JP7395817B2 - Method for producing patterned cured film, photosensitive resin composition, cured film, interlayer insulating film, cover coat layer, surface protective film, and electronic components - Google Patents
Method for producing patterned cured film, photosensitive resin composition, cured film, interlayer insulating film, cover coat layer, surface protective film, and electronic components Download PDFInfo
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- JP7395817B2 JP7395817B2 JP2018188071A JP2018188071A JP7395817B2 JP 7395817 B2 JP7395817 B2 JP 7395817B2 JP 2018188071 A JP2018188071 A JP 2018188071A JP 2018188071 A JP2018188071 A JP 2018188071A JP 7395817 B2 JP7395817 B2 JP 7395817B2
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- photosensitive resin
- resin composition
- cured film
- film
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- 239000011342 resin composition Substances 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 33
- 239000010410 layer Substances 0.000 title claims description 31
- 239000011229 interlayer Substances 0.000 title claims description 23
- 230000001681 protective effect Effects 0.000 title claims description 11
- 229920005989 resin Polymers 0.000 claims description 43
- 239000011347 resin Substances 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 26
- 239000004642 Polyimide Substances 0.000 claims description 23
- 125000001931 aliphatic group Chemical group 0.000 claims description 23
- 229920001721 polyimide Polymers 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000001451 organic peroxides Chemical class 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 230000003449 preventive effect Effects 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- 239000000126 substance Substances 0.000 description 27
- -1 bis(trifluoromethyl)methylene group Chemical group 0.000 description 15
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- 238000000034 method Methods 0.000 description 12
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 6
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
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- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 3
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 2
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
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- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000004151 rapid thermal annealing Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
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- 238000004335 scaling law Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 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
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- HAQMPJFWQWLQDO-UHFFFAOYSA-N tert-butyl-ethyl-hydroxy-phenylsilane Chemical compound CC[Si](O)(C(C)(C)C)C1=CC=CC=C1 HAQMPJFWQWLQDO-UHFFFAOYSA-N 0.000 description 1
- UNAYGNMKNYRIHL-UHFFFAOYSA-N tert-butyl-hydroxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](O)(C(C)(C)C)C1=CC=CC=C1 UNAYGNMKNYRIHL-UHFFFAOYSA-N 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- UNKMHLWJZHLPPM-UHFFFAOYSA-N triethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CCO[Si](OCC)(OCC)COCC1CO1 UNKMHLWJZHLPPM-UHFFFAOYSA-N 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- GSUGNQKJVLXBHC-UHFFFAOYSA-N triethoxy-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCOCC1CO1 GSUGNQKJVLXBHC-UHFFFAOYSA-N 0.000 description 1
- HPEPIADELDNCED-UHFFFAOYSA-N triethoxysilylmethanol Chemical compound CCO[Si](CO)(OCC)OCC HPEPIADELDNCED-UHFFFAOYSA-N 0.000 description 1
- RHCQSXFNFRBOMC-UHFFFAOYSA-N triethoxysilylmethylurea Chemical compound CCO[Si](OCC)(OCC)CNC(N)=O RHCQSXFNFRBOMC-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- FCVNATXRSJMIDT-UHFFFAOYSA-N trihydroxy(phenyl)silane Chemical compound O[Si](O)(O)C1=CC=CC=C1 FCVNATXRSJMIDT-UHFFFAOYSA-N 0.000 description 1
- QQUBYBOFPPCWDM-UHFFFAOYSA-N trihydroxy-(4-trihydroxysilylphenyl)silane Chemical compound O[Si](O)(O)C1=CC=C([Si](O)(O)O)C=C1 QQUBYBOFPPCWDM-UHFFFAOYSA-N 0.000 description 1
- LFBULLRGNLZJAF-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](OC)(OC)COCC1CO1 LFBULLRGNLZJAF-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-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
- GUKYSRVOOIKHHB-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCOCC1CO1 GUKYSRVOOIKHHB-UHFFFAOYSA-N 0.000 description 1
- SPHALHRGAQVBKI-UHFFFAOYSA-N trimethoxysilylmethanol Chemical compound CO[Si](CO)(OC)OC SPHALHRGAQVBKI-UHFFFAOYSA-N 0.000 description 1
- UOTGHAMTHYCXIM-UHFFFAOYSA-N trimethoxysilylmethylurea Chemical compound CO[Si](OC)(OC)CNC(N)=O UOTGHAMTHYCXIM-UHFFFAOYSA-N 0.000 description 1
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- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
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- Polymerisation Methods In General (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、パターン硬化膜の製造方法、感光性樹脂組成物、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品に関する。 The present invention relates to a method for producing a patterned cured film, a photosensitive resin composition, a cured film, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.
従来、半導体素子の表面保護膜及び層間絶縁膜には、優れた耐熱性と電気特性、機械特性等を併せ持つポリイミドやポリベンゾオキサゾールが用いられている。近年、これらの樹脂自身に感光特性を付与した感光性樹脂組成物が用いられており、これを用いるとパターン硬化膜の製造工程が簡略化でき、煩雑な製造工程を短縮できる(例えば、特許文献1参照)。 Conventionally, polyimide and polybenzoxazole, which have excellent heat resistance, electrical properties, mechanical properties, etc., have been used for surface protection films and interlayer insulating films of semiconductor devices. In recent years, photosensitive resin compositions in which these resins themselves have been given photosensitivity properties have been used, and by using these, the manufacturing process of patterned cured films can be simplified and the complicated manufacturing process can be shortened (for example, as disclosed in Patent Document (see 1).
ところで、近年、コンピュータの高性能化を支えてきたトランジスタの微細化は、スケーリング則の限界に来ており、さらなる高性能化や高速化のために半導体素子を3次元的に積層する積層デバイス構造が注目を集めている。 By the way, in recent years, the miniaturization of transistors, which has supported the high performance of computers, has reached the limit of the scaling law, and in order to further improve performance and speed, a stacked device structure in which semiconductor elements are stacked three-dimensionally is being developed. is attracting attention.
積層デバイス構造の中でも、マルチダイファンアウトウエハレベルパッケージ(Multi-die Fanout Wafer Level Packaging)は、一つのパッケージの中に複数のダイを一括封止して製造するパッケージであり、従来から提案されているファンアウトウエハレベルパッケージ(一つのパッケージの中に一つのダイを封止して製造する)よりも低コスト化、高性能化が期待できるので、非常に注目を集めている。 Among stacked device structures, multi-die fanout wafer level packaging (Multi-die Fanout Wafer Level Packaging) is a package manufactured by sealing multiple dies in one package, and has not been proposed in the past. It is attracting a lot of attention because it is expected to be lower cost and have higher performance than conventional fan-out wafer-level packages (manufactured by sealing one die in one package).
マルチダイファンアウトウエハレベルパッケージの作製においては、高性能なダイの保護や耐熱性の低い封止材を保護し、歩留まりを向上させる観点から、例えば200℃以下での低温硬化性が強く求められている(例えば、特許文献2参照)。また、集積度、機能向上及びチップサイズ矮小化に伴い、パッケージを多層配線化するため、硬化膜には有機溶剤等の薬液に対する高い薬液耐性が求められる。 In the production of multi-die fan-out wafer-level packages, low-temperature curing at temperatures below 200°C, for example, is strongly required in order to protect high-performance dies, protect encapsulants with low heat resistance, and improve yields. (For example, see Patent Document 2). Further, as the degree of integration, functionality improves, and chip size becomes smaller, packages are made to have multilayer wiring, so the cured film is required to have high resistance to chemicals such as organic solvents.
しかしながら、200℃以下の硬化反応で得られた硬化膜は薬液耐性が低いという問題があった。 However, there is a problem in that the cured film obtained by the curing reaction at 200° C. or lower has low chemical resistance.
本発明の目的は、200℃以下で硬化した場合であっても、高い薬液耐性を有するパターン硬化膜を製造可能なパターン硬化膜の製造方法、及び感光性樹脂組成物を提供することである。また、当該感光性樹脂組成物の硬化膜、当該硬化膜を用いて作製された層間絶縁膜等、及び当該層間絶縁膜等を含む電子部品を提供することである。 An object of the present invention is to provide a method for producing a patterned cured film and a photosensitive resin composition that can produce a patterned cured film with high chemical resistance even when cured at 200° C. or lower. Another object of the present invention is to provide a cured film of the photosensitive resin composition, an interlayer insulating film made using the cured film, and an electronic component including the interlayer insulating film.
本発明者らは、硬化膜の薬液耐性が低い原因について以下のように考えた。即ち、通常、感光性樹脂組成物に用いられる重合性モノマー(架橋剤)は、露光による架橋反応でパターンを形成した後、硬化のための加熱処理工程で揮発することが期待されるが、200℃以下の低温硬化では架橋剤が十分に揮発せず膜中に残存する場合がある。低重合度又は未反応モノマー状態の架橋剤が膜中に残存すると、薬液が浸潤しやすい脆弱な硬化膜となってしまう。
本発明者らは、残存する架橋剤を有効利用し、これらを十分に架橋させることで緻密な高次構造が得られると考え、硬化反応で架橋を促す熱ラジカル発生剤を添加することにより当該目的を達成できることを見出し、本発明を完成した。
The present inventors considered the reason for the low chemical resistance of the cured film as follows. That is, the polymerizable monomer (crosslinking agent) normally used in photosensitive resin compositions is expected to volatilize in the heat treatment process for curing after forming a pattern through crosslinking reaction by exposure to light. When curing at a low temperature of .degree. C. or lower, the crosslinking agent may not volatilize sufficiently and may remain in the film. If the crosslinking agent with a low degree of polymerization or in an unreacted monomer state remains in the film, the cured film becomes brittle and easily infiltrated by the chemical solution.
The present inventors believe that a dense higher-order structure can be obtained by effectively utilizing the remaining crosslinking agents and sufficiently crosslinking them. The inventors discovered that the object could be achieved and completed the present invention.
本発明によれば、以下のパターン硬化膜の製造方法等が提供される。
1.(A)重合性の不飽和結合を有するポリイミド前駆体と、(B)重合性モノマーと、(C)光重合開始剤と、(D)熱ラジカル発生剤と、を含む感光性樹脂組成物を基板上に塗布、乾燥して感光性樹脂膜を形成する工程と、
前記感光性樹脂膜をパターン露光して、樹脂膜を得る工程と、
前記パターン露光後の樹脂膜を、有機溶剤を用いて現像し、パターン樹脂膜を得る工程と、
前記パターン樹脂膜を加熱処理する工程と、
を含むパターン硬化膜の製造方法。
2.前記加熱処理の温度が200℃以下である1に記載のパターン硬化膜の製造方法。
3.前記(D)成分が、有機過酸化物である1又は2に記載のパターン硬化膜の製造方法。
4.前記(D)成分が、ジアルキルパーオキサイドである1~3のいずれかに記載のパターン硬化膜の製造方法。
5.前記(A)成分が、下記式(11)で表される構造単位を有するポリイミド前駆体である1~4のいずれかに記載のパターン硬化膜の製造方法。
6.(A)重合性の不飽和結合を有するポリイミド前駆体と、
(B)重合性モノマーと、
(C)光重合開始剤と、
(D)熱ラジカル発生剤と、
を含む感光性樹脂組成物。
7.前記(D)成分が、有機過酸化物である6に記載の感光性樹脂組成物。
8.前記(D)成分が、ジアルキルパーオキサイドである6又は7に記載の感光性樹脂組成物。
9.前記(A)成分が、下記式(11)で表される構造単位を有するポリイミド前駆体である6~8のいずれかに記載の感光性樹脂組成物。
10.6~9のいずれかに記載の感光性樹脂組成物を硬化した硬化膜。
11.パターン硬化膜である10に記載の硬化膜。
12.10又は11に記載の硬化膜を用いて作製された層間絶縁膜、カバーコート層又は表面保護膜。
13.12に記載の層間絶縁膜、カバーコート層又は表面保護膜を含む電子部品。
According to the present invention, the following method for manufacturing a patterned cured film, etc. are provided.
1. A photosensitive resin composition containing (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer, (C) a photopolymerization initiator, and (D) a thermal radical generator. A step of coating and drying on the substrate to form a photosensitive resin film,
pattern-exposing the photosensitive resin film to obtain a resin film;
developing the resin film after the pattern exposure using an organic solvent to obtain a patterned resin film;
a step of heat treating the patterned resin film;
A method for producing a patterned cured film.
2. 2. The method for producing a patterned cured film according to 1, wherein the temperature of the heat treatment is 200° C. or lower.
3. 3. The method for producing a patterned cured film according to 1 or 2, wherein the component (D) is an organic peroxide.
4. 4. The method for producing a patterned cured film according to any one of 1 to 3, wherein the component (D) is a dialkyl peroxide.
5. 5. The method for producing a patterned cured film according to any one of 1 to 4, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11).
6. (A) a polyimide precursor having a polymerizable unsaturated bond;
(B) a polymerizable monomer;
(C) a photopolymerization initiator;
(D) a thermal radical generator;
A photosensitive resin composition containing.
7. 7. The photosensitive resin composition according to 6, wherein the component (D) is an organic peroxide.
8. 8. The photosensitive resin composition according to 6 or 7, wherein the component (D) is a dialkyl peroxide.
9. 9. The photosensitive resin composition according to any one of 6 to 8, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11).
10. A cured film obtained by curing the photosensitive resin composition according to any one of 6 to 9.
11. 11. The cured film according to 10, which is a patterned cured film.
12. An interlayer insulating film, cover coat layer, or surface protective film produced using the cured film described in 10 or 11.
13. An electronic component comprising an interlayer insulating film, a cover coat layer, or a surface protective film according to 12.
本発明によれば、200℃以下で硬化した場合であっても、高い薬液耐性を有するパターン硬化膜を製造可能なパターン硬化膜の製造方法、及び感光性樹脂組成物が提供できる。また、当該感光性樹脂組成物の硬化膜、当該硬化膜を用いて作製された層間絶縁膜等、及び当該層間絶縁膜等を含む電子部品が提供できる。 According to the present invention, a method for producing a patterned cured film and a photosensitive resin composition that can produce a patterned cured film having high chemical resistance even when cured at 200° C. or lower can be provided. Moreover, a cured film of the photosensitive resin composition, an interlayer insulating film, etc. produced using the cured film, and an electronic component including the interlayer insulating film, etc. can be provided.
以下に、本発明のパターン硬化膜の製造方法、感光性樹脂組成物、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品の実施の形態を詳細に説明する。尚、以下の実施の形態により本発明が限定されるものではない。 EMBODIMENT OF THE INVENTION Below, embodiment of the manufacturing method of the patterned cured film of this invention, a photosensitive resin composition, a cured film, an interlayer insulation film, a cover coat layer, a surface protection film, and an electronic component is described in detail. Note that the present invention is not limited to the following embodiments.
本明細書において「A又はB」とは、AとBのどちらか一方を含んでいればよく、両方とも含んでいてもよい。また、本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。また、本明細書において組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。さらに、例示材料は特に断らない限り単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
本明細書における「(メタ)アクリル基」とは、「アクリル基」及び「メタクリル基」を意味する。
In this specification, "A or B" may include either A or B, or may include both. In addition, in this specification, the term "process" does not only refer to an independent process, but also refers to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved. included.
A numerical range indicated using "~" indicates a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively. In addition, in this specification, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, the content of each component in the composition refers to the total content of the multiple substances present in the composition. means quantity. Furthermore, unless otherwise specified, the exemplified materials may be used alone or in combination of two or more.
The "(meth)acrylic group" in this specification means an "acrylic group" and a "methacrylic group."
[感光性樹脂組成物]
本発明の感光性樹脂組成物は、(A)重合性の不飽和結合を有するポリイミド前駆体(以下、「(A)成分」ともいう。)、(B)重合性モノマー(以下、「(B)成分」ともいう。)、(C)光重合開始剤(以下、「(C)成分」ともいう。)、及び(D)熱ラジカル発生剤(以下、「(D)成分」ともいう。)を含む。本発明の感光性樹脂組成物は、好ましくはネガ型感光性樹脂組成物である。
[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter also referred to as "component (A)"), (B) a polymerizable monomer (hereinafter referred to as "(B ), (C) a photopolymerization initiator (hereinafter also referred to as "component (C)"), and (D) a thermal radical generator (hereinafter also referred to as "component (D)"). including. The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.
本発明の感光性樹脂組成物は、上記の成分を有するため、高い薬液耐性を有するパターン硬化膜を製造することができる。具体的には、本発明の感光性樹脂組成物から得られるパターン硬化膜は、薬液に浸漬させた後の膜厚変化率が小さく、薬液の浸みこみによる膜の膨潤が少ない。また、クラックやひび割れがなく、外観に優れる。
さらに、本発明の感光性樹脂組成物は、加熱処理工程時に(B)重合性モノマー(架橋剤)の架橋反応が促されるため、当該成分の揮発量が少ない。そのため、硬化膜にしたときの膜収縮(シュリンク)が少なく寸法精度に優れる。
以下、各成分について説明する。
Since the photosensitive resin composition of the present invention has the above-mentioned components, it is possible to produce a patterned cured film having high chemical resistance. Specifically, the patterned cured film obtained from the photosensitive resin composition of the present invention has a small rate of change in film thickness after being immersed in a chemical solution, and has little swelling of the film due to permeation of the chemical solution. It also has an excellent appearance with no cracks or cracks.
Furthermore, in the photosensitive resin composition of the present invention, since the crosslinking reaction of the polymerizable monomer (crosslinking agent) (B) is promoted during the heat treatment step, the amount of volatilization of the component is small. Therefore, when it is made into a cured film, there is less film shrinkage (shrink) and it has excellent dimensional accuracy.
Each component will be explained below.
((A)成分:重合性の不飽和結合を有するポリイミド前駆体)
(A)成分は、重合性の不飽和結合を有するポリイミド前駆体であれば特に制限はされないが、パターニング時の光源にi線を用いた場合の透過率が高く、200℃以下の低温硬化時にも高い硬化膜特性を示すポリイミド前駆体が好ましい。
重合性の不飽和結合としては、炭素原子間の二重結合等が挙げられる。
(Component (A): polyimide precursor having polymerizable unsaturated bonds)
Component (A) is not particularly limited as long as it is a polyimide precursor having polymerizable unsaturated bonds, but it has high transmittance when i-line is used as the light source during patterning, and when cured at low temperatures of 200°C or less. Polyimide precursors that also exhibit high cured film properties are preferred.
Examples of the polymerizable unsaturated bond include double bonds between carbon atoms.
(A)成分は、好ましくは下記式(11)で表される構造単位を有するポリイミド前駆体である。これにより、i線の透過率が高く、200℃以下の低温で硬化を行った場合であっても良好な物性を有する硬化膜を形成できる。
式(11)のX1の1以上(好ましくは1~3、より好ましくは1又は2)の芳香族基を有する4価の基は、4価の芳香族炭化水素基(炭素数は例えば6~20)であってもよく、4価の芳香族複素環基(原子数は例えば5~20)であってもよい。X1は4価の芳香族炭化水素基が好ましい。 The tetravalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups in X 1 of formula (11) is a tetravalent aromatic hydrocarbon group (the number of carbon atoms is, for example, 6). ~20) or a tetravalent aromatic heterocyclic group (for example, the number of atoms is 5 to 20). X 1 is preferably a tetravalent aromatic hydrocarbon group.
X1の芳香族炭化水素基としては、ベンゼン環から形成される2~4価(2価、3価又は4価)の基、ナフタレンから形成される2~4価の基、ペリレンから形成される2~4価の基等が挙げられる。 The aromatic hydrocarbon group of X 1 is a divalent to tetravalent (bivalent, trivalent or tetravalent) group formed from a benzene ring, a divalent to tetravalent group formed from naphthalene, and a divalent to tetravalent group formed from perylene. Examples include di- to tetravalent groups.
X1の1以上の芳香族基を有する4価の基としては、例えば以下に示す基が挙げられるが、これらに限定されるものではない。
Z1及びZ2の2価の基は、-O-、-S-、メチレン基、ビス(トリフルオロメチル)メチレン基、又はジフルオロメチレン基であることが好ましく、-O-がより好ましい。
Z3は、-O-が好ましい。
The divalent groups Z 1 and Z 2 are preferably -O-, -S-, a methylene group, a bis(trifluoromethyl)methylene group, or a difluoromethylene group, and -O- is more preferable.
Z 3 is preferably -O-.
式(11)のY1の2価の芳香族基は、2価の芳香族炭化水素基(炭素数は例えば6~20)であってもよく、2価の芳香族複素環基(原子数は例えば5~20)であってもよい。Y1は2価の芳香族炭化水素基が好ましい。 The divalent aromatic group of Y 1 in formula (11) may be a divalent aromatic hydrocarbon group (for example, the number of carbon atoms is 6 to 20), or a divalent aromatic heterocyclic group (the number of atoms is 6 to 20). may be, for example, 5 to 20). Y 1 is preferably a divalent aromatic hydrocarbon group.
Y1の2価の芳香族炭化水素基としては、例えば下記式(13)で表される基が挙げられるが、これに限定されるものではない。
R21~R28の1価の脂肪族炭化水素基(好ましくは炭素数1~10、より好ましくは炭素数1~6)としてはメチル基が好ましい。 The monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) of R 21 to R 28 is preferably a methyl group.
R21~R28のハロゲン原子(好ましくはフッ素原子)を有する1価の有機基は、ハロゲン原子を有する1価の脂肪族炭化水素基(好ましくは炭素数1~10、より好ましくは炭素数1~6)が好ましく、トリフルオロメチル基が好ましい。 The monovalent organic group having a halogen atom (preferably a fluorine atom) of R 21 to R 28 is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms, more preferably having 1 carbon atom). -6) are preferred, and trifluoromethyl group is preferred.
式(13)において、例えば、R22及びR23が1価の脂肪族炭化水素基(例えばメチル基)であり、R21及びR24~R28が水素原子であってもよい。 In formula (13), for example, R 22 and R 23 may be monovalent aliphatic hydrocarbon groups (eg, methyl groups), and R 21 and R 24 to R 28 may be hydrogen atoms.
式(11)のR11及びR12の炭素数1~4(好ましくは1又は2)の脂肪族炭化水素基としては、メチル基、エチル基、n-プロピル基、2-プロピル基、n-ブチル基等が挙げられる。 Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 or 2) for R 11 and R 12 in formula (11) include methyl group, ethyl group, n-propyl group, 2-propyl group, n- Examples include butyl group.
式(11)において、R11及びR12の少なくとも一方が式(12)で表される基であり、好ましくはR11及びR12の両方が式(12)で表される基である。 In formula (11), at least one of R 11 and R 12 is a group represented by formula (12), and preferably both R 11 and R 12 are groups represented by formula (12).
式(12)のR13~R15の炭素数1~3(好ましくは1又は2)の脂肪族炭化水素基としては、メチル基、エチル基、n-プロピル基、2-プロピル基等が挙げられる。メチル基が好ましい。 Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms (preferably 1 or 2) for R 13 to R 15 in formula (12) include methyl group, ethyl group, n-propyl group, 2-propyl group, etc. It will be done. Methyl group is preferred.
式(11)で表される構造単位を有するポリイミド前駆体は、例えば、下記式(14)で表されるテトラカルボン酸二無水物と、下記式(15)で表されるジアミノ化合物とを、N-メチルピロリドン等の有機溶剤中にて反応させてポリアミド酸を製造し、下記式(16)で表される化合物を加え、有機溶剤中で反応させて全体的又は部分的にエステル基を導入することで製造することができる。
式(14)で表されるテトラカルボン酸二無水物及び式(15)で表されるジアミノ化合物は、1種単独で用いてもよく、2種以上を組み合わせてもよい。 The tetracarboxylic dianhydride represented by formula (14) and the diamino compound represented by formula (15) may be used alone or in combination of two or more.
式(11)で表される構造単位の含有量は、(A)成分の全構造単位に対して、50モル%以上であることが好ましく、80モル%以上がより好ましく、90モル%以上がさらに好ましい。上限は特に限定されず、100モル%でもよい。 The content of the structural unit represented by formula (11) is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% or more based on the total structural units of component (A). More preferred. The upper limit is not particularly limited, and may be 100 mol%.
(A)成分は、式(11)で表される構造単位以外の構造単位を有してもよい。式(11)で表される構造単位以外の構造単位としては、下記式(17)で表される構造単位等が挙げられる。
式(17)のX12の1以上の芳香族基を有する4価の基としては、式(11)のX1の1以上の芳香族基を有する4価の基と同じ基が挙げられる。Y12の2価の芳香族基としては、式(11)のY1の2価の芳香族基と同じ基が挙げられる。R31及びR32の炭素数1~4の脂肪族炭化水素基としては、式(11)のR11及びR12の炭素数1~4の脂肪族炭化水素基と同じ基が挙げられる。 Examples of the tetravalent group having one or more aromatic groups represented by X 12 in formula (17) include the same groups as the tetravalent group having one or more aromatic groups represented by X 1 in formula (11). Examples of the divalent aromatic group for Y 12 include the same groups as the divalent aromatic group for Y 1 in formula (11). Examples of the aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R 31 and R 32 include the same groups as the aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R 11 and R 12 in formula (11).
式(11)で表される構造単位以外の構造単位の含有量は、(A)成分の全構造単位に対して50モル%未満であることが好ましい。
式(11)で表される構造単位以外の構造単位は、1種単独で用いてもよく、2種以上を組み合わせてもよい。
The content of structural units other than the structural unit represented by formula (11) is preferably less than 50 mol% based on the total structural units of component (A).
Structural units other than the structural unit represented by formula (11) may be used alone or in combination of two or more.
(A)成分において、ポリイミド前駆体中の全カルボキシ基及び全カルボキシエステルに対して、式(12)で表される基でエステル化されたカルボキシ基の割合が、50モル%以上であることが好ましく、60~100モル%がより好ましく、70~90モル%がより好ましい。 In component (A), the proportion of carboxy groups esterified with the group represented by formula (12) is 50 mol% or more with respect to all the carboxy groups and all carboxy esters in the polyimide precursor. It is preferably 60 to 100 mol%, more preferably 70 to 90 mol%.
(A)成分の分子量に特に制限はないが、数平均分子量で10,000~200,000であることが好ましい。
数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)によって測定し、標準ポリスチレン検量線を用いて換算することによって求める。具体的な測定条件等は実施例に記載の通りとする。
There is no particular restriction on the molecular weight of component (A), but it is preferably a number average molecular weight of 10,000 to 200,000.
The number average molecular weight is determined by measuring by gel permeation chromatography (GPC) and converting using a standard polystyrene calibration curve. Specific measurement conditions and the like are as described in Examples.
((B)成分:重合性モノマー)
本発明の感光性樹脂組成物は(B)重合性モノマーを含む。(B)成分は、(A)成分と架橋し、又は(B)成分同士が重合して架橋ネットワークを形成する。これにより、光反応によりパターン樹脂膜の形成が可能となり、さらに、その後の熱処理反応においても(D)成分により架橋反応が促進されるため、緻密な高次構造を有し、薬液耐性の高い硬化膜(硬化物)が得られる。
((B) component: polymerizable monomer)
The photosensitive resin composition of the present invention contains (B) a polymerizable monomer. The component (B) crosslinks with the component (A), or the components (B) polymerize with each other to form a crosslinked network. This makes it possible to form a patterned resin film through photoreaction, and furthermore, in the subsequent heat treatment reaction, the crosslinking reaction is promoted by component (D), resulting in a cure with a dense higher-order structure and high chemical resistance. A film (cured product) is obtained.
(B)成分は、重合性の不飽和二重結合を含む基を有することが好ましく、架橋密度向上、光感度向上、及び現像後のパターンの膨潤の抑制のため、2~4の重合性の不飽和二重結合を含む基を有することが好ましい。当該基は、好ましくは、光重合開始剤により重合可能である観点から(メタ)アクリル基又はアリル基である。 Component (B) preferably has a group containing a polymerizable unsaturated double bond, and in order to improve crosslinking density, improve photosensitivity, and suppress pattern swelling after development, component (B) has 2 to 4 polymerizable groups. It is preferable to have a group containing an unsaturated double bond. The group is preferably a (meth)acrylic group or an allyl group from the viewpoint of being polymerizable with a photopolymerization initiator.
(B)成分として、例えば下記式(21)で表される基を有する化合物が挙げられるが、これらに限定されるものではない。
式(21)の炭素数1~3の脂肪族炭化水素基としては、式(12)のR13~R15の炭素数1~3の脂肪族炭化水素基と同様のものが挙げられる。 Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms in formula (21) include the same aliphatic hydrocarbon groups having 1 to 3 carbon atoms as R 13 to R 15 in formula (12).
(B)成分として、好ましくは下記式(22)で表される化合物を用いることができる。
また、(B)成分として、好ましくは下記式(23)で表される化合物を用いることができる。
R46~R48は、それぞれ独立に、例えば、アリル基又は式(21)で表される基である。
Moreover, as component (B), preferably a compound represented by the following formula (23) can be used.
R 46 to R 48 are each independently, for example, an allyl group or a group represented by formula (21).
(B)成分として、具体的には、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、1,4-ブタンジオールジアクリレート、1,6-ヘキサンジオールジアクリレート、1,4-ブタンジオールジメタクリレート、1,6-ヘキサンジオールジメタクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパンジメタクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、テトラメチロールメタンテトラアクリレート、テトラメチロールメタンテトラメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、トリアリルイソシアヌレート、エトキシ化イソシアヌル酸トリアクリレート、エトキシ化イソシアヌル酸トリメタクリレート、アクリロイルオキシエチルイソシアヌレート、メタクリロイルオキシエチルイソシアヌレート等が挙げられる。 Component (B) specifically includes diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and 1,4-butane diol diacrylate. Acrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane Trimethacrylate, Pentaerythritol Triacrylate, Pentaerythritol Tetraacrylate, Ethoxylated Pentaerythritol Tetraacrylate, Pentaerythritol Trimethacrylate, Pentaerythritol Tetramethacrylate, Tetramethylolmethane Tetraacrylate, Tetramethylolmethane Tetramethacrylate, Dipentaerythritol Hexaacrylate, Dipenta Examples include erythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, triallyl isocyanurate, ethoxylated isocyanuric triacrylate, ethoxylated isocyanuric trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, and the like.
(B)成分の含有量は、(A)成分100質量部に対して、1~50質量部が好ましく、より好ましくは5~50質量部であり、さらに好ましくは5~40質量部である。上記範囲内である場合、実用的なレリーフパターンが得られやすく、未露光部の現像後残滓を抑制しやすい。 The content of component (B) is preferably 1 to 50 parts by weight, more preferably 5 to 50 parts by weight, and still more preferably 5 to 40 parts by weight, based on 100 parts by weight of component (A). When it is within the above range, it is easy to obtain a practical relief pattern, and it is easy to suppress post-development residue in unexposed areas.
((C)成分:光重合開始剤)
(C)成分の光重合開始剤としては、例えば、ベンゾフェノン、o-ベンゾイル安息香酸メチル、4-ベンゾイル-4’-メチルジフェニルケトン、ジベンジルケトン、フルオレノン等のベンゾフェノン誘導体;2,2’-ジエトキシアセトフェノン、2-ヒドロキシ-2-メチルプロピオフェノン、1-ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン誘導体;チオキサントン、2-メチルチオキサントン、2-イソプロピルチオキサントン、ジエチルチオキサントン等のチオキサントン誘導体;ベンジル、ベンジルジメチルケタール、ベンジル-β-メトキシエチルアセタール等のベンジル誘導体;ベンゾイン、ベンゾインメチルエーテル等のベンゾイン誘導体;1-フェニル-1,2-ブタンジオン-2-(O-メトキシカルボニル)オキシム、1-フェニル-1,2-プロパンジオン-2-(O-メトキシカルボニル)オキシム、1-フェニル-1,2-プロパンジオン-2-(O-エトキシカルボニル)オキシム、1-フェニル-1,2-プロパンジオン-2-(O-ベンゾイル)オキシム、1,3-ジフェニルプロパントリオン-2-(O-エトキシカルボニル)オキシム、1-フェニル-3-エトキシプロパントリオン-2-(O-ベンゾイル)オキシム、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)、下記式で表される化合物等のオキシムエステル類などが好ましく挙げられるが、これらに限定されるものではない。光感度の点で、オキシムエステル類が好ましい。
Examples of the photopolymerization initiator as component (C) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone; Acetophenone derivatives such as ethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone; Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzyl, benzyl dimethyl ketal, Benzyl derivatives such as benzyl-β-methoxyethyl acetal; benzoin, benzoin derivatives such as benzoin methyl ether; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2- Propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O- benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, ethanone, 1-[9-ethyl- Preferred examples include oxime esters such as 6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) and compounds represented by the following formula, but are limited to these: It is not something that will be done. Oxime esters are preferred in terms of photosensitivity.
(C)成分の含有量は、(A)成分100質量部に対して、0.1~20質量部が好ましく、より好ましくは0.1~10質量部であり、さらに好ましくは0.1~8質量部である。上記範囲内の場合、光架橋が膜厚方向で均一となりやすく、実用的なレリーフパターンを得やすくなる。 The content of component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 10 parts by mass, per 100 parts by mass of component (A). It is 8 parts by mass. Within the above range, photocrosslinking tends to be uniform in the film thickness direction, making it easier to obtain a practical relief pattern.
((D)成分:熱ラジカル発生剤)
本発明の感光性樹脂組成物は、(D)熱ラジカル発生剤を含有するため、熱処理工程において(B)成分の架橋反応が促進され、緻密な高次構造が形成される。これにより、薬液耐性に優れた硬化膜の製造が可能となる。具体的に、(D)成分は硬化時の加熱により分解してラジカルを発生し、(B)成分同士、又は(A)成分及び(B)成分の重合反応を促して架橋構造を形成する。
(Component (D): thermal radical generator)
Since the photosensitive resin composition of the present invention contains (D) a thermal radical generator, the crosslinking reaction of component (B) is promoted in the heat treatment step, and a dense higher-order structure is formed. This makes it possible to produce a cured film with excellent chemical resistance. Specifically, component (D) is decomposed by heating during curing to generate radicals, which promotes a polymerization reaction between components (B) or components (A) and (B) to form a crosslinked structure.
(D)成分としては有機過酸化物が好ましい。
有機過酸化物としては、ジアルキルパーオキシド、ケトンパーオキシド、パーオキシケタール、ハイドロパーオキシド、ジアシルパーオキシド、パーオキシジカーボネート、パーオキシエステル等が挙げられ、ジアルキルパーオキシドが好ましい。
Component (D) is preferably an organic peroxide.
Examples of the organic peroxide include dialkyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, diacyl peroxide, peroxydicarbonate, peroxy ester, and the like, with dialkyl peroxide being preferred.
ジアルキルパーオキシドは下記一般式で表される化合物である。
R-O-O-R’
式中、R及びR’は、それぞれ独立に、置換もしくは無置換のアルキル基である。置換基としては炭素数6~10のアリール基等が挙げられる。アルキル基の炭素数は、例えば1~20又は1~10である。
Dialkyl peroxide is a compound represented by the following general formula.
R-O-O-R'
In the formula, R and R' each independently represent a substituted or unsubstituted alkyl group. Examples of the substituent include an aryl group having 6 to 10 carbon atoms. The number of carbon atoms in the alkyl group is, for example, 1 to 20 or 1 to 10.
ジアルキルパーオキシドの具体例としては、ジクミルパーオキシド、ジ-t-ブチルパーオキシド、ジ(2-t-ブチルパーオキシイソプロピル)ベンゼン、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン、t-ブチルクミルパーオキシド、ジ-t-ヘキシルパーオキシド、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキシン-3等が挙げられる。 Specific examples of dialkyl peroxide include dicumyl peroxide, di-t-butyl peroxide, di(2-t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butyl) peroxy)hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and the like.
市販品としては、商品名「パークミルD」、「パーブチルP」、「パーヘキサ25B」、「パーブチルC」、「パーヘキシルD」、「パーブチルD」、「パーヘキシン25B」、「パーヘキシン25B-40」(以上、日油株式会社製)等が挙げられる。 Commercially available products include the product names "Percmil D", "Perbutyl P", "Perhexa 25B", "Perbutyl C", "Perhexyl D", "Perbutyl D", "Perhexin 25B", "Perhexin 25B-40" (and above). , NOF Corporation), etc.
有機過酸化物は、1時間半減期温度が50℃以上200℃以下の化合物が好ましく、より低温で重合反応を促進する観点から、1時間半減期温度が50℃以上175℃以下の化合物がより好ましい。 The organic peroxide is preferably a compound with a 1-hour half-life temperature of 50°C or more and 200°C or less, and from the viewpoint of promoting the polymerization reaction at a lower temperature, a compound with a 1-hour half-life temperature of 50°C or more and 175°C or less is more preferable. preferable.
1時間半減期温度は以下のようにして測定する。
有機過酸化物をベンゼンに溶解させて0.1mol/Lの溶液を調製し、窒素置換を行ったガラス管中に密封する。これを所定温度にセットした恒温槽に浸して熱分解、時間(t)ln a/(a-x)の関係をプロットし、得られた直線の傾きからkを求め、下記式から半減期(t1/2)を求める。
dx/dt=k(a-x)
ln a/(a-x)=kt
x=a/2
kt1/2=ln2
x:分解有機過酸化物量
k:分解速度定数
t:時間
a:有機過酸化物初期濃度
kは下記式で表されるので、数点の温度についてkを測定し、lnk~1/Tの関係をプロットして得られた直線の傾きから活性化エネルギーΔEを求め、y切片から頻度因子Aを求める。
k=Aexp[-ΔE/RT]
lnk=lnA-ΔE/RT
A:頻度因子(1/h)
ΔE:活性化エネルギー(J/mol)
R:気体定数(8.314J/mol・K)
T:絶対温度(K)
lnkの代わりにlnt1/2~1/Tの関係をプロットして得られた直線から任意の温度における有機過酸化物の半減期が得られ、任意の半減期(1時間)を得る分解温度が得られる。
The 1-hour half-life temperature is measured as follows.
An organic peroxide is dissolved in benzene to prepare a 0.1 mol/L solution, and the solution is sealed in a glass tube that has been purged with nitrogen. Plot the relationship between thermal decomposition time (t) ln a/(ax) by immersing it in a constant temperature bath set at a predetermined temperature, calculate k from the slope of the obtained straight line, and calculate the half-life ( t 1/2 ).
dx/dt=k(ax)
ln a/(ax)=kt
x=a/2
kt 1/2 = ln2
x: amount of decomposed organic peroxide k: decomposition rate constant t: time a: initial concentration of organic peroxide Since k is expressed by the following formula, k was measured at several temperatures and the relationship lnk ~ 1/T was determined. The activation energy ΔE is determined from the slope of the straight line obtained by plotting, and the frequency factor A is determined from the y-intercept.
k=Aexp[-ΔE/RT]
lnk=lnA-ΔE/RT
A: Frequency factor (1/h)
ΔE: activation energy (J/mol)
R: gas constant (8.314J/mol・K)
T: Absolute temperature (K)
The half-life of organic peroxide at any temperature can be obtained from the straight line obtained by plotting the relationship between lnt 1/2 and 1/T instead of lnk, and the decomposition temperature at which an arbitrary half-life (1 hour) can be obtained. is obtained.
(D)成分の含有量は、(A)成分100質量部に対して、0.1~20質量部が好ましく、0.2~20質量部がより好ましく、0.3~10質量部がさらに好ましい。 The content of component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 20 parts by mass, and further preferably 0.3 to 10 parts by mass, per 100 parts by mass of component (A). preferable.
((E)成分:溶剤)
本発明の感光性樹脂組成物は、通常、溶剤を含む。
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、3-メトキシ-N,N-ジメチルプロパンアミド(例えばKJケミカルズ株式会社製「KJCMPA-100」)、N-ジメチルモルホリン等の有機溶剤などが挙げられる。
溶剤の含有量は、特に限定されないが、一般的に、(A)成分100質量部に対して、50~1000質量部である。
((E) component: solvent)
The photosensitive resin composition of the present invention usually contains a solvent.
As a solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethylsulfoxide, 3-methoxy-N,N-dimethylpropanamide (for example, "KJCMPA-100" manufactured by KJ Chemicals Co., Ltd.) , N-dimethylmorpholine, and other organic solvents.
The content of the solvent is not particularly limited, but is generally from 50 to 1000 parts by weight per 100 parts by weight of component (A).
(他の成分)
本発明の感光性樹脂組成物は、上記成分以外に、さらに、カップリング剤(接着助剤)、界面活性剤又はレベリング剤、増感剤、防錆剤及び重合禁止剤等を含有してもよい。
(other ingredients)
In addition to the above components, the photosensitive resin composition of the present invention may further contain a coupling agent (adhesive aid), a surfactant or a leveling agent, a sensitizer, a rust preventive, a polymerization inhibitor, etc. good.
(カップリング剤)
カップリング剤は、通常、現像後の加熱処理において、(A)成分と反応して架橋するか、又は加熱処理する工程においてカップリング剤自身が重合する。これにより、得られる硬化膜と基板との接着性をより向上させることができる。
(coupling agent)
The coupling agent usually reacts with component (A) and crosslinks in the heat treatment after development, or the coupling agent itself polymerizes in the heat treatment step. Thereby, the adhesiveness between the resulting cured film and the substrate can be further improved.
カップリング剤としてはシランカップリング剤が好ましい。
好ましいシランカップリング剤としては、ウレア結合(-NH-CO-NH-)を有する化合物が挙げられる。これにより、200℃以下の低温下で硬化を行った場合も基板との接着性をさらに高めることができる。
低温での硬化を行った際の接着性の発現に優れる点で、下記式(31)で表される化合物がより好ましい。
Preferred silane coupling agents include compounds having a urea bond (-NH-CO-NH-). Thereby, even when curing is performed at a low temperature of 200° C. or lower, the adhesiveness to the substrate can be further improved.
A compound represented by the following formula (31) is more preferable because it exhibits excellent adhesive properties when cured at low temperatures.
式(31)で表される化合物の具体例としては、ウレイドメチルトリメトキシシラン、ウレイドメチルトリエトキシシラン、2-ウレイドエチルトリメトキシシラン、2-ウレイドエチルトリエトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、4-ウレイドブチルトリメトキシシラン、4-ウレイドブチルトリエトキシシラン等が挙げられ、好ましくは3-ウレイドプロピルトリエトキシシランである。 Specific examples of the compound represented by formula (31) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, etc., with 3-ureidopropyltriethoxysilane being preferred.
シランカップリング剤として、ヒドロキシ基又はグリシジル基を有するシランカップリング剤を用いてもよい。ヒドロキシ基又はグリシジル基を有するシランカップリング剤、及び分子内にウレア結合を有するシランカップリング剤を併用すると、さらに低温硬化時の硬化膜の基板への接着性を向上することができる。 As the silane coupling agent, a silane coupling agent having a hydroxy group or a glycidyl group may be used. When a silane coupling agent having a hydroxy group or a glycidyl group and a silane coupling agent having a urea bond in the molecule are used together, the adhesion of the cured film to the substrate during low temperature curing can be further improved.
ヒドロキシ基又はグリシジル基を有するシランカップリング剤としては、メチルフェニルシランジオール、エチルフェニルシランジオール、n-プロピルフェニルシランジオール、イソプロピルフェニルシランジオール、n-ブチルフェニルシランジオール、イソブチルフェニルシランジオール、tert-ブチルフェニルシランジオール、ジフェニルシランジオール、エチルメチルフェニルシラノール、n-プロピルメチルフェニルシラノール、イソプロピルメチルフェニルシラノール、n-ブチルメチルフェニルシラノール、イソブチルメチルフェニルシラノール、tert-ブチルメチルフェニルシラノール、エチルn-プロピルフェニルシラノール、エチルイソプロピルフェニルシラノール、n-ブチルエチルフェニルシラノール、イソブチルエチルフェニルシラノール、tert-ブチルエチルフェニルシラノール、メチルジフェニルシラノール、エチルジフェニルシラノール、n-プロピルジフェニルシラノール、イソプロピルジフェニルシラノール、n-ブチルジフェニルシラノール、イソブチルジフェニルシラノール、tert-ブチルジフェニルシラノール、フェニルシラントリオール、1,4-ビス(トリヒドロキシシリル)ベンゼン、1,4-ビス(メチルジヒドロキシシリル)ベンゼン、1,4-ビス(エチルジヒドロキシシリル)ベンゼン、1,4-ビス(プロピルジヒドロキシシリル)ベンゼン、1,4-ビス(ブチルジヒドロキシシリル)ベンゼン、1,4-ビス(ジメチルヒドロキシシリル)ベンゼン、1,4-ビス(ジエチルヒドロキシシリル)ベンゼン、1,4-ビス(ジプロピルヒドロキシシリル)ベンゼン、1,4-ビス(ジブチルヒドロキシシリル)ベンゼン、及び下記式(32)で表わされる化合物等が挙げられる。中でも、特に、基板との接着性をより向上させるため、式(32)で表される化合物が好ましい。
式(32)で表される化合物としては、ヒドロキシメチルトリメトキシシラン、ヒドロキシメチルトリエトキシシラン、2-ヒドロキシエチルトリメトキシシラン、2-ヒドロキシエチルトリエトキシシラン、3-ヒドロキシプロピルトリメトキシシラン、3-ヒドロキシプロピルトリエトキシシラン、4-ヒドロキシブチルトリメトキシシラン、4-ヒドロキシブチルトリエトキシシラン、グリシドキシメチルトリメトキシシラン、グリシドキシメチルトリエトキシシラン、2-グリシドキシエチルトリメトキシシラン、2-グリシドキシエチルトリエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、4-グリシドキシブチルトリメトキシシラン、4-グリシドキシブチルトリエトキシシラン等が挙げられる。 Examples of the compound represented by formula (32) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Examples include glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, etc. It will be done.
ヒドロキシ基又はグリシジル基を有するシランカップリング剤は、さらに、窒素原子を有する基を含むことが好ましく、さらにアミノ基又はアミド結合を有するシランカップリング剤が好ましい。
さらにアミノ基を有するシランカップリング剤としては、ビス(2-ヒドロキシメチル)-3-アミノプロピルトリエトキシシラン、ビス(2-ヒドロキシメチル)-3-アミノプロピルトリメトキシシラン、ビス(2-グリシドキシメチル)-3-アミノプロピルトリエトキシシラン、ビス(2-ヒドロキシメチル)-3-アミノプロピルトリメトキシシラン等が挙げられる。
The silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a group having a nitrogen atom, and further preferably has an amino group or an amide bond.
Furthermore, examples of silane coupling agents having an amino group include bis(2-hydroxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, and bis(2-glycid). Examples include oxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, and the like.
さらにアミド結合を有するシランカップリング剤としては、下記式(33)で表される化合物等が挙げられる。
R56-(CH2)q-CO-NH-(CH2)r-Si(OR57)3 (33)
(式(33)中、R56はヒドロキシ基又はグリシジル基であり、q及びrは、それぞれ独立に、1~3の整数であり、R57はメチル基、エチル基又はプロピル基である。)
Furthermore, examples of the silane coupling agent having an amide bond include a compound represented by the following formula (33).
R 56 -(CH 2 ) q -CO-NH-(CH 2 ) r -Si(OR 57 ) 3 (33)
(In formula (33), R 56 is a hydroxy group or a glycidyl group, q and r are each independently an integer of 1 to 3, and R 57 is a methyl group, ethyl group, or propyl group.)
シランカップリング剤を用いる場合、シランカップリング剤の含有量は、(A)成分100質量部に対して、0.1~20質量部が好ましく、0.3~10質量部がより好ましく、1~10質量部がさらに好ましい。 When using a silane coupling agent, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and 1 to 10 parts by mass, based on 100 parts by mass of component (A). More preferably 10 parts by mass.
(界面活性剤又はレベリング剤)
界面活性剤又はレベリング剤を含むことで、塗布性(例えばストリエーション(膜厚のムラ)の抑制)及び現像性を向上させることができる。
(Surfactant or leveling agent)
By including a surfactant or a leveling agent, coating properties (for example, suppression of striations (unevenness in film thickness)) and developability can be improved.
界面活性剤又はレベリング剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェノールエーテル等が挙げられ、市販品としては、商品名「メガファックF171」、「F173」、「R-08」(以上、DIC株式会社製)、商品名「フロラードFC430」、「FC431」(以上、スリーエム ジャパン株式会社製)、商品名「オルガノシロキサンポリマーKP341」、「KBM303」、「KBM403」、「KBM803」(以上、信越化学工業株式会社製)等が挙げられる。 Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc. Commercially available products include the product name "Megafac F171". ", "F173", "R-08" (manufactured by DIC Corporation), product name "Florado FC430", "FC431" (manufactured by 3M Japan Ltd.), product name "Organosiloxane Polymer KP341", " KBM303," "KBM403," and "KBM803" (all manufactured by Shin-Etsu Chemical Co., Ltd.).
界面活性剤又はレベリング剤を含む場合、界面活性剤又はレベリング剤の含有量は、(A)成分100質量部に対して0.01~10質量部が好ましく、0.05~5質量部がより好ましく、0.05~3質量部がさらに好ましい。 When a surfactant or leveling agent is included, the content of the surfactant or leveling agent is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of component (A). It is preferably 0.05 to 3 parts by mass, and more preferably 0.05 to 3 parts by mass.
(重合禁止剤)
重合禁止剤を含有することで、良好な保存安定性を確保することができる。
重合禁止剤としては、ラジカル重合禁止剤、ラジカル重合抑制剤等が挙げられる。
重合禁止剤としては、例えば、p-メトキシフェノール、ジフェニル-p-ベンゾキノン、ベンゾキノン、ハイドロキノン、ピロガロール、フェノチアジン、レゾルシノール、オルトジニトロベンゼン、パラジニトロベンゼン、メタジニトロベンゼン、フェナントラキノン、N-フェニル-2-ナフチルアミン、クペロン、2,5-トルキノン、タンニン酸、パラベンジルアミノフェノール、ニトロソアミン類等が挙げられる。
(Polymerization inhibitor)
By containing a polymerization inhibitor, good storage stability can be ensured.
Examples of the polymerization inhibitor include radical polymerization inhibitors and radical polymerization inhibitors.
Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2- Examples include naphthylamine, cuperone, 2,5-torquinone, tannic acid, parabenzylaminophenol, and nitrosamines.
重合禁止剤を含有する場合、重合禁止剤の含有量としては、感光性樹脂組成物の保存安定性及び得られる硬化膜の耐熱性の観点から、(A)成分100質量部に対して、0.01~30質量部が好ましく、0.01~10質量部がより好ましく、0.05~5質量部がさらに好ましい。 When containing a polymerization inhibitor, the content of the polymerization inhibitor is 0 to 100 parts by mass of component (A) from the viewpoint of storage stability of the photosensitive resin composition and heat resistance of the obtained cured film. The amount is preferably from 0.01 to 30 parts by weight, more preferably from 0.01 to 10 parts by weight, and even more preferably from 0.05 to 5 parts by weight.
(その他の成分)
本発明の感光性樹脂組成物は、増感剤を含有してもよい。
増感剤としては、例えば、7-N,N-ジエチルアミノクマリン、7-ジエチルアミノ-3-テノニルクマリン、3,3’-カルボニルビス(7-N,N-ジエチルアミノ)クマリン、3,3’-カルボニルビス(7-N,N-ジメトキシ)クマリン、3-チエニルカルボニル-7-N,N-ジエチルアミノクマリン、3-ベンゾイルクマリン、3-ベンゾイル-7-N,N-メトキシクマリン、3-(4’-メトキシベンゾイル)クマリン、3,3’-カルボニルビス-5,7-(ジメトキシ)クマリン、ベンザルアセトフェノン、4’-N,N-ジメチルアミノベンザルアセトフェノン、4’-アセトアミノベンザル-4-メトキシアセトフェノン、ジメチルアミノベンゾフェノン、ジエチルアミノベンゾフェノン、4,4’-ビス(N-エチル,N-メチル)ベンゾフェノン、4,4’-ビス-(ジエチルアミノ)ベンゾフェノン等が挙げられる
(Other ingredients)
The photosensitive resin composition of the present invention may contain a sensitizer.
Examples of the sensitizer include 7-N,N-diethylaminocoumarin, 7-diethylamino-3-tenonylcoumarin, 3,3'-carbonylbis(7-N,N-diethylamino)coumarin, 3,3'- Carbonylbis(7-N,N-dimethoxy)coumarin, 3-thienylcarbonyl-7-N,N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-N,N-methoxycoumarin, 3-(4' -methoxybenzoyl)coumarin, 3,3'-carbonylbis-5,7-(dimethoxy)coumarin, benzalacetophenone, 4'-N,N-dimethylaminobenzalacetophenone, 4'-acetaminobenzal-4- Examples include methoxyacetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, 4,4'-bis(N-ethyl,N-methyl)benzophenone, 4,4'-bis-(diethylamino)benzophenone, etc.
増感剤を含有する場合、(a)ポリイミド前駆体100質量部に対して、0.1~3.0質量部とすることがより好ましく、0.1~1.0質量部とすることがさらに好ましい。 When containing a sensitizer, it is more preferably 0.1 to 3.0 parts by mass, and preferably 0.1 to 1.0 parts by mass, based on 100 parts by mass of (a) polyimide precursor. More preferred.
本発明の感光性樹脂組成物は、防錆性をより向上させる観点から防錆剤を含んでもよい。防錆剤としては、5-アミノ-1H-テトラゾール、1-メチル-5-アミノ-テトラゾール、1-メチル-5-メルカプト-1H-テトラゾール、1-カルボキシメチル-5-アミノ-テトラゾール等が挙げられる。これらのテトラゾール化合物は、その水溶性塩であってもよい。
防錆剤を含む場合の含有量は、(a)成分100質量部に対して0.05~5.0質量部が好ましく、0.1~4.0質量部がより好ましい。
The photosensitive resin composition of the present invention may contain a rust preventive agent from the viewpoint of further improving rust prevention properties. Examples of rust preventives include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole, etc. . These tetrazole compounds may be water-soluble salts thereof.
When a rust preventive is included, the content is preferably 0.05 to 5.0 parts by weight, more preferably 0.1 to 4.0 parts by weight, per 100 parts by weight of component (a).
また、本発明の感光性樹脂組成物は安定剤を含んでもよい。安定剤としては、1,4,4-トリメチル-2,3-ジアザビシクロ[3.2.2]-ノナ-2-エン-N,N-ジクソイド等公知の化合物を用いることができる。
安定剤を含む場合の含有量は、(a)成分100質量部に対して0.05~5.0質量部が好ましく、0.1~2.0質量部がより好ましい。
The photosensitive resin composition of the present invention may also contain a stabilizer. As the stabilizer, known compounds such as 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-zixoid can be used.
When a stabilizer is included, the content is preferably 0.05 to 5.0 parts by weight, more preferably 0.1 to 2.0 parts by weight, per 100 parts by weight of component (a).
本発明の感光性樹脂組成物は、溶剤を除いて、本質的に、(A)~(D)成分、並びに、カップリング剤(接着助剤)、界面活性剤、レベリング剤、増感剤、防錆剤及び重合禁止剤からなる群から選択される1以上の成分からなっており、本発明の効果を損なわない範囲で他に不可避不純物を含んでもよい。
本発明の感光性樹脂組成物の、例えば、80質量%以上、90質量%以上、95質量%以上、98質量%以上、99質量%以上、99.5質量%以上、99.9質量%以上又は100質量%が、溶剤を除いて、
(A)~(D)成分、又は
(A)~(D)成分並びに、カップリング剤(接着助剤)、界面活性剤、レベリング剤、増感剤、防錆剤及び重合禁止剤からなる群から選択される1以上の成分からなっていてもよい。
The photosensitive resin composition of the present invention, excluding the solvent, essentially consists of components (A) to (D), as well as a coupling agent (adhesion aid), a surfactant, a leveling agent, a sensitizer, It consists of one or more components selected from the group consisting of rust preventives and polymerization inhibitors, and may contain other unavoidable impurities as long as the effects of the present invention are not impaired.
For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more of the photosensitive resin composition of the present invention. or 100% by mass, excluding the solvent,
A group consisting of components (A) to (D), or components (A) to (D), a coupling agent (adhesion aid), a surfactant, a leveling agent, a sensitizer, a rust preventive, and a polymerization inhibitor. It may consist of one or more components selected from.
[硬化膜]
本発明の硬化膜は、上述の感光性樹脂組成物の硬化することで得ることができる。本発明の硬化膜は、パターン硬化膜として用いてもよく、パターンがない硬化膜として用いてもよい。本発明の硬化膜の膜厚は、5~20μmが好ましい。
[Cured film]
The cured film of the present invention can be obtained by curing the above-mentioned photosensitive resin composition. The cured film of the present invention may be used as a patterned cured film or as a cured film without a pattern. The thickness of the cured film of the present invention is preferably 5 to 20 μm.
[パターン硬化膜の製造方法]
本発明のパターン硬化膜の製造方法では、上述の感光性樹脂組成物を基板上に塗布、乾燥して感光性樹脂膜を形成する工程と、前記感光性樹脂膜をパターン露光して、樹脂膜を得る工程と、前記パターン露光後の樹脂膜を、有機溶剤を用いて現像し、パターン樹脂膜を得る工程と、前記パターン樹脂膜を加熱処理する工程と、を含む。これにより、パターン硬化膜を得ることができる。
[Method for manufacturing patterned cured film]
The method for producing a patterned cured film of the present invention includes a step of coating the above-described photosensitive resin composition on a substrate and drying it to form a photosensitive resin film, and exposing the photosensitive resin film in a pattern to form a resin film. Developing the resin film after pattern exposure using an organic solvent to obtain a patterned resin film; and heat-treating the patterned resin film. Thereby, a patterned cured film can be obtained.
本発明のパターン硬化膜の製造方法は、上述した本発明の感光性樹脂組成物を用いて、上記の工程を経ることで、加熱処理工程時に(B)重合性モノマー(架橋剤)の架橋反応が促され、(B)成分同士又は(A)成分と(B)成分との間で架橋が進み、高次構造が得られる。これにより、薬液の浸潤が少ない、高い薬液耐性を有するパターン硬化膜を製造することができる。また、加熱処理工程時の(B)重合性モノマー(架橋剤)の揮発量が少ないため、膜収縮(シュリンク)が少なく寸法精度に優れる。 The method for producing a patterned cured film of the present invention uses the above-described photosensitive resin composition of the present invention and undergoes the above-mentioned steps to cause the crosslinking reaction of (B) the polymerizable monomer (crosslinking agent) during the heat treatment step. is promoted, crosslinking progresses between the (B) components or between the (A) components and the (B) components, and a higher-order structure is obtained. This makes it possible to produce a patterned cured film with high chemical resistance and less infiltration of chemical liquid. Furthermore, since the amount of volatilization of the polymerizable monomer (crosslinking agent) (B) during the heat treatment step is small, there is little membrane shrinkage (shrink) and excellent dimensional accuracy is achieved.
パターンがない硬化膜を製造する方法は、例えば、上述の感光性樹脂膜を形成する工程と加熱処理する工程とを備える。さらに、露光する工程を備えてもよい。 A method for manufacturing a cured film without a pattern includes, for example, the step of forming the above-described photosensitive resin film and the step of heat treatment. Furthermore, a step of exposing may be included.
基板としては、ガラス基板、Si基板(シリコンウエハ)等の半導体基板、TiO2基板、SiO2基板等の金属酸化物絶縁体基板、窒化ケイ素基板、銅基板、銅合金基板などが挙げられる。 Examples of the substrate include semiconductor substrates such as glass substrates and Si substrates (silicon wafers), metal oxide insulator substrates such as TiO 2 substrates and SiO 2 substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.
塗布方法に特に制限はないが、スピナー等を用いて行うことができる。 There are no particular restrictions on the coating method, but a spinner or the like can be used.
乾燥は、ホットプレート、オーブン等を用いて行うことができる。
乾燥温度は90~150℃が好ましく、溶解コントラスト確保の観点から、(A)成分と(B)成分の反応を抑制するために90~120℃がより好ましい。
乾燥時間は、30秒間~5分間が好ましい。
乾燥は、2回以上行ってもよい。
これにより、上述の感光性樹脂組成物を膜状に形成した感光性樹脂膜を得ることができる。
Drying can be performed using a hot plate, oven, or the like.
The drying temperature is preferably 90 to 150°C, and more preferably 90 to 120°C from the viewpoint of ensuring dissolution contrast and suppressing the reaction between components (A) and (B).
The drying time is preferably 30 seconds to 5 minutes.
Drying may be performed two or more times.
Thereby, a photosensitive resin film formed from the above-described photosensitive resin composition can be obtained.
感光性樹脂膜の膜厚は、5~100μmが好ましく、8~50μmがより好ましく、10~30μmがさらに好ましい。 The thickness of the photosensitive resin film is preferably 5 to 100 μm, more preferably 8 to 50 μm, and even more preferably 10 to 30 μm.
パターン露光は、例えばフォトマスクを介して所定のパターンに露光する。
照射する活性光線は、i線等の紫外線、可視光線、放射線などが挙げられるが、i線であることが好ましい。
露光装置としては、平行露光機、投影露光機、ステッパ、スキャナ露光機等を用いることができる。
In the pattern exposure, for example, a predetermined pattern is exposed through a photomask.
The active light to be irradiated includes ultraviolet rays such as i-line, visible light, radiation, etc., but i-line is preferable.
As the exposure device, a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, etc. can be used.
現像することで、パターン形成された樹脂膜(パターン樹脂膜)を得ることができる。一般的に、ネガ型感光性樹脂組成物を用いた場合には、未露光部を現像液で除去する。
現像液として用いる有機溶剤は、感光性樹脂膜の良溶媒を単独で、又は良溶媒と貧溶媒を適宜混合して用いることができる。
良溶媒としては、N-メチルピロリドン、N-アセチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、シクロペンタノン、シクロヘキサノン等が挙げられる。
貧溶媒としては、トルエン、キシレン、メタノール、エタノール、イソプロパノール、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル及び水等が挙げられる。
By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, unexposed areas are removed with a developer.
As the organic solvent used as the developer, a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be mixed as appropriate.
Good solvents include N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, and cyclopentanone. , cyclohexanone and the like.
Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.
現像液に界面活性剤を添加してもよい。添加量としては、現像液100質量部に対して、0.01~10質量部が好ましく、0.1~5質量部がより好ましい。 A surfactant may be added to the developer. The amount added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the developer.
現像時間は、例えば感光性樹脂膜を浸漬して溶解するまでの時間の2倍とすることができる。
現像時間は、用いる(A)成分によっても異なるが、10秒間~15分間が好ましく、10秒間~5分間より好ましく、生産性の観点からは、20秒間~5分間がさらに好ましい。
The development time can be, for example, twice the time taken for the photosensitive resin film to be immersed and dissolved.
The development time varies depending on the component (A) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.
現像後、リンス液により洗浄を行ってもよい。
リンス液としては、蒸留水、メタノール、エタノール、イソプロパノール、トルエン、キシレン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル等を単独又は適宜混合して用いてもよく、また段階的に組み合わせて用いてもよい。
After development, cleaning may be performed with a rinse solution.
As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in appropriate mixtures, or may be used in stepwise combinations. good.
パターン樹脂膜を加熱処理することにより、パターン硬化膜を得ることができる。(A)成分のポリイミド前駆体は、加熱処理工程によって、脱水閉環反応を起こし、一部又は全部がポリイミドとなる。 A patterned cured film can be obtained by heat-treating the patterned resin film. The polyimide precursor of component (A) undergoes a dehydration ring-closing reaction through a heat treatment step, and part or all of the polyimide precursor becomes polyimide.
加熱処理の温度は、250℃以下が好ましく、120~250℃がより好ましく、200℃以下又は150~200℃がさらに好ましい。
上記範囲内であることにより、基板やデバイスへのダメージを小さく抑えることができ、デバイスを歩留り良く生産することが可能となり、プロセスの省エネルギー化を実現することができる。
The temperature of the heat treatment is preferably 250°C or lower, more preferably 120 to 250°C, and even more preferably 200°C or lower or 150 to 200°C.
By being within the above range, damage to the substrate and devices can be suppressed to a minimum, making it possible to produce devices with a high yield, and realizing energy saving in the process.
加熱処理の時間は、5時間以下が好ましく、30分間~3時間がより好ましい。上記範囲内であることにより、架橋反応又は脱水閉環反応を充分に進行することができる。
加熱処理の雰囲気は大気中であっても、窒素等の不活性雰囲気中であってもよいが、パターン樹脂膜の酸化を防ぐことができる観点から、窒素雰囲気下が好ましい。
The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. By being within the above range, the crosslinking reaction or dehydration ring closure reaction can proceed sufficiently.
The atmosphere for the heat treatment may be air or an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the patterned resin film.
加熱処理に用いられる装置としては、石英チューブ炉、ホットプレート、ラピッドサーマルアニール、縦型拡散炉、赤外線硬化炉、電子線硬化炉、マイクロ波硬化炉等が挙げられる。 Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, and the like.
[層間絶縁膜、カバーコート層、表面保護膜、電子部品]
本発明の硬化膜は、パッシベーション膜、バッファーコート膜、層間絶縁膜、カバーコート層又は表面保護膜等として用いることができる。
上記パッシベーション膜、バッファーコート膜、層間絶縁膜、カバーコート層及び表面保護膜等からなる群から選択される1以上を用いて、信頼性の高い、半導体装置、多層配線板、各種電子デバイス等の電子部品などを製造することができる。
[Interlayer insulation film, cover coat layer, surface protection film, electronic components]
The cured film of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, a surface protection film, etc.
By using one or more selected from the group consisting of the above-mentioned passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protection film, etc., highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, etc. It can manufacture electronic parts, etc.
本発明の電子部品である半導体装置の製造工程の一例を、図面を参照して説明する。
図1は、本発明の一実施形態に係る電子部品である多層配線構造の半導体装置の製造工程図である。
図1において、回路素子を有するSi基板等の半導体基板1は、回路素子の所定部分を除いてシリコン酸化膜等の保護膜2などで被覆され、露出した回路素子上に第1導体層3が形成される。その後、前記半導体基板1上に層間絶縁膜4が形成される。
An example of the manufacturing process of a semiconductor device, which is an electronic component of the present invention, will be described with reference to the drawings.
FIG. 1 is a manufacturing process diagram of a semiconductor device with a multilayer wiring structure, which is an electronic component according to an embodiment of the present invention.
In FIG. 1, a
次に、塩化ゴム系、フェノールノボラック系等の感光樹脂層5が、層間絶縁膜4上に形成され、公知の写真食刻技術によって所定部分の層間絶縁膜4が露出するように窓6Aが設けられる。
Next, a photosensitive resin layer 5 made of chloride rubber, phenol novolac, etc. is formed on the
窓6Aが露出した層間絶縁膜4は、選択的にエッチングされ、窓6Bが設けられる。
次いで、窓6Bから露出した第1導体層3を腐食することなく、感光樹脂層5を腐食するようなエッチング溶液を用いて感光樹脂層5が除去される。
The
Next, the photosensitive resin layer 5 is removed using an etching solution that corrodes the photosensitive resin layer 5 without corroding the
さらに公知の写真食刻技術を用いて、第2導体層7を形成し、第1導体層3との電気的接続を行う。
3層以上の多層配線構造を形成する場合には、上述の工程を繰り返して行い、各層を形成することができる。
Further, a
When forming a multilayer wiring structure of three or more layers, each layer can be formed by repeating the above steps.
次に、上述の感光性樹脂組成物を用いて、パターン露光により窓6Cを開口し、表面保護膜8を形成する。表面保護膜8は、第2導体層7を外部からの応力、α線等から保護するものであり、得られる半導体装置は信頼性に優れる。
尚、前記例において、層間絶縁膜を本発明の感光性樹脂組成物を用いて形成することも可能である。
Next, using the photosensitive resin composition described above, the
In addition, in the above example, it is also possible to form the interlayer insulating film using the photosensitive resin composition of the present invention.
以下、実施例及び比較例に基づき、本発明について具体的に説明する。尚、本発明は下記実施例に限定されるものではない。 The present invention will be specifically described below based on Examples and Comparative Examples. Note that the present invention is not limited to the following examples.
合成例1(ポリマーA1の合成)
3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物(ODPA)7.07gと2,2’-ジメチルビフェニル-4,4’-ジアミン(DMAP)4.12gとをN-メチル-2-ピロリドン(NMP)30gに溶解し、30℃で4時間撹拌し、その後室温下で一晩撹拌してポリアミド酸を得た。そこに水冷下で無水トリフルオロ酢酸を9.45g加え、45℃で3時間撹拌し、メタクリル酸2-ヒドロキシエチル(HEMA)7.08gを加えた。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリイミド前駆体を得た(以下、ポリマーA1とする)。
Synthesis example 1 (synthesis of polymer A1)
N-methyl- It was dissolved in 30 g of 2-pyrrolidone (NMP), stirred at 30° C. for 4 hours, and then stirred overnight at room temperature to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added thereto under water cooling, stirred at 45° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as Polymer A1).
ゲルパーミエーションクロマトグラフィー(GPC)を用いて、標準ポリスチレン換算により、以下の条件でポリマーA1の数平均分子量を求めた。ポリマーA1の数平均分子量は40,000であった。数平均分子量は、0.5mgのポリマーA1に対して溶剤[テトラヒドロフラン(THF)/ジメチルホルムアミド(DMF)=1/1(容積比)]1mLの溶液を用いて測定した。
測定装置:検出器 株式会社日立製作所製L4000UV
ポンプ:株式会社日立製作所製L6000
株式会社島津製作所製C-R4A Chromatopac
測定条件:カラムGelpack GL-S300MDT-5×2本
溶離液:THF/DMF=1/1(容積比)
LiBr(0.03mol/L)、H3PO4(0.06mol/L)
流速:1.0mL/分、検出器:UV270nm
Using gel permeation chromatography (GPC), the number average molecular weight of Polymer A1 was determined in terms of standard polystyrene under the following conditions. The number average molecular weight of Polymer A1 was 40,000. The number average molecular weight was measured using a solution of 1 mL of a solvent [tetrahydrofuran (THF)/dimethylformamide (DMF)=1/1 (volume ratio)] for 0.5 mg of polymer A1.
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: L6000 manufactured by Hitachi, Ltd.
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5
LiBr (0.03mol/L), H3PO4 ( 0.06mol /L)
Flow rate: 1.0mL/min, detector: UV270nm
また、ポリマーA1のエステル化率(ODPAに由来するカルボキシ基とHEMAとの反応率)を、以下の条件でNMR測定を行って算出した。エステル化率はポリアミド酸の全カルボキシ基に対し80モル%であった(残り20モル%はカルボキシ基であった)。
測定機器:ブルカー・バイオスピン社製 AV400M
磁場強度:400MHz
基準物質:テトラメチルシラン(TMS)
溶剤:ジメチルスルホキシド(DMSO)
Further, the esterification rate (reaction rate of the carboxy group derived from ODPA and HEMA) of the polymer A1 was calculated by performing NMR measurement under the following conditions. The esterification rate was 80 mol % based on the total carboxy groups of the polyamic acid (the remaining 20 mol % was carboxy groups).
Measuring equipment: Bruker Biospin AV400M
Magnetic field strength: 400MHz
Reference material: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)
以下の実施例及び比較例で用いた各成分は以下の通りである。 Each component used in the following Examples and Comparative Examples is as follows.
((A)成分:重合性の不飽和結合を有するポリイミド前駆体)
ポリマーA1:合成例1で得られたポリマーA1
(Component (A): polyimide precursor having polymerizable unsaturated bonds)
Polymer A1: Polymer A1 obtained in Synthesis Example 1
((B)成分:重合性モノマー)
B1:「TAIC」(東京化成工業株式会社、トリアリルイソシアヌレート、下記式で表される化合物)
B1: "TAIC" (Tokyo Kasei Kogyo Co., Ltd., triallylisocyanurate, compound represented by the following formula)
((C)成分:光重合開始剤)
C1:「NCI-930」(株式会社ADEKA製、O-アシルオキシム系化合物、下記式で表される化合物)
C1: "NCI-930" (manufactured by ADEKA Co., Ltd., O-acyloxime compound, compound represented by the following formula)
((D)成分:熱ラジカル発生剤)
D1:「パークミルD」(日油株式会社製、ジクミルパーオキシド、下記式で表される化合物、1時間半減期温度135.7℃)
D1: "Percmil D" (manufactured by NOF Corporation, dicumyl peroxide, compound represented by the following formula, 1 hour half-life temperature 135.7 ° C.)
((E)成分:溶剤)
E1:NMP
E2:「KJCMPA-100」(KJケミカルズ株式会社製、下記式で表される化合物)
E1:NMP
E2: "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd., a compound represented by the following formula)
(他の成分:重合禁止剤)
「Taobn」(1,4,4-トリメチル-2,3-ジアザビシクロ[3.2.2]-ノナ-2-エン-N,N-ジクソイド、Hampford Research社製)
(Other ingredients: polymerization inhibitor)
"Taobn" (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-zixoid, manufactured by Hampford Research)
(他の成分:防錆剤)
「5ATz」(東京化成工業株式会社製、商品名「5-アミノ-1H-テトラゾール」、下記式で表される化合物)
"5ATz" (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "5-amino-1H-tetrazole", compound represented by the following formula)
(他の成分:接着助剤)
「UCT-801」(3-ウレイドプロピルトリエトキシシラン、United Chemical Technologies社製)
(Other ingredients: adhesion aid)
"UCT-801" (3-ureidopropyltriethoxysilane, manufactured by United Chemical Technologies)
(他の成分:増感剤)
「EMK」(Aldrich社製、下記式で表される化合物、Etはエチル基を表す)
"EMK" (manufactured by Aldrich, a compound represented by the following formula, Et represents an ethyl group)
実施例1~3及び比較例1
[感光性樹脂組成物の調製]
表1に示す成分及び配合量にて、実施例1~3及び比較例1の感光性樹脂組成物を調製した。表1の配合量は、100質量部の(A)成分に対する各成分の質量部である。
Examples 1 to 3 and comparative example 1
[Preparation of photosensitive resin composition]
Photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were prepared using the components and blending amounts shown in Table 1. The blending amounts in Table 1 are parts by mass of each component relative to 100 parts by mass of component (A).
[パターン硬化膜の製造及び評価]
(パターン硬化膜の製造)
得られた感光性樹脂組成物を、塗布装置「Act8」(東京エレクトロン株式会社製)を用いてシリコンウエハ上にスピンコートし、100℃で2分間乾燥後、110℃で2分間乾燥して乾燥膜厚が13μmの感光性樹脂膜を形成した。得られた感光性樹脂膜をシクロペンタノンに浸漬して完全に溶解するまでの時間の2倍を現像時間として設定した。
上記と同様に感光性樹脂膜を作製し、得られた感光性樹脂膜に、i線ステッパ「FPA-3000iW」(キヤノン株式会社製)を用いて、400mJ/cm2のi線を所定のパターンに照射して露光を行った。露光後の樹脂膜を、「Act8」により、シクロペンタノンを用いて上記現像時間でパドル現像した後、プロピレングリコールモノメチルエーテルアセテート(PGMEA)でリンス洗浄を行い、パターン樹脂膜を得た。得られたパターン樹脂膜を、縦型拡散炉「μ-TF」(光洋サーモシステム株式会社製)を用いて、窒素雰囲気下、175℃で1時間加熱し、パターン硬化膜(硬化後膜厚10μm)を得た。
[Manufacture and evaluation of patterned cured film]
(Manufacture of patterned cured film)
The obtained photosensitive resin composition was spin-coated onto a silicon wafer using a coating device "Act8" (manufactured by Tokyo Electron Ltd.), dried at 100°C for 2 minutes, and then dried at 110°C for 2 minutes. A photosensitive resin film having a thickness of 13 μm was formed. The development time was set to be twice the time required for the obtained photosensitive resin film to be completely dissolved by immersing it in cyclopentanone.
A photosensitive resin film was prepared in the same manner as above, and an i-line of 400 mJ/cm 2 was applied to the resulting photosensitive resin film in a predetermined pattern using an i-line stepper "FPA-3000iW" (manufactured by Canon Inc.). Exposure was performed by irradiating the The exposed resin film was paddle developed using cyclopentanone for the above development time according to "Act 8", and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film. The obtained patterned resin film was heated at 175°C for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace "μ-TF" (manufactured by Koyo Thermo Systems Co., Ltd.) to form a patterned cured film (film thickness after curing: 10 μm). ) was obtained.
(薬液耐性の評価:外観)
得られたパターン硬化膜を、80℃に加熱したNMP(薬液)に30分浸漬した。その後、パターン硬化膜を冷却し、アセトンで洗浄し、乾燥した。
乾燥後のパターン硬化膜を光学顕微鏡で観察してパターンのダメージを以下のように評価した。結果を表1に示す。
A:クラックが観察されなかった。
B:開口部の角周辺に微細なクラックが見られた。
C:開口部の角周辺にクラックが見られた。
D:硬化膜の全面に渡ってクラックが見られた。
(Evaluation of chemical resistance: appearance)
The obtained patterned cured film was immersed in NMP (chemical solution) heated to 80° C. for 30 minutes. Thereafter, the patterned cured film was cooled, washed with acetone, and dried.
The patterned cured film after drying was observed with an optical microscope, and damage to the pattern was evaluated as follows. The results are shown in Table 1.
A: No cracks were observed.
B: Fine cracks were observed around the corners of the opening.
C: Cracks were observed around the corners of the opening.
D: Cracks were observed over the entire surface of the cured film.
実施例4及び比較例2
[感光性樹脂組成物の調製]
表2に示す成分及び配合量にて、実施例4及び比較例2の感光性樹脂組成物を調製した。表2の配合量は、100質量部の(A)成分に対する各成分の質量部である。
Example 4 and comparative example 2
[Preparation of photosensitive resin composition]
Photosensitive resin compositions of Example 4 and Comparative Example 2 were prepared using the components and blending amounts shown in Table 2. The blending amounts in Table 2 are parts by mass of each component relative to 100 parts by mass of component (A).
[パターン硬化膜の製造及び評価]
(パターン硬化膜の製造)
biasHAST(高速加速寿命試験)用テスト基板(シリコンウエハ/ポリイミド層(7μm)/TiCuシード層(25/150nm)/Cu層(3.5μm)という層構成のウエハ、TiCuシード層及びCu層は櫛歯パターン(櫛歯の線幅:2μm、歯の数:陽極10本、陰極10本、間隔:2μm)を有する)を用いた。
得られた感光性樹脂組成物を、biasHAST用テスト基板上にスピンコートし、105℃で2分間乾燥後、110℃で2分間乾燥して、乾燥後膜厚が7μmの感光性樹脂膜を形成した。尚、biasHAST用テスト基板の表面にはパッド部分があり、塗布は、パッド部分に感光性樹脂組成物を塗布しないように行った。得られた感光性樹脂膜に、「マスクアライナーMA-8」(ズース・マイクロテック社製)を用いて、ブロードバンド露光(i線換算:500mJ/cm2)を行った。その後、露光後の樹脂膜をμ-TFを用いて窒素雰囲気下、180℃で2時間加熱し、硬化膜(硬化後膜厚6μm)付きテスト基板を得た。
[Manufacture and evaluation of patterned cured film]
(Manufacture of patterned cured film)
BiasHAST (high speed accelerated life test) test substrate (wafer with layer configuration of silicon wafer/polyimide layer (7 μm)/TiCu seed layer (25/150 nm)/Cu layer (3.5 μm), TiCu seed layer and Cu layer are combed. A tooth pattern (having a comb tooth line width: 2 μm, number of teeth: 10 anodes, 10 cathodes, interval: 2 μm) was used.
The obtained photosensitive resin composition was spin coated onto a test substrate for biasHAST, dried at 105°C for 2 minutes, and then dried at 110°C for 2 minutes to form a photosensitive resin film with a thickness of 7 μm after drying. did. Note that there was a pad portion on the surface of the biasHAST test substrate, and the photosensitive resin composition was applied so as not to be applied to the pad portion. Broadband exposure (i-line equivalent: 500 mJ/cm 2 ) was performed on the obtained photosensitive resin film using "Mask Aligner MA-8" (manufactured by SUSS Microtech). Thereafter, the exposed resin film was heated at 180° C. for 2 hours in a nitrogen atmosphere using μ-TF to obtain a test substrate with a cured film (film thickness after curing: 6 μm).
(薬液耐性の評価:膜厚変化率)
得られた硬化膜を、80℃に加熱したNMP(薬液)に30分浸漬した。その後、硬化膜を冷却し、アセトンで洗浄して乾燥した。
乾燥後の硬化膜の膜厚を測定し、「(薬液浸漬後の膜厚)-(薬液浸漬前の膜厚)」を(薬液浸漬前の膜厚)で除して百分率にすることで膜厚変化率を算出した。結果を表2に示す。
(Evaluation of chemical resistance: film thickness change rate)
The obtained cured film was immersed in NMP (chemical solution) heated to 80° C. for 30 minutes. Thereafter, the cured film was cooled, washed with acetone, and dried.
The film thickness of the cured film after drying is measured and calculated by dividing "(film thickness after chemical immersion) - (film thickness before chemical immersion)" by (film thickness before chemical immersion) to make a percentage. The rate of change in thickness was calculated. The results are shown in Table 2.
表1,2より、本発明の感光性樹脂組成物から得られた硬化膜は、薬液に浸漬させた後の膜厚変化率が小さく、薬液の浸みこみによる膜の膨潤が少ないことが分かる。また、クラックやひび割れが抑制され、外観に優れることが分かる。 From Tables 1 and 2, it can be seen that the cured film obtained from the photosensitive resin composition of the present invention has a small rate of change in film thickness after being immersed in a chemical solution, and there is little swelling of the film due to permeation of the chemical solution. It can also be seen that cracks and cracks are suppressed and the appearance is excellent.
本発明の感光性樹脂組成物は、層間絶縁膜、カバーコート層又は表面保護膜等に用いることができ、本発明の層間絶縁膜、カバーコート層又は表面保護膜は、電子部品等に用いることができる。 The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer, a surface protective film, etc., and the interlayer insulating film, cover coat layer, or surface protective film of the present invention can be used for electronic components, etc. I can do it.
1 半導体基板
2 保護膜
3 第1導体層
4 層間絶縁膜
5 感光樹脂層
6A、6B、6C 窓
7 第2導体層
8 表面保護膜
Claims (17)
前記感光性樹脂膜をパターン露光して、樹脂膜を得る工程と、
前記パターン露光後の樹脂膜を、有機溶剤を用いて現像し、パターン樹脂膜を得る工程と、
前記パターン樹脂膜を加熱処理する工程と、
を含み、
前記(B)成分が、下記式(23)で表される化合物を含む、パターン硬化膜の製造方法。
pattern-exposing the photosensitive resin film to obtain a resin film;
developing the resin film after the pattern exposure using an organic solvent to obtain a patterned resin film;
a step of heat treating the patterned resin film;
including;
A method for producing a patterned cured film, wherein the component (B) contains a compound represented by the following formula (23).
(B)重合性モノマーと、
(C)光重合開始剤と、
(D)熱ラジカル発生剤と、
を含み、
前記(B)成分が、下記式(23)で表される化合物を含む感光性樹脂組成物(脂肪族環状骨格を有する重合性モノマーを含む感光性樹脂組成物を除く)。
(B) a polymerizable monomer;
(C) a photopolymerization initiator;
(D) a thermal radical generator;
including;
A photosensitive resin composition in which the component (B) contains a compound represented by the following formula (23) (excluding photosensitive resin compositions containing a polymerizable monomer having an aliphatic cyclic skeleton) .
An electronic component comprising the interlayer insulating film, cover coat layer, or surface protection film according to claim 16.
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