−フルオロフタル酸、２−フルオロフタル酸、２−フルオロテレフタル酸、２，４，５，６−テトラフルオロイソフタル酸、３，４，５，６−テトラフルオロフタル酸、４，４’−ヘキサフルオロイソプロピリデンジフェニル−１，１’−ジカルボン酸、パーフルオロスベリン酸、２，２’−ビス（トリフルオロメチル）−４，４’−ビフェニレンジカルボン酸、４，４’−オキシビス安息香酸等であるが、必ずしもこれらに限定されるものではない。また、２種類以上のジカルボン酸化合物を組み合わせて使用することも可能である。ジカルボン酸化合物についても、フルオロフタル酸や４，４’−ヘキサフルオロイソプロピリデンジフェニル−１，１’−ジカルボン酸のようにフッ素基またはフルオロアルキル基を有するものは、特に低い誘電率が得られるので好ましい。
【００３３】
一般式（６）で表されるビスアミノフェノール化合物の例としては、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、３，３’−ジヒドロキシ−４，４’−ジアミノビフェニル、２，２−ビス （３− アミノ−４−ヒドロキシフェニル）プロパン、２，２−ビス （３− アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン、１，４−ビス（３− アミノ−４−ヒドロキシフェニル）テトラフルオロベンゼン、２，２−ビス （３− アミノ−４−ヒドロキシ−５−トリフルオロメチルフェニル）ヘキサフルオロプロパン等が挙げられるが、これらに限定されるものではない。２，２−ビス （３− アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパンや１，４−ビス（３− アミノ−４−ヒドロキシフェニル）テトラフルオロベンゼンのように、フルオロアルキル基またはフッ素基を有するものは、特に低い誘電率が得られるので好ましい。
【００３４】
一般式（７），（８）で表されるカルボン酸化合物の例としては、ステアリン酸、ラウリン酸、パルミチン酸、ミリスチン酸等の脂肪酸や一般式（１８）で表されるエチレングリコール基を有するカルボン酸化合物や一般式（１９）で表されるプロピレングリコール基を有するカルボン酸化合物、ポリ（エチレングリコール）モノアルキルエーテルとジカルボン酸のハーフエステル、ポリ（プロピレングリコール）モノアルキルエーテルとジカルボン酸のハーフエステル等が挙げられるが、これらに限定されるものではない。また２種以上を併用することも可能である。これらのうち、エチレングリコール基を有するカルボン酸化合物やプロピレングリコール基を有する化合物のようにグリコール基を有する化合物は、熱処理により分解・揮散しやすく好ましい。
【００３５】
【化１９】
【００３６】
【化２０】
【００３７】
前記一般式（９），（１０）で表されるイソシアネート化合物の例としては、ｎ−ブタンイソシアネート、ｎ−ヘキサンイソシアネート、ｎ−ドデカンイソシアネート等の脂肪族イソシアネート化合物や一般式（２０）で表されるエチレングリコール基を有するイソシアネート化合物や一般式（２１）で表されるプロピレングリコール基を有するイソシアネート化合物、ポリ（エチレングリコール）モノアルキルエーテルをジイソシアネート化合物の一方のイソシアネート基のみに反応させたもの、ポリ（プロピレングリコール）モノアルキルエーテルをジイソシアネート化合物の一方のイソシアネート基のみに反応させたもの、メタノールやエタノール等のアルコールを両末端イソシアネートのプロピレングリコールオリゴマーやエチレングリコールオリゴマーの一方のイソシアネート基のみに反応させたもの等が挙げられるが、これらに限定されるものではない。また２種以上を併用することも可能である。これらのうち、エチレングリコール基を有するカルボン酸化合物やプロピレングリコール基を有する化合物のようにグリコール基を有する化合物は、熱処理により、分解・揮散しやすく好ましい。ジイソシアネート化合物の例としては、２，４−トルエンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート等が挙げられるが、これらに限定されるものではない。
【００３８】
【化２１】
【００３９】
【化２２】
【００４０】
前記一般式（１１），（１２）で表されるグリシジル化合物の例としては、フェニルグリシジルエーテル、トリエチレングリコールメチルグリシジルエーテル、ポリ（エチレングリコール）モノメチルエーテルのグリシジルエーテル、ポリ（プロピレングリコール）モノメチルエーテルのグリシジルエーテル等が挙げられるが、これらに限定されるものではない。また2種以上を併用することも可能である。これらのうち、エチレングリコール基を有するカルボン酸化合物やプロピレングリコール基を有する化合物のように、グリコール基を有する化合物は、熱処理により分解・揮散しやすく好ましい。
【００４１】
酸クロリド法によるポリベンゾオキサゾール前駆体の合成の例を挙げると、まず前記ジカルボン酸化合物を、Ｎ，Ｎ−ジメチルホルムアミド等の触媒存在下、過剰量の塩化チオニルと、室温から７５℃で反応させ、過剰の塩化チオニルを加熱及び減圧により留去する。その後、残査をヘキサン等の溶媒で再結晶することにより、酸クロリドであるジカルボン酸クロリドを得る。次いで、前記ビスアミノフェノール化合物または前記ジアミン化合物を、通常Ｎ−メチル−２−ピロリドン、ジメチルアセトアミド等の極性溶媒に溶解し、ピリジン等の酸受容剤存在下で、ジカルボン酸クロリドと、−３０℃から室温で反応することにより、ポリベンゾオキサゾール前駆体を得ることができる。
【００４２】
本発明のポリベンゾオキサゾール前駆体は、通常、これを溶剤に溶解し、ワニス状にして使用する。溶剤としては、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチル−１，３−ブチレングリコールアセテート、１，３−ブチレングリコール−３−モノメチルエーテル、ピルビン酸メチル、ピルビン酸エチル、メチル−３−メトキシプロピオネート等を１種、または２種以上混合して用いることが出来る。
【００４３】
本発明のポリベンゾオキサゾール前駆体の使用する際は、まず該前駆体を上記溶剤に溶解し、適当な支持体、例えばガラス、金属、シリコーンウエハーやセラミック基盤等に塗布する。塗布方法としては、スピンナーを用いた回転塗布、スプレーコーターを用いた噴霧塗布、浸漬、印刷、ロールコーティング等が挙げられる。このようにして、塗膜を形成した後、加熱処理をして、脱水閉環してポリベンゾオキサゾール樹脂に変換し、ポリベンゾオキサゾール樹脂組成物とすることができる。
【００４４】
本発明のポリベンゾオキサゾール樹脂組成物を用いて、更に加熱することにより、一般式（１）中のＹで結合されたＲ7およびＲ8が、脱離し、熱分解して揮散するこにより、微細な空隙を構成することにより、誘電率の低い膜を形成し、絶縁材を得ることができる。この際、Ｒ7およびＲ8の数平均分子量が、４０未満であると、誘電率が効果的に低くできず、また分子量が、１０００００を超えるものでは、空隙が大きくなりすぎて膜の機械的強度が弱くなったり膜表面に達する連続気泡ができてしまう等の問題が発生する。
【００４５】
必要により、ポリベンゾオキサゾール前駆体、各種添加剤として、界面活性剤やカップリング剤等を添加し、ポリベンゾオキサゾール樹脂組成物とし、更に絶縁材とすることができる。
【００４６】
本発明のポリベンゾオキサゾール前駆体、ポリベンゾオキサゾール樹脂組成物及び絶縁材は、半導体用層間絶縁膜、保護膜、多層回路の層間絶縁膜、フレキシブル銅張板のカバーコート、ソルダーレジスト膜、液晶配向膜等として用いることができる。
【００４７】
【実施例】
以下に、実施例により本発明を具体的に説明するが、本発明は、実施例の内容になんら限定されるものではない。
【００４８】
酸クロリドの合成例
（合成例１）
４，４’−ヘキサフルオロイソプロピリデンジフェニル−１，１’−ジカルボン酸２５ｇ、塩化チオニル４５ｍｌ及び乾燥ジメチルホルムアミド（ＤＭＦ）０．５ｍｌを反応容器に入れ、６０℃で２時間反応させた。反応終了後、過剰の塩化チオニルを加熱及び減圧により留去した。残査をヘキサンを用いて再結晶させて、４，４’−ヘキサフルオロイソプロピリデンジフェニル−１，１’−ジカルボン酸クロリドを得た。
【００４９】
ポリ（ヒドロキシアミド）の合成例
（合成例２）
攪拌装置、窒素導入管、滴下漏斗を付けたセパラブルフラスコ中、２，２−ビス （３− アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン１４．６５ｇ（０．０４ｍｏｌ）を、乾燥したジメチルアセトアミド２００ｇに溶解し、ピリジン７．９２ｇ（０．２０ｍｏｌ）を添加後、乾燥窒素導入下、−１５℃でジメチルアセトアミド１００ｇに、４，４’−ヘキサフルオロイソプロピリデンジフェニル−１，１’−ジカルボン酸クロリド１６．９２ｇ（０．０４ｍｏｌ）を溶解したものを、３０分かけて滴下した。滴下終了後、室温まで戻し、室温で５時間攪拌した。その後、反応液を蒸留水１０００ｍｌに滴下し、沈殿物を集め、乾燥してポリ（ヒドロキシアミド）の粉末を得た。得られたポリ（ヒドロキシアミド）の数平均分子量は２１，０００、重量平均分子量は４２，０００であった。
【００５０】
ジアミン化合物を用いたポリベンゾオキサゾール前駆体及びポリベンゾオキサゾール樹脂の実施例
（実施例１）
攪拌装置、窒素導入管、滴下漏斗を付けたセパラブルフラスコ中、前記式（１４）の構造である２，２−ビス （３− アミノ−４−（１，４，７，１０−テトラオキサウンデシル）フェニル）ヘキサフルオロプロパン１３．１７ｇ（０．０２ｍｏｌ）を、乾燥したジメチルアセトアミド１００ｇに溶解し、ピリジン３．９６ｇ（０．０５ｍｏｌ）を添加後、乾燥窒素導入下、−１５℃でジメチルアセトアミド５０ｇに、合成例１で得た４，４’−ヘキサフルオロイソプロピリデンジフェニル−１，１’−ジカルボン酸クロリド８．４６ｇ（０．０２ｍｏｌ）を溶解したものを、３０分掛けて滴下した。滴下終了後、室温まで戻し、室温で５時間攪拌した。その後、反応液を蒸留水１０００ｍｌに滴下し、沈殿物を集め、乾燥することにより、ポリベンゾオキサゾール前駆体（１）を得た。得られたポリベンゾオキサゾール前駆体（１）の数平均分子量は２５，０００、重量平均分子量は５０，０００であった
【００５１】
ポリベンゾオキサゾール前駆体（１）を、濃度が２０重量％のＮ−メチル−２−ピロリドン（ＮＭＰ）溶液とし、スピンコーターを用いてアルミニウムを蒸着したシリコンウェハ上に塗布した。このとき、熱処理後の膜厚が、約１μmとなるように、スピンコーターの回転数と時間を設定した。塗布後、１００℃のホットプレート上で、１２０秒間乾燥した後、窒素を流入して酸素濃度を１００ｐｐｍ以下に制御したオーブンを用いて、１５０℃３０分間、２５０℃３０分間、４００℃３０分間の熱処理を連続して行いポリベンゾオキサゾール樹脂とし、室温まで冷却した後、空気雰囲気のオーブンで、３００℃１２０分間の熱処理を行い、ポリベンゾオキサゾール樹脂の被膜を得た。
【００５２】
皮膜上に、アルミニウムを蒸着してパターニングを行い所定の大きさの電極を形成した。シリコンウェハ側のアルミニウムとこの電極による容量を測定し、測定後に皮膜の電極隣接部を酸素プラズマによりエッチングして、表面粗さ計により膜厚を測定することにより、周波数１ＭＨｚにおける誘電率を算出したところ２．３であった。この皮膜の断面をＴＥＭにより観察したところ、平均孔径２ｎｍ非連続の空隙が観察された。また、この皮膜のＩＲスペクトルをＦＴ−ＩＲにより測定したところ、１６５６ｃｍ-1のアミドによる吸収は見られず１６２５ｃｍ-1および１０５３ｃｍ-1にオキサゾールによる吸収が観察され、ポリベンゾオキサゾールが生成していることが確認された。ＴＧ／ＤＴＡにより耐熱性を評価したところ、窒素雰囲気での５％重量減少温度は５１６℃であった。
【００５３】
イソシアネート化合物を用いたポリベンゾオキサゾール前駆体及びポリベンゾオキサゾール樹脂の実施例
（実施例２）
攪拌装置、窒素導入管、滴下漏斗を付けたセパラブルフラスコへ、ドライボックス中で、乾燥したＮＭＰ６０ｇ中に４，４’−ジフェニルメタンジイソシアネート１．２５ｇ（０．００５ｍｏｌ）を溶解する。乾燥窒素導入下、系の温度を２０℃に制御しながら、平均分子量１２００のポリ（プロピレングリコール）モノメチルエーテル１２．００ｇ（０．０１ｍｏｌ）をＮＭＰ６０ｇに溶解した溶液を、滴下漏斗から滴下する。２０℃で１時間攪拌を行った後、ＮＭＰ８０ｇに水酸基が０．０１ｍｏｌとなる濃度に合成例２で得たポリ（ヒドロキシアミド）粉末を溶解した溶液を滴下する。滴下終了後、５０℃で１２時間攪拌を行うことによりポリベンゾオキサゾール前駆体（２）のＮＭＰ溶液を得た。得られた前駆体の数平均分子量は９０，０００、重量平均分子量は１８０，０００であった。実施例１のポリベンゾオキサゾール樹脂の被膜を得る工程においてポリベンゾオキサゾール前駆体（１）を濃度が２０重量％のＮＭＰ溶液に替えてポリベンゾオキサゾール前駆体（２）の濃度が１５重量％のＮＭＰ溶液を用いた以外は、実施例１と同様にして、ポリベンゾオキサゾール樹脂の被膜を作製し、評価した。
【００５４】
（実施例３）
攪拌装置、窒素導入管、滴下漏斗を付けたセパラブルフラスコへ、ドライボックス中で、乾燥したＮＭＰ１２０ｇ中に、数平均分子量２５００の両末端イソシアネートのプロピレングリコールオリゴマー１２．５０ｇ（０．００５ｍｏｌ）を溶解する。乾燥窒素導入下、系の温度を２０℃に制御しながら、メタノール０．３２ｇ（０．０１ｍｏｌ）を滴下漏斗から滴下する。２０℃で１時間攪拌を行った後、ＮＭＰ８０ｇに水酸基が０．０１ｍｏｌとなる濃度に合成例２で得たポリ（ヒドロキシアミド）粉末を溶解した溶液を滴下する。滴下終了後、５０℃で１２時間攪拌を行うことにより、ポリベンゾオキサゾール前駆体（３）のＮＭＰ溶液を得た。得られた前駆体の数平均分子量は１７０，０００、重量平均分子量は３４０，０００であった。
実施例１のポリベンゾオキサゾール樹脂の被膜を得る工程においてポリベンゾオキサゾール前駆体（１）を濃度が２０重量％のＮＭＰ溶液に替えてポリベンゾオキサゾール前駆体（３）の濃度が１５重量％のＮＭＰ溶液を用いた以外は、実施例１と同様にして、ポリベンゾオキサゾール樹脂の被膜を作製し、評価した。
【００５５】
グリシジル化合物を用いたポリベンゾオキサゾール前駆体及びポリベンゾオキサゾール樹脂の実施例
（実施例４）
攪拌装置、窒素導入管、滴下漏斗を付けたセパラブルフラスコへ、乾燥したＮＭＰ１２０ｇ中に水酸基が０．０１ｍｏｌとなる濃度に合成例２で得たポリ（ヒドロキシアミド）粉末を溶解する。乾燥窒素導入下、系の温度を２０℃に制御しながら、ＮＭＰ８０ｇ中に数平均分子量３１００のポリ（エチレングリコール）モノメチルエーテルのグリシジルエーテル３１．００ｇ（０．０１ｍｏｌ）を溶解した溶液を滴下漏斗から滴下する。滴下終了後、２０℃で１時間、続いて５０℃で１２時間攪拌を行うことにより、ポリベンゾオキサゾール前駆体（４）のＮＭＰ溶液を得た。得られた前駆体の数平均分子量は１８０，０００、重量平均分子量は３６０，０００であった。
実施例１のポリベンゾオキサゾール樹脂の被膜を得る工程においてポリベンゾオキサゾール前駆体（１）を濃度が２０重量％のＮＭＰ溶液に替えてポリベンゾオキサゾール前駆体（４）の濃度が１５重量％のＮＭＰ溶液を用いた以外は、実施例１と同様にして、ポリベンゾオキサゾール樹脂の被膜を作製し、評価した。
【００５６】
カルボン酸化合物を用いたポリベンゾオキサゾール前駆体及びポリベンゾオキサゾール樹脂の実施例
（実施例５）
攪拌装置、窒素導入管、滴下漏斗を付けたセパラブルフラスコへ、乾燥したＮＭＰ２００ｇ中に水酸基が０．０１ｍｏｌとなる濃度に合成例２で得たポリ（ヒドロキシアミド）粉末と、数平均分子量２５００のポリ（プロピレングリコール）モノアルキルエーテルとジカルボン酸のハーフエステル２５．００ｇ（０．０１ｍｏｌ）を、を溶解する。乾燥窒素導入下、系の温度を２０℃に制御しながら、ＮＭＰ２０ｇ中にジシクロヘキシルカルボジイミド２．０６ｇ（０．０１ｍｏｌ）を溶解した溶液を、滴下漏斗から滴下する。滴下終了後、２０℃で１２時間攪拌を行った後、吸引濾過を行い副生成物であるジシクロヘキシルカルボジウレアの固形物を濾別することにより、ポリベンゾオキサゾール前駆体（５）のＮＭＰ溶液を得た。得られた前駆体の数平均分子量は１５０，０００、重量平均分子量は３００，０００であった。
実施例１のポリベンゾオキサゾール樹脂の被膜を得る工程においてポリベンゾオキサゾール前駆体（１）を濃度が２０重量％のＮＭＰ溶液に替えてポリベンゾオキサゾール前駆体（５）の濃度が１５重量％のＮＭＰ溶液を用いた以外は、実施例１と同様にして、ポリベンゾオキサゾール樹脂の被膜を作製し、評価した。
【００５７】
表１に実施例２〜５の評価結果を示す。
【表１】
（比較例１）
実施例１のポリベンゾオキサゾール樹脂の被膜を得る工程においてポリベンゾオキサゾール前駆体（１）のかわりに合成例２で得たポリ（ヒドロキシアミド）粉末を用いた以外は実施例１と同様にして、ポリベンゾオキサゾール樹脂の被膜を作製し、評価した。皮膜とした場合の誘電率は２．６であり、ＩＲスペクトルからはポリベンゾオキサゾールが生成していることが確認され、ＴＧ／ＤＴＡによる窒素雰囲気での５％重量減少温度は５１６℃であった。
【００５９】
（比較例２）
実施例１のポリベンゾオキサゾール前駆体（１）を得る工程において２，２'−ビス （３− アミノ−４−（１，４，７，１０−テトラオキサウンデシル）フェニル）ヘキサフルオロプロパン１３．１７ｇ（０．０２ｍｏｌ）のかわりに２，２−ビス （３− アミノ−４−メトキシフェニル）ヘキサフルオロプロパン７．８９ｇ（０．０２ｍｏｌ）を用いた以外は実施例１と同様にして、合成を行いポリベンゾオキサゾール前駆体（５）を得た。得られた前駆体の数平均分子量は２２，０００、重量平均分子量は４４，０００であった。
実施例１のポリベンゾオキサゾール樹脂の被膜を得る工程においてポリベンゾオキサゾール前駆体（１）のかわりにポリベンゾオキサゾール前駆体（５）を用いた以外は実施例１と同様にして、ポリベンゾオキサゾール樹脂の被膜を作製し、評価した。皮膜とした場合の誘電率は２．６であり、ＩＲスペクトルからはポリベンゾオキサゾールが生成していることが確認され、ＴＧ／ＤＴＡによる窒素雰囲気での５％重量減少温度は５１６℃であった。
【００６０】
（比較例３）
実施例３のポリベンゾオキサゾール前駆体（３）を得る工程において、数平均分子量２５００の両末端イソシアネートのプロピレングリコールオリゴマー５０．００ｇ（０．０２ｍｏｌ）のかわりに数平均分子量１２０，０００の両末端イソシアネートのポリ（プロピレングリコール）１２０．００ｇ（０．００１ｍｏｌ）を用い、溶液の粘度が高くなり攪拌が困難になることを避けるために、ＮＭＰの量を２倍にした以外は実施例３と同様にして、ポリベンゾオキサゾール前駆体（６）のＮＭＰ溶液を得た。得られた前駆体の数平均分子量は３，１７１，０００、重量平均分子量は６，３４２，０００であった。
実施例１のポリベンゾオキサゾール樹脂の被膜を得る工程においてポリベンゾオキサゾール前駆体（１）のかわりにポリベンゾオキサゾール前駆体（６）を用いた以外は実施例１と同様にして、ポリベンゾオキサゾール樹脂の被膜を作製し、皮膜の誘電率の測定を行ったところ、短絡により測定できなかった。
【００６１】
実施例１〜４の本発明のポリベンゾオキサゾール前駆体を用いて作製したポリベンゾオキサゾール皮膜はいずれも誘電率が低く２．０〜２．３であり、さらに耐熱性が高いという良好な特性を示した。
【００６２】
比較例１では一般的なポリベンゾオキサゾール前駆体であるポリ（ヒドロキシアミド）粉末を用いたため、耐熱性は同等で良好であるが誘電率は実施例１〜４より大幅に高い２．６であった。
【００６３】
比較例２では一般式（４）で示されるＲ7およびＲ8の数平均分子量が４０未満と小さかったために、誘電率は２．６と一般的なポリベンゾオキサゾール前駆体であるポリ（ヒドロキシアミド）粉末を用いた場合と同様に、実施例１〜４より大幅に高かった。
【００６４】
比較例３では一般式（４）で示されるＲ7およびＲ8の数平均分子量が１０００００を超える高分子量物であったために、膜厚約１μmの皮膜を形成した場合には上下に貫通する穴が生成してしまい上下電極がショートしてしまった。
【００６５】
【発明の効果】
本発明のポリベンゾオキサゾール前駆体、絶縁材用樹脂組成物およびこれを用いた絶縁材は、電気特性および熱特性、特に誘電率が非常に低い固形物を得ることができる材料である。従って、半導体装置の層間絶縁膜、保護膜、多層回路の層間絶縁膜、フレキシブル銅張版のカバーコートなどとして極めて有用なものでる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an insulating material, and more particularly to a polybenzoxazole precursor having excellent characteristics for electrical and electronic equipment and semiconductor devices, a resin composition for insulating material, and an insulating material using the same. .
[0002]
[Prior art]
Of the characteristics required for materials for electrical and electronic equipment and semiconductor devices, electrical characteristics and heat resistance are the most important characteristics. Particularly in recent years, with the miniaturization of circuits and the speeding up of signals, insulating materials having a low dielectric constant are required. In order to achieve both of these characteristics, an organic insulating film with high heat resistance is expected. For example, conventionally used inorganic insulating films such as silicon dioxide exhibit high heat resistance, but have a high dielectric constant, and it is becoming difficult to achieve both the above-mentioned characteristics. An organic insulating film typified by a polyimide resin is excellent in electrical characteristics and heat resistance and can satisfy both characteristics, and is actually used for solder resists, coverlays, liquid crystal alignment films, and the like.
[0003]
However, with the recent increase in functionality and performance of semiconductors, there has been a need for significant improvements in electrical characteristics and heat resistance, and therefore higher performance resins are required. In particular, low dielectric constant materials with a dielectric constant of less than 2.5 are expected. Even in polyimide resins, both electrical properties and heat resistance can be achieved by introducing fluorine and trifluoromethyl groups into the polymer. Has been attempted but has not reached the required level at this time.
[0004]
Among resins other than polyimide resins, polybenzoxazole resins are expected. The polyimide resin has two carboxyl groups in the imide ring, and thus has an adverse effect on electrical characteristics. Therefore, in general, polybenzoxazole resins are extremely useful resins because they have better electrical characteristics than polyimide resins and have the same heat resistance. However, the required level of electrical properties is very high, and the level required by conventional polybenzoxazole resins has not been reached.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a polybenzoxazole precursor, a resin composition for an insulating material, and an insulating material using the same, which have an extremely low dielectric constant and good insulating properties and are excellent in heat resistance. .
[0006]
[Means for Solving the Problems]
As a result of intensive studies in view of the above-described conventional problems, the present inventors have found a polybenzoxazole precursor having a repeating unit represented by the general formula (1), and have completed the present invention. .
[0007]
That is, the following (a) to ( e ).
(A) A polybenzoxazole precursor having a repeating unit represented by the general formula (1).
[0008]
[Formula 4]
(In the formula, X and Y represent a divalent organic group or a single bond, and Z represents a divalent organic group. R 1 ~ R 6 Are H, F or fluoroalkyl groups, which may be the same or different. R 7 And R 8 Has a number average molecular weight of 40 to 100,000 With glycol groups It is a monovalent organic group and may be the same or different. n is an integer of 1 to 10,000. )
[0010]
(B) The polybenzoxazole precursor according to (a), wherein one of X and Z in the general formula (1), or both X and Z are divalent organic groups having a fluorine group or a fluoroalkyl group body.
[0012]
( c The item (a), wherein Y in the general formula (1) is the formula (2) or (3) Or (b) The polybenzoxazole precursor described in 1.
[0013]
[Chemical formula 5]
[Chemical 6]
( d (A) to (a) (C) A polybenzoxazole resin composition having a structure obtained by dehydrating and ring-closing the polybenzoxazole precursor according to any one of the items.
[0016]
( e ) Said ( d An insulating material obtained using the polybenzoxazole resin composition described in the item).
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The polybenzoxazole precursor of the present invention is a condensation of a diamine compound represented by the general formula (4) and a dicarboxylic acid compound represented by the general formula (5) in the presence of a dehydration condensing agent such as dicyclohexylcarbodiimide. Polymerization is performed by a method such as reaction or acid chloride method,
[0018]
[Chemical 7]
[0019]
[Chemical 8]
[0020]
After the bisaminophenol compound represented by the general formula (6) and the dicarboxylic acid compound represented by the general formula (5) are polymerized by an active ester method or an acid chloride method to obtain poly (hydroxyamide) , A hydroxyl group of poly (hydroxyamide), a carboxylic acid compound represented by general formula (7), (8), an isocyanate compound represented by general formula (9), (10), or general formula (11), ( It can be produced by reacting the glycidyl compound represented by 12).
[0021]
[Chemical 9]
[0022]
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[0023]
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[0024]
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[0025]
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[0026]
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[0027]
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[0028]
Examples of the diamine compound represented by the general formula (4) include, but are not limited to, compounds represented by the formulas (13) to (17). Two or more kinds can be used in combination. Among these, those having a fluoroalkyl group and those having a fluorine group, such as the compounds represented by the formulas (14) and (15), are particularly preferable because a low dielectric constant is obtained. Furthermore, in order to balance various properties such as the solubility of the resin, it is possible to carry out copolymerization with various bisaminophenol compounds within the range where the effects of the present invention can be obtained.
[0029]
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Examples of the dicarboxylic acid compound represented by the general formula (5) are isophthalic acid, terephthalic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 3-fluorophthalic acid, 2-fluorophthalic acid, 2- Fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 3,4,5,6-tetrafluorophthalic acid, 4,4′-hexafluoroisopropylidenediphenyl-1,1′-dicarboxylic acid, Fluorosberic acid, 2,2′-bis (trifluoromethyl) -4,4′-biphenylenedicarboxylic acid, 4,4′-oxybisbenzoic acid, etc. are not necessarily limited thereto. It is also possible to use a combination of two or more dicarboxylic acid compounds. As for dicarboxylic acid compounds, those having a fluorine group or a fluoroalkyl group such as fluorophthalic acid or 4,4′-hexafluoroisopropylidenediphenyl-1,1′-dicarboxylic acid have a particularly low dielectric constant. preferable.
[0033]
Examples of the bisaminophenol compound represented by the general formula (6) include 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,4-bis (3-amino-4-hydroxyphenyl) tetra Examples include, but are not limited to, fluorobenzene, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, and the like. Those having a fluoroalkyl group or a fluorine group, such as 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1,4-bis (3-amino-4-hydroxyphenyl) tetrafluorobenzene Is preferable because a particularly low dielectric constant can be obtained.
[0034]
Examples of the carboxylic acid compounds represented by the general formulas (7) and (8) include fatty acids such as stearic acid, lauric acid, palmitic acid, and myristic acid, and ethylene glycol groups represented by the general formula (18). Carboxylic acid compounds and carboxylic acid compounds having a propylene glycol group represented by the general formula (19), poly (ethylene glycol) monoalkyl ether and dicarboxylic acid half ester, poly (propylene glycol) monoalkyl ether and dicarboxylic acid half Examples include, but are not limited to, esters. Two or more kinds can be used in combination. Among these, compounds having a glycol group such as a carboxylic acid compound having an ethylene glycol group and a compound having a propylene glycol group are preferable because they are easily decomposed and volatilized by heat treatment.
[0035]
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[0036]
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[0037]
Examples of the isocyanate compounds represented by the general formulas (9) and (10) include aliphatic isocyanate compounds such as n-butane isocyanate, n-hexane isocyanate, and n-dodecane isocyanate, and the general formula (20). An isocyanate compound having an ethylene glycol group, an isocyanate compound having a propylene glycol group represented by the general formula (21), a poly (ethylene glycol) monoalkyl ether reacted with only one isocyanate group of a diisocyanate compound, poly (Propylene glycol) monoalkyl ether reacted with only one isocyanate group of a diisocyanate compound, alcohol such as methanol or ethanol, propylene glycol oligomer or ethylene of both end isocyanate And those obtained by reacting only one of the isocyanate groups of the recall oligomer, and the like, but not limited thereto. Two or more kinds can be used in combination. Among these, a compound having a glycol group such as a carboxylic acid compound having an ethylene glycol group or a compound having a propylene glycol group is preferable because it is easily decomposed and volatilized by heat treatment. Examples of the diisocyanate compound include 2,4-toluene diisocyanate and 4,4′-diphenylmethane diisocyanate, but are not limited thereto.
[0038]
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[0039]
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[0040]
Examples of the glycidyl compounds represented by the general formulas (11) and (12) include phenyl glycidyl ether, triethylene glycol methyl glycidyl ether, glycidyl ether of poly (ethylene glycol) monomethyl ether, and poly (propylene glycol) monomethyl ether. However, it is not limited to these. Two or more kinds can be used in combination. Among these, compounds having a glycol group, such as a carboxylic acid compound having an ethylene glycol group and a compound having a propylene glycol group, are preferable because they are easily decomposed and volatilized by heat treatment.
[0041]
An example of the synthesis of a polybenzoxazole precursor by the acid chloride method is as follows. First, the dicarboxylic acid compound is reacted with an excess amount of thionyl chloride in the presence of a catalyst such as N, N-dimethylformamide at room temperature to 75 ° C. Excess thionyl chloride is distilled off by heating and reduced pressure. Thereafter, the residue is recrystallized with a solvent such as hexane to obtain dicarboxylic acid chloride which is acid chloride. Next, the bisaminophenol compound or the diamine compound is usually dissolved in a polar solvent such as N-methyl-2-pyrrolidone or dimethylacetamide, and in the presence of an acid acceptor such as pyridine, -30 ° C. The polybenzoxazole precursor can be obtained by reacting at room temperature.
[0042]
The polybenzoxazole precursor of the present invention is usually used by dissolving it in a solvent and varnishing it. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropio Nate or the like can be used alone or in combination of two or more.
[0043]
When the polybenzoxazole precursor of the present invention is used, the precursor is first dissolved in the above solvent and applied to a suitable support such as glass, metal, silicone wafer or ceramic substrate. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Thus, after forming a coating film, it can heat-process, spin-dry | dehydrate and ring-close, convert into polybenzoxazole resin, and can be set as a polybenzoxazole resin composition.
[0044]
By further heating using the polybenzoxazole resin composition of the present invention, R bonded by Y in the general formula (1) 7 And R 8 However, desorption, thermal decomposition, and volatilization make up fine voids, whereby a film with a low dielectric constant can be formed and an insulating material can be obtained. At this time, R 7 And R 8 If the number average molecular weight is less than 40, the dielectric constant cannot be effectively lowered, and if the molecular weight exceeds 100000, the voids become too large and the mechanical strength of the film becomes weak or the film surface Problems such as the formation of continuous bubbles that reach are generated.
[0045]
If necessary, as a polybenzoxazole precursor and various additives, a surfactant, a coupling agent, and the like can be added to obtain a polybenzoxazole resin composition and further as an insulating material.
[0046]
The polybenzoxazole precursor, the polybenzoxazole resin composition and the insulating material of the present invention are a semiconductor interlayer insulating film, a protective film, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment It can be used as a film or the like.
[0047]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the contents of the examples.
[0048]
Synthesis example of acid chloride
(Synthesis Example 1)
25 g of 4,4′-hexafluoroisopropylidenediphenyl-1,1′-dicarboxylic acid, 45 ml of thionyl chloride and 0.5 ml of dry dimethylformamide (DMF) were placed in a reaction vessel and reacted at 60 ° C. for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off by heating and reduced pressure. The residue was recrystallized using hexane to obtain 4,4′-hexafluoroisopropylidenediphenyl-1,1′-dicarboxylic acid chloride.
[0049]
Synthesis example of poly (hydroxyamide)
(Synthesis Example 2)
In a separable flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel, 14.65 g (0.04 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to 200 g of dried dimethylacetamide. After adding 7.92 g (0.20 mol) of pyridine, 4,4′-hexafluoroisopropylidenediphenyl-1,1′-dicarboxylic acid chloride was added to 100 g of dimethylacetamide at −15 ° C. with introduction of dry nitrogen. What melt | dissolved 16.92g (0.04mol) was dripped over 30 minutes. After completion of the dropping, the temperature was returned to room temperature and stirred at room temperature for 5 hours. Thereafter, the reaction solution was dropped into 1000 ml of distilled water, and the precipitate was collected and dried to obtain poly (hydroxyamide) powder. The resulting poly (hydroxyamide) had a number average molecular weight of 21,000 and a weight average molecular weight of 42,000.
[0050]
Examples of polybenzoxazole precursors and polybenzoxazole resins using diamine compounds
Example 1
In a separable flask equipped with a stirrer, a nitrogen introducing tube, and a dropping funnel, 2,2-bis (3-amino-4- (1,4,7,10-tetraoxaun) having the structure of the above formula (14) was used. Decyl) phenyl) hexafluoropropane (13.17 g, 0.02 mol) is dissolved in 100 g of dried dimethylacetamide, and 3.96 g (0.05 mol) of pyridine is added, and then dimethylacetamide is introduced at −15 ° C. under introduction of dry nitrogen. A solution prepared by dissolving 8.46 g (0.02 mol) of 4,4′-hexafluoroisopropylidenediphenyl-1,1′-dicarboxylic acid chloride obtained in Synthesis Example 1 was added dropwise to 50 g over 30 minutes. After completion of the dropping, the temperature was returned to room temperature and stirred at room temperature for 5 hours. Thereafter, the reaction solution was added dropwise to 1000 ml of distilled water, and the precipitate was collected and dried to obtain a polybenzoxazole precursor (1). The resulting polybenzoxazole precursor (1) had a number average molecular weight of 25,000 and a weight average molecular weight of 50,000.
[0051]
The polybenzoxazole precursor (1) was applied as a N-methyl-2-pyrrolidone (NMP) solution having a concentration of 20% by weight on a silicon wafer on which aluminum was deposited using a spin coater. At this time, the rotation speed and time of the spin coater were set so that the film thickness after the heat treatment was about 1 μm. After coating, after drying for 120 seconds on a 100 ° C. hot plate, using an oven in which nitrogen is introduced and the oxygen concentration is controlled to 100 ppm or less, the temperature is 150 ° C. for 30 minutes, 250 ° C. for 30 minutes, 400 ° C. for 30 minutes. Heat treatment was continuously performed to obtain a polybenzoxazole resin, which was cooled to room temperature, and then heat-treated at 300 ° C. for 120 minutes in an air atmosphere oven to obtain a polybenzoxazole resin film.
[0052]
On the film, aluminum was deposited and patterned to form electrodes of a predetermined size. The dielectric constant at a frequency of 1 MHz was calculated by measuring the capacitance of the silicon wafer side aluminum and the capacity of this electrode, etching the electrode adjacent portion of the film with oxygen plasma after measurement, and measuring the film thickness with a surface roughness meter. However, it was 2.3. When the cross section of this film was observed by TEM, voids having a discontinuous average pore diameter of 2 nm were observed. Moreover, when the IR spectrum of this film was measured by FT-IR, it was 1656 cm. -1 Absorption by amide is not seen 1625cm -1 And 1053 cm -1 Absorption due to oxazole was observed in the sample, and it was confirmed that polybenzoxazole was formed. When heat resistance was evaluated by TG / DTA, the 5% weight reduction temperature in a nitrogen atmosphere was 516 ° C.
[0053]
Examples of polybenzoxazole precursors and polybenzoxazole resins using isocyanate compounds
(Example 2)
In a separable flask equipped with a stirrer, a nitrogen introducing tube, and a dropping funnel, 1.25 g (0.005 mol) of 4,4′-diphenylmethane diisocyanate is dissolved in 60 g of dried NMP in a dry box. A solution of 12.00 g (0.01 mol) of poly (propylene glycol) monomethyl ether having an average molecular weight of 1200 in 60 g of NMP is added dropwise from a dropping funnel while controlling the temperature of the system at 20 ° C. while introducing dry nitrogen. After stirring at 20 ° C. for 1 hour, a solution in which the poly (hydroxyamide) powder obtained in Synthesis Example 2 is dissolved in 80 g of NMP at a concentration such that the hydroxyl group becomes 0.01 mol is added dropwise. After completion of dropping, the mixture was stirred at 50 ° C. for 12 hours to obtain an NMP solution of the polybenzoxazole precursor (2). The obtained precursor had a number average molecular weight of 90,000 and a weight average molecular weight of 180,000. In the step of obtaining the polybenzoxazole resin film of Example 1, the polybenzoxazole precursor (1) was replaced with an NMP solution having a concentration of 20% by weight, and the concentration of the polybenzoxazole precursor (2) was 15% by weight. A polybenzoxazole resin film was prepared and evaluated in the same manner as in Example 1 except that the solution was used.
[0054]
(Example 3)
Dissolve 12.50 g (0.005 mol) of propylene glycol oligomer of both end isocyanates with number average molecular weight of 2500 in dry NMP 120 g in a separable flask equipped with a stirrer, nitrogen inlet tube and dropping funnel in a dry box. To do. Under the introduction of dry nitrogen, 0.32 g (0.01 mol) of methanol is dropped from the dropping funnel while controlling the temperature of the system at 20 ° C. After stirring at 20 ° C. for 1 hour, a solution in which the poly (hydroxyamide) powder obtained in Synthesis Example 2 is dissolved in 80 g of NMP at a concentration such that the hydroxyl group becomes 0.01 mol is added dropwise. After completion of the dropping, the mixture was stirred at 50 ° C. for 12 hours to obtain an NMP solution of the polybenzoxazole precursor (3). The number average molecular weight of the obtained precursor was 170,000, and the weight average molecular weight was 340,000.
In the step of obtaining the polybenzoxazole resin film of Example 1, the polybenzoxazole precursor (1) was replaced with an NMP solution having a concentration of 20% by weight, and the concentration of the polybenzoxazole precursor (3) was 15% by weight. A polybenzoxazole resin film was prepared and evaluated in the same manner as in Example 1 except that the solution was used.
[0055]
Examples of polybenzoxazole precursors and polybenzoxazole resins using glycidyl compounds
(Example 4)
In a separable flask equipped with a stirrer, a nitrogen introducing tube, and a dropping funnel, the poly (hydroxyamide) powder obtained in Synthesis Example 2 is dissolved in a concentration of 0.01 mol of hydroxyl group in 120 g of dried NMP. A solution of 31.00 g (0.01 mol) of glycidyl ether of poly (ethylene glycol) monomethyl ether having a number average molecular weight of 3100 in 80 g of NMP was added from a dropping funnel while controlling the temperature of the system at 20 ° C. while introducing dry nitrogen. Dripping. After completion of dropping, the mixture was stirred at 20 ° C. for 1 hour and then at 50 ° C. for 12 hours to obtain an NMP solution of a polybenzoxazole precursor (4). The obtained precursor had a number average molecular weight of 180,000 and a weight average molecular weight of 360,000.
In the step of obtaining the polybenzoxazole resin film of Example 1, the polybenzoxazole precursor (1) was replaced with an NMP solution having a concentration of 20% by weight, and the concentration of the polybenzoxazole precursor (4) was 15% by weight. A polybenzoxazole resin film was prepared and evaluated in the same manner as in Example 1 except that the solution was used.
[0056]
Examples of polybenzoxazole precursors and polybenzoxazole resins using carboxylic acid compounds
(Example 5)
To a separable flask equipped with a stirrer, a nitrogen introduction tube, and a dropping funnel, the poly (hydroxyamide) powder obtained in Synthesis Example 2 and having a number average molecular weight of 2500 in a concentration of 0.01 mol of hydroxyl group in 200 g of dried NMP Dissolve 25.00 g (0.01 mol) of poly (propylene glycol) monoalkyl ether and half ester of dicarboxylic acid. A solution prepared by dissolving 2.06 g (0.01 mol) of dicyclohexylcarbodiimide in 20 g of NMP is dropped from a dropping funnel while controlling the temperature of the system at 20 ° C. while introducing dry nitrogen. After completion of the dropwise addition, the mixture was stirred at 20 ° C. for 12 hours, and then suction filtration was performed to separate a solid product of dicyclohexylcarbodiurea as a by-product, thereby obtaining an NMP solution of the polybenzoxazole precursor (5). It was. The number average molecular weight of the obtained precursor was 150,000, and the weight average molecular weight was 300,000.
In the step of obtaining the polybenzoxazole resin film of Example 1, the polybenzoxazole precursor (1) is replaced with an NMP solution having a concentration of 20% by weight, and the concentration of the polybenzoxazole precursor (5) is 15% by weight. A polybenzoxazole resin film was prepared and evaluated in the same manner as in Example 1 except that the solution was used.
[0057]
Table 1 shows the evaluation results of Examples 2 to 5.
[Table 1]
(Comparative Example 1)
Except for using the poly (hydroxyamide) powder obtained in Synthesis Example 2 instead of the polybenzoxazole precursor (1) in the step of obtaining the polybenzoxazole resin film of Example 1, A polybenzoxazole resin film was prepared and evaluated. The dielectric constant in the case of the film was 2.6, and it was confirmed from the IR spectrum that polybenzoxazole was produced, and the 5% weight loss temperature in a nitrogen atmosphere by TG / DTA was 516 ° C. .
[0059]
(Comparative Example 2)
In the step of obtaining the polybenzoxazole precursor (1) of Example 1, 2,2′-bis (3-amino-4- (1,4,7,10-tetraoxaundecyl) phenyl) hexafluoropropane13. Synthesis was carried out in the same manner as in Example 1 except that 7.89 g (0.02 mol) of 2,2-bis (3-amino-4-methoxyphenyl) hexafluoropropane was used instead of 17 g (0.02 mol). A polybenzoxazole precursor (5) was obtained. The number average molecular weight of the obtained precursor was 22,000, and the weight average molecular weight was 44,000.
A polybenzoxazole resin was obtained in the same manner as in Example 1 except that the polybenzoxazole precursor (5) was used instead of the polybenzoxazole precursor (1) in the step of obtaining the polybenzoxazole resin film of Example 1. A coating was prepared and evaluated. The dielectric constant in the case of the film was 2.6, and it was confirmed from the IR spectrum that polybenzoxazole was produced, and the 5% weight loss temperature in a nitrogen atmosphere by TG / DTA was 516 ° C. .
[0060]
(Comparative Example 3)
In the step of obtaining the polybenzoxazole precursor (3) of Example 3, both terminal isocyanates having a number average molecular weight of 120,000 instead of 50.00 g (0.02 mol) of propylene glycol oligomers of both terminal isocyanates having a number average molecular weight of 2500 The same procedure as in Example 3 except that 120.00 g (0.001 mol) of poly (propylene glycol) was used and the amount of NMP was doubled in order to prevent the solution from becoming too viscous and difficult to stir. Thus, an NMP solution of the polybenzoxazole precursor (6) was obtained. The number average molecular weight of the obtained precursor was 3,171,000, and the weight average molecular weight was 6,342,000.
A polybenzoxazole resin was obtained in the same manner as in Example 1 except that the polybenzoxazole precursor (6) was used instead of the polybenzoxazole precursor (1) in the step of obtaining the polybenzoxazole resin film of Example 1. When the dielectric constant of the film was measured, it was not possible to measure due to a short circuit.
[0061]
Each of the polybenzoxazole films prepared using the polybenzoxazole precursors of Examples 1 to 4 of the present invention has a low dielectric constant of 2.0 to 2.3, and further has good characteristics of high heat resistance. Indicated.
[0062]
In Comparative Example 1, poly (hydroxyamide) powder, which is a general polybenzoxazole precursor, was used, so the heat resistance was equivalent and good, but the dielectric constant was 2.6, which is significantly higher than those of Examples 1-4. It was.
[0063]
In Comparative Example 2, R represented by the general formula (4) 7 And R 8 Since the number average molecular weight of the polymer was as small as less than 40, the dielectric constant was 2.6, which was much larger than in Examples 1 to 4 as in the case of using a poly (hydroxyamide) powder which is a general polybenzoxazole precursor. It was expensive.
[0064]
In Comparative Example 3, R represented by the general formula (4) 7 And R 8 Therefore, when a film having a film thickness of about 1 μm was formed, a hole penetrating vertically was formed and the upper and lower electrodes were short-circuited.
[0065]
【The invention's effect】
The polybenzoxazole precursor of the present invention, the resin composition for an insulating material, and the insulating material using the same are materials capable of obtaining a solid material having a very low electrical property and thermal property, particularly a dielectric constant. Therefore, it is extremely useful as an interlayer insulating film for semiconductor devices, a protective film, an interlayer insulating film for multilayer circuits, and a cover coat for flexible copper-clad plates.
Claims (5)
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