JP6060541B2 - Thermosetting resin composition for semiconductor encapsulation and semiconductor device using the same - Google Patents
Thermosetting resin composition for semiconductor encapsulation and semiconductor device using the same Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims description 40
- 239000011342 resin composition Substances 0.000 title claims description 39
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 39
- 238000005538 encapsulation Methods 0.000 title claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 40
- 239000005011 phenolic resin Substances 0.000 claims description 37
- -1 maleimide compound Chemical class 0.000 claims description 32
- 125000006017 1-propenyl group Chemical group 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 22
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 22
- 239000011256 inorganic filler Substances 0.000 claims description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 17
- 238000007789 sealing Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 238000001721 transfer moulding Methods 0.000 description 11
- 239000003566 sealing material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000005350 fused silica glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 238000005937 allylation reaction Methods 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
- 238000006596 Alder-ene reaction Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- DRKKXODCPQWHNU-UHFFFAOYSA-N O=C(C=CC1=O)N1c1ccc(C(c(cc2)ccc2N(C(C=C2)=O)C2=O)c(cc2)ccc2N(C(C=C2)=O)C2=O)cc1 Chemical compound O=C(C=CC1=O)N1c1ccc(C(c(cc2)ccc2N(C(C=C2)=O)C2=O)c(cc2)ccc2N(C(C=C2)=O)C2=O)cc1 DRKKXODCPQWHNU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Description
本発明は、半導体素子等の封止に用いられる半導体封止用熱硬化性樹脂組成物およびそれを用いた半導体装置に関するものである。 The present invention relates to a thermosetting resin composition for semiconductor sealing used for sealing semiconductor elements and the like, and a semiconductor device using the same.
従来から、トランジスター、ＩＣ、ＬＳＩ等の各種半導体素子は、外部環境からの保護および半導体素子のハンドリングを簡易にする観点から、プラスチックパッケージ等により封止され半導体装置化されている。上記プラスチックパッケージとしては、成形性、接着性、電気特性、機械特性、耐湿性に優れたエポキシ樹脂組成物により樹脂封止されたものが主流となっている。 2. Description of the Related Art Conventionally, various semiconductor elements such as transistors, ICs, and LSIs are sealed with a plastic package or the like from the viewpoint of protection from the external environment and easy handling of the semiconductor elements. As the above-mentioned plastic packages, those sealed with an epoxy resin composition excellent in moldability, adhesiveness, electrical characteristics, mechanical characteristics, and moisture resistance are mainly used.
しかし、半導体装置が高密度化、小型化されていくにつれ、半導体装置の駆動温度が高くなり、その封止樹脂に対する耐熱性に関してもより高いものが要求されている。例えば、耐熱性に優れた樹脂としては、マレイミド・アリル樹脂が広く知られているが、この樹脂は硬化性が悪く、生産性を重視する分野への適用が困難であった。 However, as the semiconductor device is increased in density and size, the driving temperature of the semiconductor device is increased, and higher heat resistance is required for the sealing resin. For example, as a resin excellent in heat resistance, maleimide allyl resin is widely known. However, this resin has poor curability and is difficult to be applied to a field where productivity is important.
このような問題を有していることから、硬化性の向上，改善を図る目的で、１−プロペニル基を有する化合物を硬化剤に加える手法が検討されている（特許文献１参照）。また、耐熱性・耐電圧の向上を目的に、珪素含有硬化性組成物を用いるというような別の異なる樹脂系による封止材料も検討されている（特許文献２参照）。 Since it has such a problem, the method of adding the compound which has 1-propenyl group to a hardening | curing agent is examined for the purpose of improving and improving sclerosis | hardenability (refer patent document 1). Further, for the purpose of improving heat resistance and withstand voltage, a sealing material using another different resin system such as using a silicon-containing curable composition has been studied (see Patent Document 2).
しかしながら、上記特許文献１等の封止材料において、特に無機質充填剤を配合，混練した封止材料による硬化物系の場合には、適切な硬化性と流動性の制御が困難であり、これが工業化への大きな障害となっていた。 However, in the sealing material of the above-mentioned Patent Document 1 or the like, particularly in the case of a cured product system using a sealing material in which an inorganic filler is blended and kneaded, it is difficult to control appropriate curability and fluidity. It was a big obstacle to the.
また、上記特許文献２の樹脂系は、ポッティングによる樹脂封止を念頭において開発された材料であるが、工業的な生産性を考慮した場合、上記ポッティングよりも生産性およびコスト的に優れた製造方法であるトランスファー成形に使用可能な樹脂系の封止材料であることが望ましいといえる。したがって、トランスファー成形のような工業生産性に適した封止材料の開発が強く望まれている。 In addition, the resin system of Patent Document 2 is a material that was developed with the resin sealing by potting in mind. However, when industrial productivity is taken into consideration, the manufacturing is superior in productivity and cost than the potting. It can be said that a resin-based sealing material that can be used for transfer molding, which is a method, is desirable. Therefore, development of a sealing material suitable for industrial productivity such as transfer molding is strongly desired.
本発明は、このような事情に鑑みなされたもので、生産性に優れたトランスファー成形可能な流動性と硬化性の両立を維持しつつ、耐熱性に優れた半導体封止用熱硬化性樹脂組成物およびそれを用いた半導体装置の提供をその目的とする。 The present invention has been made in view of such circumstances, and the thermosetting resin composition for semiconductor encapsulation having excellent heat resistance while maintaining both the fluidity and curability capable of transfer molding excellent in productivity. It is an object to provide a product and a semiconductor device using the product.
上記目的を達成するため、本発明は、下記の（Ａ）〜（Ｄ）成分を含有する半導体封止用熱硬化性樹脂組成物であって、下記の条件（ｘ）〜（ｚ）を満たす半導体封止用熱硬化性樹脂組成物を第１の要旨とする。
（Ａ）１分子中に２個以上のマレイミド基を有するマレイミド化合物。
（Ｂ）下記の式（１）で表される構造単位を含有するアリル化フェノール樹脂。
（ｘ）上記（Ｂ）成分中に含まれるアリル基の合計モル量（ｂ）と、上記（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｃ）の比（ｂ：ｃ）が、ｂ：ｃ＝９５：５〜５０：５０である。
（ｙ）上記（Ｄ）成分の含有量が、熱硬化性樹脂組成物全体の５５〜９３重量％である。
（ｚ）上記（Ｂ）成分中に含まれるアリル基および上記（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｂｃ）と、上記（Ａ）成分中に含まれるマレイミド基の合計モル量（ａ）の比（ｂｃ：ａ）が、ｂｃ：ａ＝１５：８５〜７５：２５である。
In order to achieve the above object, the present invention is a thermosetting resin composition for semiconductor encapsulation containing the following components (A) to (D), which satisfies the following conditions (x) to (z): A thermosetting resin composition for semiconductor encapsulation is a first gist.
(A) A maleimide compound having two or more maleimide groups in one molecule.
(B) An allylated phenol resin containing a structural unit represented by the following formula (1).
(X) Ratio (b: c) of the total molar amount (b) of allyl groups contained in the component (B) and the total molar amount (c) of 1-propenyl groups contained in the component (C) However, it is b: c = 95: 5-50: 50.
(Y) Content of the said (D) component is 55 to 93 weight% of the whole thermosetting resin composition.
(Z) The total molar amount (bc) of the allyl group contained in the component (B) and the 1-propenyl group contained in the component (C), and the sum of the maleimide groups contained in the component (A) The molar amount (a) ratio (bc: a) is bc: a = 15: 85-75: 25.
そして、本発明は、上記半導体封止用熱硬化性樹脂組成物を用いて、半導体素子を樹脂封止してなる半導体装置を第２の要旨とする。 And this invention makes the 2nd summary the semiconductor device formed by resin-sealing a semiconductor element using the said thermosetting resin composition for semiconductor sealing.
本発明者は、トランスファー成形に適した流動性および硬化性を備えるとともに、マレイミド樹脂の有する高い耐熱性を生かした封止材料を得るために鋭意検討を重ねた。その結果、上記特定のアリル化フェノール樹脂〔（Ｂ）成分〕、および、上記特定の構造単位を有する化合物〔（Ｃ）成分〕を用いるとともに、上記（Ｂ）成分中に含まれるアリル基の合計モル量（ｂ）と、上記（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｃ）の比（ｂ：ｃ）を、ｂ：ｃ＝９５：５〜５０：５０に〔条件（ｘ）〕、上記（Ｄ）成分の含有量を、熱硬化性樹脂組成物全体の５５〜９３重量％に〔条件（ｙ）〕、上記（Ｂ）成分中に含まれるアリル基および上記（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｂｃ）と、上記（Ａ）成分中に含まれるマレイミド基の合計モル量（ａ）の比（ｂｃ：ａ）を、ｂｃ：ａ＝１５：８５〜７５：２５〔条件（ｚ）〕にそれぞれ設定すると、封止材料としてトランスファー成形可能な流動性および硬化性を維持した状態で、優れた耐熱性を有する封止材料が得られることを見出し、本発明に到達した。 The present inventor has intensively studied to obtain a sealing material having fluidity and curability suitable for transfer molding and taking advantage of the high heat resistance of the maleimide resin. As a result, the specific allylated phenol resin [component (B)] and the compound having the specific structural unit [component (C)] were used, and the total of allyl groups contained in the component (B) The ratio (b: c) between the molar amount (b) and the total molar amount (c) of 1-propenyl groups contained in the component (C) is set to b: c = 95: 5 to 50:50 [conditions (X)], the content of the component (D) is 55 to 93% by weight of the entire thermosetting resin composition [condition (y)], the allyl group contained in the component (B) and the above ( C) The ratio (bc: a) of the total molar amount (bc) of 1-propenyl groups contained in the component to the total molar amount (a) of maleimide groups contained in the component (A) is expressed as bc: a = 15: 85 to 75:25 [Condition (z)], respectively, a transformer as a sealing material While maintaining § over moldable fluidity and curability, it found that sealing material having excellent heat resistance can be obtained, thereby achieving the present invention.
上記（Ｂ）成分および（Ｃ）成分の併用、ならびに上記各条件とすることによって上記目的が達成される要因はつぎの理由によるものと推測される。すなわち、マレイミド化合物〔（Ａ）成分〕におけるマレイミド基はアリル基と２段階にて反応するため硬化速度は遅いものである。一方、このマレイミド基は１−プロペニル基と１段階にて反応するため硬化速度が速いものである。ただし、上記１−プロペニル基はラジカルによる付加重合も進行することがあり、エン反応から始まるアリル基の場合に比べ硬化速度が速くなるが、過剰に添加すると耐熱性を下げる要因となる。これらの事項を踏まえ、エポキシ樹脂に比べて耐熱性に優れるマレイミド化合物を、マレイミド基と、アリル基および１−プロペニル基を適正な割合にて反応・硬化させるとともに、上記（Ｄ）成分である無機質充填剤の含有量を適正な範囲とすることによって、優れた耐熱性とともに良好な流動性および硬化性を実現させることに至ったのである。 It is presumed that the reason why the object is achieved by the combined use of the component (B) and the component (C) and the above conditions is as follows. That is, since the maleimide group in the maleimide compound [component (A)] reacts with the allyl group in two stages, the curing rate is slow. On the other hand, the maleimide group reacts with the 1-propenyl group in one step, so that the curing rate is high. However, the 1-propenyl group may also undergo addition polymerization by radicals, and the curing rate is faster than in the case of an allyl group starting from an ene reaction. However, if it is added excessively, it causes a decrease in heat resistance. Based on these matters, the maleimide compound, which is superior in heat resistance as compared with the epoxy resin, is reacted and cured with an appropriate ratio of maleimide group, allyl group and 1-propenyl group, and the inorganic component (D) above By setting the content of the filler within an appropriate range, it has been possible to realize excellent fluidity and curability as well as excellent heat resistance.
このように、本発明は、マレイミド化合物〔（Ａ）成分〕、特定のアリル化フェノール樹脂〔（Ｂ）成分〕、特定の構造単位を有する化合物〔（Ｃ）成分〕、および、無機質充填剤〔（Ｄ）成分〕を用いるとともに、上記（Ｂ）成分中に含まれるアリル基の合計モル量（ｂ）と、上記（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｃ）の比（ｂ：ｃ）を特定範囲とし〔条件（ｘ）〕、上記（Ｄ）成分の含有量を、熱硬化性樹脂組成物全体の特定範囲とし〔条件（ｙ）〕、上記（Ｂ）成分中に含まれるアリル基および上記（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｂｃ）と、上記（Ａ）成分中に含まれるマレイミド基の合計モル量（ａ）の比（ｂｃ：ａ）を特定範囲とする〔条件（ｚ）〕半導体封止用熱硬化性樹脂組成物である。このため、封止材料としてトランスファー成形可能な良好な流動性および硬化性を備えるとともに、優れた耐熱性を有するようになる。したがって、上記半導体封止用熱硬化性樹脂組成物を用いて得られる半導体装置では、高い生産効率にて耐熱信頼性等の特性を備えたものを得ることができる。 Thus, the present invention provides a maleimide compound [component (A)], a specific allylated phenol resin [component (B)], a compound having a specific structural unit [component (C)], and an inorganic filler [ (D) component] and the total molar amount (b) of allyl groups contained in the component (B) and the total molar amount (c) of 1-propenyl groups contained in the component (C). The ratio (b: c) is a specific range [condition (x)], and the content of the component (D) is a specific range of the entire thermosetting resin composition [condition (y)], and the component (B) Ratio of the total molar amount (bc) of the allyl group contained therein and the 1-propenyl group contained in the component (C) to the total molar amount (a) of the maleimide group contained in the component (A) ( bc: Thermosetting resin set for semiconductor encapsulation with a) in a specific range [Condition (z)] Thing is. For this reason, it has the favorable fluidity | liquidity and sclerosis | hardenability which can be transfer-molded as a sealing material, and has the outstanding heat resistance. Therefore, in the semiconductor device obtained using the thermosetting resin composition for semiconductor encapsulation, a semiconductor device having characteristics such as heat resistance reliability can be obtained with high production efficiency.
そして、上記特定のアリル化フェノール樹脂〔（Ｂ）成分〕の数平均分子量が、２５０〜１０００であると、封止工程の際の成形・硬化温度にて蒸発することなく良好な反応性が維持され、かつ耐熱性が良好な熱硬化性樹脂組成物が得られる。 And when the number average molecular weight of the said specific allylated phenol resin [(B) component] is 250-1000, favorable reactivity is maintained, without evaporating at the shaping | molding and hardening temperature in the sealing process. And a thermosetting resin composition having good heat resistance is obtained.
つぎに、本発明を実施するための形態について説明する。 Next, an embodiment for carrying out the present invention will be described.
本発明の半導体封止用熱硬化性樹脂組成物（以下、「熱硬化性樹脂組成物」と略すことがある）は、マレイミド化合物（Ａ成分）と、特定のアリル化フェノール樹脂（Ｂ成分）と、特定の化合物（Ｃ）成分と、無機質充填剤（Ｄ成分）とを用いて得られるものであって、通常、粉末状もしくはこれを打錠したタブレット状になっている。 The thermosetting resin composition for semiconductor encapsulation of the present invention (hereinafter sometimes abbreviated as “thermosetting resin composition”) includes a maleimide compound (A component) and a specific allylated phenol resin (B component). And a specific compound (C) component and an inorganic filler (D component), which are usually in the form of a powder or tablet obtained by tableting this.
〈Ａ：マレイミド化合物〉
上記マレイミド化合物（Ａ成分）は、１分子中に２個以上のマレイミド基を有する化合物であり、例えば、下記の一般式（３）で表されるマレイミド化合物、下記の一般式（４）で表されるマレイミド化合物、下記の構造式（５）で表されるマレイミド化合物等があげられる。これらは単独でもしくは２種以上併せて用いることができる。
<A: Maleimide compound>
The maleimide compound (component A) is a compound having two or more maleimide groups in one molecule. For example, the maleimide compound represented by the following general formula (3) and the following general formula (4) And maleimide compounds represented by the following structural formula (5). These may be used alone or in combination of two or more.
〈Ｂ：特定のアリル化フェノール樹脂〉
上記マレイミド化合物（Ａ成分）とともに用いられる特定のアリル化フェノール樹脂（Ｂ成分）は、上記マレイミド化合物（Ａ成分）を硬化させる作用を有する硬化剤であり、下記の式（１）で表される構造単位を含有するフェノール樹脂である。
<B: Specific allylated phenol resin>
The specific allylated phenol resin (B component) used together with the maleimide compound (component A) is a curing agent having a function of curing the maleimide compound (component A), and is represented by the following formula (1). It is a phenol resin containing a structural unit.
そして、上記アリル化フェノール樹脂（Ｂ成分）における上記式（１）で表される構造単位の占める割合は、熱硬化性樹脂組成物の耐熱性という観点から、アリル化率が６０％以上であることが好ましい。これは、上記式（１）で表される構造単位〔構造単位（１）〕とフェノール構造単位の合計量に対する構造単位（１）のモル比率［構造単位（１）／〔構造単位（１）＋フェノール構造単位〕×１００］が好ましくは６０％以上であるということである。すなわち、この上記構造単位（１）とフェノール構造単位の合計量に対する構造単位（１）のモル比率［構造単位（１）／〔構造単位（１）＋フェノール構造単位〕×１００］をアリル化率といい、好ましくはこれが６０％以上であるということである。上記アリル化率が上記範囲を下回り小さすぎると、得られる硬化物のガラス転移温度が低くなり耐熱性に劣る傾向がみられる。 And the ratio for which the structural unit represented by the said Formula (1) in the said allylated phenol resin (B component) occupies is 60% or more from a viewpoint of the heat resistance of a thermosetting resin composition. It is preferable. This is the molar ratio of the structural unit (1) to the total amount of the structural unit represented by the above formula (1) [structural unit (1)] and the phenol structural unit [structural unit (1) / [structural unit (1)]. + Phenol structural unit] × 100] is preferably 60% or more. That is, the molar ratio of the structural unit (1) to the total amount of the structural unit (1) and the phenol structural unit [structural unit (1) / [structural unit (1) + phenol structural unit] × 100] is allylation ratio. Preferably, this is 60% or more. If the allylation rate is below the above range and is too small, the glass transition temperature of the resulting cured product tends to be low and the heat resistance tends to be poor.
上記アリル化フェノール樹脂（Ｂ成分）は、例えば、つぎのようにして合成することができる。すなわち、フェノールノボラック樹脂、ハロゲン化アリル、塩基性化合物および溶媒を混合して加熱撹拌することにより、アリルエーテル化したフェノール樹脂が得られる。つぎに、得られたアリルエーテル化したフェノール樹脂を１８０〜２００℃にて加熱して、上記アリルエーテル化したフェノール樹脂の一部または全部のアリル基がクライゼン転位することにより目的の上記式（１）で表される構造単位を含有するアリル化フェノール樹脂（Ｂ成分）を合成することができる。 The allylated phenol resin (component B) can be synthesized, for example, as follows. That is, an allyl etherified phenol resin can be obtained by mixing a phenol novolac resin, an allyl halide, a basic compound and a solvent and stirring with heating. Next, the obtained allyl etherified phenol resin is heated at 180 to 200 ° C., and a part or all of the allyl group of the allyl etherified phenol resin undergoes Claisen rearrangement, thereby achieving the target formula (1). The allylated phenol resin (component B) containing the structural unit represented by
また、オルソアリルフェノールとホルマリンとを混合し、これに酸触媒を添加して加熱撹拌することによっても同様に、アリル化フェノール樹脂（Ｂ成分）を合成することができる。 Alternatively, an allylated phenol resin (component B) can be synthesized in the same manner by mixing orthoallylphenol and formalin, adding an acid catalyst thereto and stirring with heating.
上記アリル化フェノール樹脂（Ｂ）成分としては、数平均分子量が２００〜２０００であることが好ましく、より好ましくは２５０〜１０００である。すなわち、数平均分子量が小さ過ぎると、樹脂封止の工程の際に成形・硬化温度にて蒸発しやすくなる傾向がみられる。また、数平均分子量が大き過ぎると、耐熱性が低下する傾向がみられる。 As said allylated phenol resin (B) component, it is preferable that a number average molecular weight is 200-2000, More preferably, it is 250-1000. That is, if the number average molecular weight is too small, it tends to evaporate easily at the molding / curing temperature during the resin sealing step. Moreover, when the number average molecular weight is too large, the heat resistance tends to decrease.
なお、アリル化フェノール樹脂の数平均分子量は、例えば、つぎのようにして測定，算出される。すなわち、アリル化フェノール樹脂を０．１重量％テトラヒドロフラン（ＴＨＦ）溶液に調整し、２５℃で１日放置する。その後、０．４５μｍメンブランフィルターにて濾過し、得られた濾液について分子量測定を行なう。この分子量測定には、例えば、ＧＰＣ（東ソー社製、ＨＬＣ−８１２０ＧＰＣ、カラム：東ソー社製ＧＭＨXL、ＧＭＨXL、Ｇ３０００ＨXL）が用いられる。また、この場合の測定条件は、カラム温度４０℃、溶離液テトラヒドロフラン、流速０．８ｍＬ／分、注入量１００μＬである。そして、検出器は、示差屈折計を用い、ポリスチレン換算により数平均分子量を算出する。 The number average molecular weight of the allylated phenol resin is measured and calculated as follows, for example. That is, the allylated phenol resin is adjusted to a 0.1 wt% tetrahydrofuran (THF) solution and left at 25 ° C. for 1 day. Then, it filters with a 0.45 micrometer membrane filter, and molecular weight measurement is performed about the obtained filtrate. For this molecular weight measurement, for example, GPC (manufactured by Tosoh Corporation, HLC-8120GPC, column: Tosoh Corporation GMH XL , GMH XL , G3000H XL ) is used. The measurement conditions in this case are a column temperature of 40 ° C., an eluent tetrahydrofuran, a flow rate of 0.8 mL / min, and an injection volume of 100 μL. And a detector calculates a number average molecular weight by polystyrene conversion using a differential refractometer.
〈Ｃ：特定の化合物〉
上記Ａ成分およびＢ成分とともに用いられる特定の化合物（Ｃ成分）は、下記の式（２）で表される構造単位を含有する化合物である。
<C: Specific compound>
The specific compound (C component) used together with the A component and the B component is a compound containing a structural unit represented by the following formula (2).
そして、上記特定の化合物（Ｃ成分）における上記式（２）で表される構造単位の占める割合は、熱硬化性樹脂組成物の耐熱性という観点から、プロペニル化率が５０％以上であることが好ましい。これは、上記式（２）で表される構造単位〔構造単位（２）〕とフェノール構造単位の合計量に対する構造単位（２）のモル比率［構造単位（２）／〔構造単位（２）＋フェノール構造単位〕×１００］が好ましくは５０％以上であるといい、この構造単位（２）とフェノール構造単位の合計量に対する構造単位（２）のモル比率［構造単位（２）／〔構造単位（２）＋フェノール構造単位〕×１００］をプロペニル化率という。 And the ratio for which the structural unit represented by the said Formula (2) in the said specific compound (C component) occupies has a propenylation rate of 50% or more from a viewpoint of the heat resistance of a thermosetting resin composition. Is preferred. This is the molar ratio of the structural unit (2) to the total amount of the structural unit represented by the above formula (2) [structural unit (2)] and the phenol structural unit [structural unit (2) / [structural unit (2)]. + Phenol structural unit] × 100] is preferably 50% or more, and the molar ratio of the structural unit (2) to the total amount of the structural unit (2) and the phenol structural unit [structural unit (2) / [structure Unit (2) + phenol structural unit] × 100] is referred to as propenylation rate.
上記式（２）で表される構造単位を含有する化合物（Ｃ成分）としては、例えば、上記アリル化フェノール樹脂（Ｂ成分）におけるアリル基を異性化させて、フェノール性水酸基のオルト位やパラ位に、１−プロペニル基を結合させたもの〔式（２）においてＸが−Ｈである〕があげられる。このように、上記式（２）で表される構造単位を含有する化合物（Ｃ成分）は、例えば、上記アリル化フェノール樹脂（Ｂ成分）を準備し、このアリル化フェノール樹脂（Ｂ成分）におけるアリル基を異性化させることにより、フェノール性水酸基のオルト位やパラ位に、１−プロペニル基が結合した化合物が得られる。そして、上記式（２）で表される構造単位を含有する化合物（Ｃ成分）としては、コストの観点から、上記アリル化フェノール樹脂（Ｂ成分）を塩基性条件下で加熱撹拌してアリル基を異性化させることにより得られるもの〔式（２）においてＸが−Ｈである〕が用いられる。 As the compound (C component) containing the structural unit represented by the above formula (2), for example, the allyl group in the allylated phenol resin (B component) is isomerized to give the ortho position or para of the phenolic hydroxyl group. And a 1-propenyl group bonded to the position [in the formula (2), X is —H ] . Thus, the compound (C component) containing the structural unit represented by the above formula (2) prepares, for example, the allylated phenol resin (B component), and in this allylated phenol resin (B component). By isomerizing the allyl group, a compound in which a 1-propenyl group is bonded to the ortho position or para position of the phenolic hydroxyl group is obtained . Its to the above formula (2) containing a structural unit represented by the compound as component (C), from the viewpoint of cost, with the allylated phenol resin (B component) was heated and stirred under basic conditions What is obtained by isomerizing an allyl group [in the formula (2), X is —H] is used .
また、上述のように、上記Ｂ成分およびＣ成分をそれぞれ個別に準備し配合するという態様以外に、Ｂ成分の特徴的構成である前記式（１）で表される構造単位、および、Ｃ成分の特徴的構成である前記式（２）で表される構造単位の双方を備えた化合物を用いてもよい。このような化合物は、例えば、上記アリル化フェノール樹脂（Ｂ成分）を準備し、このアリル化フェノール樹脂（Ｂ成分）におけるアリル基を異性化させて、フェノール性水酸基のオルト位やパラ位に、１−プロペニル基を結合させる際の反応効率を調整することにより得ることができる。 In addition to the aspect in which the B component and the C component are separately prepared and blended as described above, the structural unit represented by the formula (1), which is a characteristic configuration of the B component, and the C component A compound having both of the structural units represented by the formula (2), which is a characteristic configuration of Such a compound is prepared, for example, by preparing the allylated phenol resin (component B), isomerizing the allyl group in the allylated phenol resin (component B), and at the ortho position or para position of the phenolic hydroxyl group. It can be obtained by adjusting the reaction efficiency when the 1-propenyl group is bonded.
そして、上記Ａ成分，Ｂ成分およびＣ成分の配合割合は、下記の条件（ｘ），（ｚ）を満たすように設定する必要がある。 The blending ratio of the A component, B component, and C component needs to be set so as to satisfy the following conditions (x) and (z).
〈条件（ｘ）〉
上記Ｂ成分中に含まれるアリル基の合計モル量（ｂ）と、上記Ｃ成分中に含まれる１−プロペニル基の合計モル量（ｃ）の比（ｂ：ｃ）を、ｂ：ｃ＝９５：５〜５０：５０とする必要がある。特に好ましくはｂ：ｃ＝９２：８〜６０：４０である。すなわち、上記両者の比が上記範囲を外れると、硬化性に劣り成形性が低下するからである。より詳しくは、上記範囲を外れアリル基の合計モル量（ｂ）の比が大きすぎると、硬化性が低下することとなり、アリル基の合計モル量（ｂ）の比が小さすぎると、混練性が低下するからである。
<Condition (x)>
The ratio (b: c) of the total molar amount (b) of the allyl group contained in the B component and the total molar amount (c) of the 1-propenyl group contained in the C component is expressed as b: c = 95. : 5 to 50:50 is required. Particularly preferably, b: c = 92: 8 to 60:40. That is, if the ratio between the two is out of the above range, the curability is poor and the moldability is lowered. More specifically, if the ratio of the total molar amount (b) of the allyl group is too large outside the above range, the curability is lowered, and if the ratio of the total molar amount (b) of the allyl group is too small, the kneadability is reduced. This is because of a decrease.
〈条件（ｚ）〉
上記Ｂ成分中に含まれるアリル基および上記Ｃ成分中に含まれる１−プロペニル基の合計モル量（ｂｃ）と、上記（Ａ）成分中に含まれるマレイミド基の合計モル量（ａ）の比（ｂｃ：ａ）を、ｂｃ：ａ＝１５：８５〜７５：２５とする必要がある。特に好ましくはｂｃ：ａ＝２５：７５〜５５：４５である。すなわち、上記両者の比が上記範囲を外れると、硬化性に劣り成形性が低下するからである。より詳しくは、上記範囲を外れマレイミド基の合計モル量（ａ）が小さすぎると、硬化性が低下し、またマレイミド基の合計モル量（ａ）が大きすぎても、硬化性が低下するからである。
<Condition (z)>
Ratio of the total molar amount (bc) of the allyl group contained in the B component and the 1-propenyl group contained in the C component and the total molar amount (a) of the maleimide group contained in the (A) component. It is necessary to set (bc: a) to bc: a = 15: 85 to 75:25. Most preferably, it is bc: a = 25: 75-55: 45. That is, if the ratio between the two is out of the above range, the curability is poor and the moldability is lowered. More specifically, if the total molar amount (a) of the maleimide group is too small outside the above range, the curability is lowered, and if the total molar amount (a) of the maleimide group is too large, the curability is lowered. It is.
〈Ｄ：無機質充填剤〉
上記Ａ〜Ｃ成分とともに用いられる無機質充填剤（Ｄ成分）としては、例えば、石英ガラス、タルク、シリカ粉末（溶融シリカ粉末や結晶性シリカ粉末等）、アルミナ粉末、窒化アルミニウム粉末、窒化珪素粉末等の各種粉末があげられる。これら無機質充填剤は、破砕状、球状、あるいは摩砕処理したもの等いずれのものでも使用可能である。そして、これら無機質充填剤は単独でもしくは２種以上併せて用いられる。なかでも、得られる熱硬化性樹脂組成物の硬化体の熱線膨張係数が低減することにより内部応力を低減することができ、その結果、封止後の基板の反りを抑制することができるという点から、上記シリカ粉末を用いることが好ましく、上記シリカ粉末の中でも溶融シリカ粉末を用いることが、高充填性、高流動性という点から特に好ましい。上記溶融シリカ粉末としては、球状溶融シリカ粉末、破砕溶融シリカ粉末があげられるが、流動性という観点から、球状溶融シリカ粉末を用いることが好ましい。
<D: Inorganic filler>
Examples of the inorganic filler (D component) used together with the components A to C include quartz glass, talc, silica powder (such as fused silica powder and crystalline silica powder), alumina powder, aluminum nitride powder, and silicon nitride powder. Various powders. These inorganic fillers can be used in any form such as crushed, spherical, or ground. And these inorganic fillers are used individually or in combination of 2 or more types. Among them, the internal stress can be reduced by reducing the thermal linear expansion coefficient of the cured body of the obtained thermosetting resin composition, and as a result, warping of the substrate after sealing can be suppressed. Therefore, it is preferable to use the above silica powder, and it is particularly preferable to use a fused silica powder among the above silica powders in terms of high filling property and high fluidity. Examples of the fused silica powder include spherical fused silica powder and crushed fused silica powder. From the viewpoint of fluidity, spherical fused silica powder is preferably used.
また、無機質充填剤（Ｄ成分）の平均粒子径は、１〜５０μｍの範囲であることが好ましく、特に好ましくは２〜４０μｍの範囲のものである。なお、上記無機質充填剤（Ｄ成分）の平均粒子径は、例えば、母集団から任意の測定試料を取り出し、市販のレーザー回折散乱式粒度分布測定装置を用いて測定することができる。 The average particle size of the inorganic filler (D component) is preferably in the range of 1 to 50 μm, particularly preferably in the range of 2 to 40 μm. In addition, the average particle diameter of the said inorganic filler (D component) can take out arbitrary measurement samples from a population, for example, and can measure it using a commercially available laser diffraction scattering type particle size distribution measuring apparatus.
そして、上記無機質充填剤（Ｄ成分）の含有量は、熱硬化性樹脂組成物全体の５５〜９３重量％の範囲に設定される〔条件（ｙ）〕。特に好ましくは６５〜９０重量％である。すなわち、無機質充填剤（Ｄ成分）の含有量が少なすぎると、耐熱性が低下する傾向がみられる。一方、無機質充填剤（Ｄ成分）の含有量が多すぎると、流動性が低下して成形性に劣る傾向がみられるからである。 And content of the said inorganic filler (D component) is set to the range of 55 to 93 weight% of the whole thermosetting resin composition [condition (y)]. Particularly preferred is 65 to 90% by weight. That is, when there is too little content of an inorganic filler (D component), the heat resistance tends to be lowered. On the other hand, when there is too much content of an inorganic filler (D component), fluidity | liquidity falls and the tendency to be inferior to a moldability is seen.
〈各種添加剤〉
また、本発明の熱硬化性樹脂組成物には、上記Ａ〜Ｄ成分以外に、必要に応じて、上記熱硬化性樹脂組成物の機能を損なわない範囲で各種添加剤を配合することができる。例えば、離型剤、カップリング剤、ハイドロタルサイト類化合物等のイオン捕捉剤、難燃剤、酸化防止剤、低応力化剤、流動性付与剤、着色剤、顔料等があげられる。
<Various additives>
Moreover, in the thermosetting resin composition of this invention, various additives can be mix | blended in the range which does not impair the function of the said thermosetting resin composition as needed other than said AD component. . For example, a release agent, a coupling agent, an ion scavenger such as a hydrotalcite compound, a flame retardant, an antioxidant, a low stress agent, a fluidity imparting agent, a colorant, a pigment, and the like can be given.
上記離型剤としては、高級脂肪酸、高級脂肪酸エステル、高級脂肪酸カルシウム等の化合物があげられ、例えば、カルナバワックスや酸化ポリエチレン系ワックス等が用いられ、これらは単独でもしくは２種以上併せて用いられる。 Examples of the mold release agent include compounds such as higher fatty acids, higher fatty acid esters, higher fatty acid calcium, and the like. For example, carnauba wax and polyethylene oxide wax are used, and these are used alone or in combination of two or more. .
上記カップリング剤としては、３−グリシドキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン等の各種カップリング剤を適宜用いることができる。 As the coupling agent, various coupling agents such as 3-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane can be appropriately used.
上記難燃剤としては、有機リン系化合物、酸化アンチモン、水酸化アルミニウムや水酸化マグネシウム等の金属水酸化物等があげられる。これらは単独でもしくは２種以上併せて用いられる。 Examples of the flame retardant include organic phosphorus compounds, antimony oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and the like. These may be used alone or in combination of two or more.
上記顔料には、静電除去効果を有するカーボンブラック等を用いることができる。 As the pigment, carbon black having an electrostatic removal effect can be used.
〈熱硬化性樹脂組成物〉
本発明の熱硬化性樹脂組成物は、例えば、つぎのようにして製造することができる。すなわち、上記Ａ〜Ｄ成分、さらに必要に応じて他の添加剤を常法に準じて適宜配合し、混練機にかけ加熱状態で溶融混練する。ついで、これを室温下にて冷却固化させた後、公知の手段によって粉砕し、必要に応じてタブレット等に打錠するという一連の工程を経由することにより目的とする熱硬化性樹脂組成物を製造することができる。
<Thermosetting resin composition>
The thermosetting resin composition of the present invention can be produced, for example, as follows. That is, the above-mentioned components A to D and further other additives as necessary are appropriately blended according to a conventional method, and are melt-kneaded in a heated state in a kneader. Next, after cooling and solidifying this at room temperature, the desired thermosetting resin composition is obtained by going through a series of steps such as pulverization by known means and tableting into tablets or the like as necessary. Can be manufactured.
〈半導体装置〉
このようにして得られる熱硬化性樹脂組成物を用いての半導体素子の封止方法は、例えば、通常のトランスファー成形等の公知のモールド方法により行うことができ、半導体装置化することができる。また、上記打錠工程を経由せず、粉砕して顆粒状態のパウダーにしたものを、圧縮成形のモールド方法に適用することも可能である。このようにして得られる半導体装置としては、ＩＣやＬＳＩ等の半導体装置等があげられる。そして、本発明の熱硬化性樹脂組成物を用いての半導体素子の樹脂封止の際には、つぎのような成形条件に設定することが好ましい。まず、１段階目の反応工程として１６０〜２００℃の加熱にて加熱硬化反応を生起させ、２段階目の反応工程として最終的に上記一段階目の加熱温度条件よりも高い設定となるよう１６０〜２８０℃の加熱にて加熱硬化させる。このようにして、本発明の熱硬化性樹脂組成物を用いて半導体素子を樹脂封止することにより半導体装置を製造することができる。
<Semiconductor device>
The semiconductor element sealing method using the thermosetting resin composition thus obtained can be performed by a known molding method such as normal transfer molding, for example, and a semiconductor device can be obtained. Moreover, it is also possible to apply what was pulverized and granulated powder without going through the tableting step to a compression molding method. Examples of the semiconductor device thus obtained include semiconductor devices such as IC and LSI. And when resin-sealing a semiconductor element using the thermosetting resin composition of the present invention, it is preferable to set the following molding conditions. First, a heat curing reaction is caused by heating at 160 to 200 ° C. as the first-stage reaction process, and the second-stage reaction process is finally set to be higher than the first-stage heating temperature condition 160. It is cured by heating at ~ 280 ° C. Thus, a semiconductor device can be manufactured by resin-sealing a semiconductor element using the thermosetting resin composition of the present invention.
本発明の熱硬化性樹脂組成物の硬化物を作製する場合、上記トランスファー成形の他に、シート成形、コンプレッション成形、スクリーン印刷、ディスベンション成形等の成形方法があげられる。 When producing the cured product of the thermosetting resin composition of the present invention, in addition to the transfer molding, there are molding methods such as sheet molding, compression molding, screen printing, and displacement molding.
本発明の熱硬化性樹脂組成物を用いて硬化反応により得られる硬化物は、耐熱性に特に優れることから、各種電子部品、例えば、半導体封止材料以外に、プリント配線板用積層板およびプリント配線板、半導体搭載モジュール等の電子材料等にも好適に用いられる。 Since the cured product obtained by the curing reaction using the thermosetting resin composition of the present invention is particularly excellent in heat resistance, in addition to various electronic components, for example, semiconductor encapsulating materials, laminated boards for printed wiring boards and printed boards It is also suitably used for electronic materials such as wiring boards and semiconductor-mounted modules.
つぎに、実施例について比較例と併せて説明する。ただし、本発明は、これら実施例に限定されるものではない。なお、例中、「部」、「％」とあるのは、断りのない限り重量基準を意味する。 Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples. In the examples, “parts” and “%” mean weight basis unless otherwise specified.
まず、熱硬化性樹脂組成物の作製に先立って各種成分を準備した。 First, various components were prepared prior to preparation of the thermosetting resin composition.
〔マレイミド化合物ａ１（Ａ成分）〕
２，２−ビス〔４−（４−マレイミドフェノキシ）フェニル〕プロパン（大和化成工業社製、ＢＭＩ−４０００）
[Maleimide compound a1 (component A)]
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo, BMI-4000)
〔マレイミド化合物ａ２（Ａ成分）〕
ビス（４−マレイミドフェニル）メタン（大和化成工業社製、ＢＭＩ−１１００）
[Maleimide compound a2 (component A)]
Bis (4-maleimidophenyl) methane (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-1100)
〔マレイミド化合物ａ３（Ａ成分）〕
下記に示す構造式（ａ３）で表されるマレイミド化合物（大和化成工業社製、ＢＭＩ−２３００）
Maleimide compound represented by structural formula (a3) shown below (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300)
〔アリル化合物ｂ１（Ｂ成分）〕
フェノール（和光純薬工業社製）１３０部、３７％ホルマリン（東京化成工業社製）９２部、蒸留水１３部、シュウ酸二水和物（関東化学社製）２部を混合し、９０分還流加熱した。これに、水３００部を加えて撹拌し、冷却した後に水層を分離した。ついで、１５０℃にて水を減圧留去し、放冷してフェノール樹脂ｂ１を得た。得られたフェノール樹脂ｂ１の数平均分子量についてＧＰＣを用い前述の方法により求めたところ、３１８（ｇ／ｍｏｌ）であった。
[Allyl compound b1 (component B)]
Mix 130 parts of phenol (manufactured by Wako Pure Chemical Industries), 92 parts of 37% formalin (manufactured by Tokyo Chemical Industry Co., Ltd.), 13 parts of distilled water and 2 parts of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) for 90 minutes. Heated to reflux. To this, 300 parts of water was added and stirred, and after cooling, the aqueous layer was separated. Subsequently, water was distilled off under reduced pressure at 150 ° C. and allowed to cool to obtain a phenol resin b1. It was 318 (g / mol) when it calculated | required by the above-mentioned method about the number average molecular weight of the obtained phenol resin b1 using GPC.
上記のようにして得られたフェノール樹脂ｂ１を３１８部とし、これに臭化アリル（東京化成工業社製）４００部、炭酸カリウム（和光純薬工業社製）４６０部、アセトン（和光純薬工業社製）５００部を混合し、窒素ガス気流下、２４時間加熱還流した。放冷後、濾過、濃縮して残渣に酢酸エチル（和光純薬工業社製）４００部を加え、５％塩酸（和光純薬工業社製を蒸留水で希釈したもの）２００部で１回、各２００部の蒸留水で２回洗浄した。その後、有機層を分離し、硫酸マグネシウム（和光純薬工業社製）で乾燥させた後、濾過、濃縮してアリルエーテル化フェノール樹脂ｂ１を得た。 The phenolic resin b1 obtained as described above was made 318 parts, and 400 parts of allyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 460 parts of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), acetone (Wako Pure Chemical Industries, Ltd.) 500 parts) was mixed and heated under reflux for 24 hours under a nitrogen gas stream. After standing to cool, it was filtered and concentrated, and 400 parts of ethyl acetate (manufactured by Wako Pure Chemical Industries) was added to the residue, and once with 200 parts of 5% hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd. diluted with distilled water), Washed twice with 200 parts each of distilled water. Thereafter, the organic layer was separated, dried over magnesium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.), filtered and concentrated to obtain an allyl etherified phenol resin b1.
上記のようにして得られたアリルエーテル化フェノール樹脂ｂ１を窒素ガス気流下、２００℃で２４時間加熱撹拌することにより、目的とするアリル化合物ｂ１〔前記式（１）で表される構造単位を有するアリル化フェノール樹脂〕を得た。得られたアリル化合物ｂ１の数平均分子量についてＧＰＣを用い前述の方法により求めたところ、４４０（ｇ／ｍｏｌ）であった。 The allyl etherified phenol resin b1 obtained as described above is heated and stirred at 200 ° C. for 24 hours under a nitrogen gas stream, whereby the target allyl compound b1 [the structural unit represented by the above formula (1) is represented. Having an allylated phenol resin]. It was 440 (g / mol) when it calculated | required by the above-mentioned method about the number average molecular weight of the obtained allyl compound b1 using GPC.
〔アリル化合物ｂ２（Ｂ成分）〕
ｏ，ｏ′−ジアリルビスフェノールＡ（大和化成工業社製、ＤＡＢＰＡ、数平均分子量３０８ｇ／ｍｏｌ）
[Allyl compound b2 (component B)]
o, o′-diallylbisphenol A (Daiwa Chemical Industries, DABPA, number average molecular weight 308 g / mol)
〔アリル化合物ｂ３（Ｂ成分）〕
上記アリル化合物ｂ１の合成方法において、３７％ホルマリンの混合量を１１５部に変えた。このようにしてフェノール樹脂ｂ３を得た。得られたフェノール樹脂ｂ３の数平均分子量についてＧＰＣを用い前述の方法により求めたところ、８３６（ｇ／ｍｏｌ）であった。
[Allyl compound b3 (component B)]
In the synthesis method of allyl compound b1, the mixed amount of 37% formalin was changed to 115 parts. Thus, phenol resin b3 was obtained. It was 836 (g / mol) when the number average molecular weight of obtained phenol resin b3 was calculated | required by the above-mentioned method using GPC.
上記のようにして得られたフェノール樹脂ｂ３を９０部とし、これに臭化アリル（東京化成工業社製）１１５部、炭酸カリウム（和光純薬工業社製）１３０部、アセトン（和光純薬工業社製）１５０部を混合し、窒素ガス気流下、２４時間加熱還流した。放冷後、濾過、濃縮して残渣に酢酸エチル（和光純薬工業社製）１２０部を加え、５％塩酸（和光純薬工業社製を蒸留水で希釈したもの）６０部で１回、各６０部の蒸留水で２回洗浄した。その後、有機層を分離し、硫酸マグネシウム（和光純薬工業社製）で乾燥させた後、濾過、濃縮してアリルエーテル化フェノール樹脂ｂ３を得た。 The phenol resin b3 obtained as described above is 90 parts, and 115 parts of allyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 130 parts of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), acetone (Wako Pure Chemical Industries, Ltd.) 150 parts) were mixed and heated under reflux for 24 hours under a nitrogen gas stream. After standing to cool, it was filtered and concentrated, and 120 parts of ethyl acetate (manufactured by Wako Pure Chemical Industries) was added to the residue, and once with 60 parts of 5% hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd. diluted with distilled water) Washed twice with 60 parts each of distilled water. Thereafter, the organic layer was separated, dried over magnesium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.), filtered and concentrated to obtain an allyl etherified phenol resin b3.
上記のようにして得られたアリルエーテル化フェノール樹脂ｂ３を窒素ガス気流下、２００℃で２４時間加熱撹拌することにより、目的とするアリル化合物ｂ３〔前記式（１）で表される構造単位を有するアリル化フェノール樹脂〕を得た。得られたアリル化合物ｂ３の数平均分子量についてＧＰＣを用い前述の方法により求めたところ、１１００（ｇ／ｍｏｌ）であった。 The allyl etherified phenol resin b3 obtained as described above is heated and stirred at 200 ° C. for 24 hours under a nitrogen gas stream, whereby the target allyl compound b3 [the structural unit represented by the above formula (1) is obtained. Having an allylated phenol resin]. It was 1100 (g / mol) when the number average molecular weight of obtained allyl compound b3 was calculated | required by the above-mentioned method using GPC.
〔１−プロペニル基を有する化合物（Ｃ成分）〕
上記で得られたアリル化合物ｂ１を１１０部、水酸化カリウム（和光純薬工業社製）１００部、メタノール（和光純薬工業社製）１５０部、ｎ−ブタノール（和光純薬工業社製）を混合した後、加熱することによってメタノールを除去し、１２０℃で６時間還流させた。放冷後、メチルイソブチルケトン（和光純薬工業社製）５００部を加え、各２５０部の１０％塩酸（和光純薬工業社製を蒸留水で希釈したもの）で３回、各２００部の蒸留水で３回洗浄した。その後、有機層を分離し、硫酸マグネシウム（和光純薬工業社製）で乾燥させた後、濾過、濃縮することにより１−プロペニル基を有する化合物〔前記式（２）で表される構造単位（Ｘ＝−Ｈ）を有する化合物〕を得た。
[Compound having 1-propenyl group (component C)]
110 parts of the allyl compound b1 obtained above, 100 parts of potassium hydroxide (manufactured by Wako Pure Chemical Industries), 150 parts of methanol (manufactured by Wako Pure Chemical Industries), n-butanol (manufactured by Wako Pure Chemical Industries) After mixing, methanol was removed by heating and refluxed at 120 ° C. for 6 hours. After standing to cool, 500 parts of methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and each 250 parts of 10% hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd. diluted with distilled water) 3 times, 200 parts of each Washed 3 times with distilled water. Thereafter, the organic layer is separated, dried over magnesium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.), filtered and concentrated to obtain a compound having a 1-propenyl group [the structural unit represented by the above formula (2) ( Compound having X = -H) was obtained.
〔無機質充填剤（Ｄ成分）〕
溶融球状シリカ粉末（平均粒子径２０μｍ）
[Inorganic filler (D component)]
Fused spherical silica powder (average particle size 20μm)
〔離型剤１〕
カルナバワックス
[Release agent 1]
Carnauba wax
〔離型剤２〕
酸化ポリエチレンワックス（クラリアント社製、ＰＥＤ５２１）
[Release agent 2]
Oxidized polyethylene wax (manufactured by Clariant, PED521)
〔カップリング剤〕
３−グリシドキシプロピルトリメトキシシラン（信越化学工業社製、ＫＢＭ−４０３）
[Coupling agent]
3-Glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-403)
〔イオン捕捉剤〕
ハイドロタルサイト類化合物（協和化学工業社製、ＤＨＴ−４Ａ）
(Ion scavenger)
Hydrotalcite compound (Kyowa Chemical Industry Co., Ltd., DHT-4A)
〔Ａ〜Ｃ成分の各官能基のモル数〕
Ａ〜Ｃ成分の各官能基（マレイミド基、アリル基、１−プロペニル基）の各モル数を、下記の式により算出した。
各官能基のモル数＝使用した各成分の添加量／各官能基当量
[Number of moles of each functional group of components A to C]
The number of moles of each functional group (maleimide group, allyl group, 1-propenyl group) of the A to C components was calculated by the following formula.
Number of moles of each functional group = added amount of each component used / each functional group equivalent
なお、上記各官能基（マレイミド基、アリル基、１−プロペニル基）当量は、下記のようにして定めた。その結果（各官能基当量）を後記の表１にまとめて示す。 In addition, each said functional group (maleimide group, allyl group, 1-propenyl group) equivalent was defined as follows. The results (each functional group equivalent) are shown in Table 1 below.
〔マレイミド基当量〕
マレイミド化合物ａ１，ａ２の各マレイミド基当量は、各々の分子量を２で除した値である（すなわち、マレイミド化合物ａ１，ａ２は各々マレイミド基を２個有する構造であるため）。また、マレイミド化合物ａ３のマレイミド基当量は、大和化成工業社製の商品カタログの値を採用した（繰り返し単位を有する構造のため）。
[Maleimide group equivalent]
Each maleimide group equivalent of maleimide compounds a1 and a2 is a value obtained by dividing each molecular weight by 2 (that is, maleimide compounds a1 and a2 each have a structure having two maleimide groups). Moreover, the value of the product catalog made by Daiwa Kasei Kogyo Co., Ltd. was adopted for the maleimide group equivalent of the maleimide compound a3 (because of the structure having a repeating unit).
〔不飽和基（アリル基、１−プロペニル基）当量〕
アリル化合物ｂ２のアリル基当量は、分子量を２で除した値である（すなわち、アリル化合物ｂ２はアリル基を２個有する構造であるため）。また、アリル化合物ｂ１，ｂ３の各アリル基当量、および、１−プロペニル基を有する化合物の１−プロペニル基当量は、ＪＩＳ Ｋ６２３５の方法に準じて決定した。
[Unsaturated group (allyl group, 1-propenyl group) equivalent]
The allyl group equivalent of the allyl compound b2 is a value obtained by dividing the molecular weight by 2 (that is, the allyl compound b2 has a structure having two allyl groups). The allyl group equivalents of allyl compounds b1 and b3 and the 1-propenyl group equivalent of the compound having a 1-propenyl group were determined according to the method of JIS K6235.
〔実施例１〜１６、比較例１〜６〕
後記の表２〜表５に示す各成分を同表に示す割合で、東洋精機社製のラボプラストミル（４Ｃ１５０−０１）を用い、条件：１１０℃×回転数５０ｒｐｍにて１０分間混練を行うことにより混練物（熱硬化性樹脂組成物）を得た。
[Examples 1-16, Comparative Examples 1-6]
Kneading is carried out for 10 minutes under the conditions: 110 ° C. × rotation speed 50 rpm using a lab plast mill (4C150-01) manufactured by Toyo Seiki Co., Ltd. at the ratio shown in Table 2 to Table 5 below. As a result, a kneaded product (thermosetting resin composition) was obtained.
このようにして得られた実施例品および比較例品を用い、下記に示す方法に従って、特性を測定・評価した。これらの結果を後記の表２〜表５に併せて示す。 Using the example product and the comparative product thus obtained, the characteristics were measured and evaluated according to the methods described below. These results are also shown in Tables 2 to 5 below.
〔混練性〕
上記混練を行った際に、トルクが低い値で安定して混練できたものを◎、トルクが高いものの混練できたものを○、トルクが不安定で混練できなかったものを×として評価した。
[Kneadability]
When the above kneading was carried out, the case where the torque was stable and kneaded at a low value was evaluated as ◎, the case where the torque was high but kneaded was evaluated as ○, and the case where the torque was unstable and could not be kneaded was evaluated as x.
〔流動性・硬化性〕
上記混練したサンプルを粉砕機にかけ、さらに打錠することによりタブレットを作製した。このタブレットをトランスファー成形機に投入し、流路長１８ｃｍ×流路厚み１ｍｍの金型を用い、１７５℃で所定の時間圧力をかけることにより硬化体を成形した。後記の表２〜表５中の流動性評価は、１０個のサンプルをトランスファー成形した中で問題なく綺麗に成形できたサンプルの個数(１０個中)を示した。
[Fluidity / Curability]
The kneaded sample was put into a pulverizer and further tableted to prepare a tablet. This tablet was put into a transfer molding machine, and a cured body was molded by applying pressure at 175 ° C. for a predetermined time using a mold having a channel length of 18 cm and a channel thickness of 1 mm. The fluidity evaluations in Tables 2 to 5 below indicate the number of samples (out of 10) that could be molded beautifully without any problems during transfer molding of 10 samples.
また、表２〜表５中の硬化性評価は、６分以内に硬化してサンプルが成形できたものを◎、６分を超えて１２分以下で硬化してサンプルが成形できたものを○、１２分以内に硬化しなかったものを×として評価した。 The evaluations of curability in Tables 2 to 5 are ◎ for samples that were cured within 6 minutes and samples were molded, and those that were cured for over 12 minutes and less than 12 minutes were ○ Those that did not cure within 12 minutes were evaluated as x.
〔ゲル化時間〕
ＪＩＳ Ｋ６９１０に記載のＢ法に従い、１７５℃にて測定した。
[Gelification time]
The measurement was performed at 175 ° C. according to the method B described in JIS K6910.
〔重量変化〕
上述のトランスファー成形により、直径５０ｍｍ×厚み１ｍｍの円板（硬化物）を作製した。この円板をさらに１７５℃で５時間、２００℃で５時間、２５０℃で１０時間硬化させ、耐熱性評価サンプルとした。このサンプルを２５０℃にて１０００時間放置した前後の重量変化にて長期耐熱性を評価した。
[Change in weight]
A disk (cured product) having a diameter of 50 mm and a thickness of 1 mm was produced by the transfer molding described above. This disk was further cured at 175 ° C. for 5 hours, 200 ° C. for 5 hours, and 250 ° C. for 10 hours to obtain a heat resistance evaluation sample. The long-term heat resistance was evaluated by the weight change before and after leaving this sample at 250 ° C. for 1000 hours.
上記結果から、実施例品は、混練性，流動性および硬化性に優れ、かつ長期耐熱性に優れていることがわかる。中でも、実施例２〜６、８、１０〜１１に関しては、混練性，流動性，硬化性の全てにおいて特に優れた評価結果が得られており、ゲル化時間に関しても特に問題の生じない測定結果であった。しかも、重量変化も小さく長期耐熱性にも優れたものであった。 From the above results, it can be seen that the example products are excellent in kneadability, fluidity and curability, and excellent in long-term heat resistance. Among them, regarding Examples 2 to 6, 8, and 10 to 11, particularly excellent evaluation results were obtained in all of kneadability, fluidity, and curability, and measurement results that did not cause any particular problems with respect to gelation time. Met. Moreover, the weight change was small and the long-term heat resistance was excellent.
これに対して、条件（ｘ）の範囲を外れ、（Ｂ）成分中に含まれるアリル基の合計モル量（ｂ）と（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｃ）の比（ｂ：ｃ）がｂ：ｃ＝９７：３となる配合割合に設定された比較例１品は、硬化性に劣ることとなり、硬化しなかった。 On the other hand, out of the range of the condition (x), the total molar amount (b) of the allyl group contained in the component (B) and the total molar amount of the 1-propenyl group contained in the component (C) (c ) Ratio (b: c) was set at a blending ratio of b: c = 97: 3, the product of Comparative Example 1 was inferior in curability and did not cure.
また、条件（ｘ）の範囲を外れ、（Ｂ）成分中に含まれるアリル基の合計モル量（ｂ）と（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｃ）の比（ｂ：ｃ）がｂ：ｃ＝４０：６０となる配合割合に設定された比較例２品は、混練性，流動性に劣り、ゲル化時間も１０秒以下であることから、トランスファー成形にてサンプルを成形することができなかった。 Further, the ratio of the total molar amount (b) of the allyl group contained in the component (B) and the total molar amount (c) of the 1-propenyl group contained in the component (C) is out of the range of the condition (x). The comparative example 2 product in which (b: c) is set to a blending ratio of b: c = 40: 60 is inferior in kneadability and fluidity, and has a gelation time of 10 seconds or less. The sample could not be molded.
そして、無機質充填剤（Ｄ成分）の含有量が条件（ｙ）を超えて９５重量％となる配合割合に設定された比較例３品は、混練性に劣り、トランスファー成形にてサンプルを成形することができなかった。 And the comparative example 3 goods set to the mixture ratio from which content of an inorganic filler (D component) exceeds condition (y) and will be 95 weight% are inferior in kneadability, and shape | mold a sample by transfer molding. I couldn't.
さらに、条件（ｚ）の範囲を外れ、（Ｂ）成分中に含まれるアリル基および（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｂｃ）と、（Ａ）成分中に含まれるマレイミド基の合計モル量（ａ）の比（ｂｃ：ａ）がｂｃ：ａ＝８０：２０となる配合割合に設定された比較例４品は、硬化性に劣ることとなり、硬化しなかった。 Further, out of the range of the condition (z), the total molar amount (bc) of the allyl group contained in the component (B) and the 1-propenyl group contained in the component (C), and contained in the component (A) The four comparative examples in which the ratio (bc: a) of the total molar amount (a) of maleimide groups to be set to bc: a = 80: 20 was inferior in curability and did not cure. .
また、無機質充填剤（Ｄ成分）の含有量が条件（ｙ）を外れ５５重量％未満となる配合割合に設定された比較例５品は、耐熱性に劣ることとなった。 Moreover, the comparative example 5 product in which the content of the inorganic filler (component D) was set to a blending ratio that deviated from the condition (y) and was less than 55% by weight was inferior in heat resistance.
そして、条件（ｚ）の範囲を外れ、（Ｂ）成分中に含まれるアリル基および（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｂｃ）と、（Ａ）成分中に含まれるマレイミド基の合計モル量（ａ）の比（ｂｃ：ａ）がｂｃ：ａ＝１０：９０となる配合割合に設定された比較例６品は、硬化性に劣ることとなり、硬化しなかった。 Then, out of the range of the condition (z), the total molar amount (bc) of the allyl group contained in the component (B) and the 1-propenyl group contained in the component (C), and contained in the component (A) 6 products of Comparative Example in which the ratio (bc: a) of the total molar amount (a) of maleimide groups to be set to bc: a = 10: 90 was inferior in curability and did not cure. .
本発明の半導体封止用熱硬化性樹脂組成物は、トランスファー成形による樹脂封止が可能であり、工業生産性に適用した、高耐熱性を備えた半導体素子用の封止材料である。 The thermosetting resin composition for semiconductor encapsulation of the present invention can be encapsulated by transfer molding, and is a sealing material for semiconductor elements having high heat resistance applied to industrial productivity.
Claims (6)
（Ａ）１分子中に２個以上のマレイミド基を有するマレイミド化合物。
（Ｂ）下記の式（１）で表される構造単位を含有するアリル化フェノール樹脂。
（ｘ）上記（Ｂ）成分中に含まれるアリル基の合計モル量（ｂ）と、上記（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｃ）の比（ｂ：ｃ）が、ｂ：ｃ＝９５：５〜５０：５０である。
（ｙ）上記（Ｄ）成分の含有量が、熱硬化性樹脂組成物全体の５５〜９３重量％である。
（ｚ）上記（Ｂ）成分中に含まれるアリル基および上記（Ｃ）成分中に含まれる１−プロペニル基の合計モル量（ｂｃ）と、上記（Ａ）成分中に含まれるマレイミド基の合計モル量（ａ）の比（ｂｃ：ａ）が、ｂｃ：ａ＝１５：８５〜７５：２５である。 A thermosetting resin composition for semiconductor encapsulation containing the following components (A) to (D), which satisfies the following conditions (x) to (z): Resin composition.
(A) A maleimide compound having two or more maleimide groups in one molecule.
(B) An allylated phenol resin containing a structural unit represented by the following formula (1).
(X) Ratio (b: c) of the total molar amount (b) of allyl groups contained in the component (B) and the total molar amount (c) of 1-propenyl groups contained in the component (C) However, it is b: c = 95: 5-50: 50.
(Y) Content of the said (D) component is 55 to 93 weight% of the whole thermosetting resin composition.
(Z) The total molar amount (bc) of the allyl group contained in the component (B) and the 1-propenyl group contained in the component (C), and the sum of the maleimide groups contained in the component (A) The molar amount (a) ratio (bc: a) is bc: a = 15: 85-75: 25.
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| US10689493B2 (en) | 2014-12-25 | 2020-06-23 | Showa Denko K.K. | Thermosetting resin composition |
| KR101900268B1 (en) * | 2014-12-25 | 2018-09-19 | 쇼와 덴코 가부시키가이샤 | Thermosetting resin composition |
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| JP6537188B2 (en) * | 2016-02-19 | 2019-07-03 | 京セラ株式会社 | Molding material for sealing and electronic component device |
| CN110225931A (en) * | 2017-04-19 | 2019-09-10 | 昭和电工株式会社 | Hardening resin composition, its solidfied material and the structural body comprising the solidfied material |
| JP6319703B1 (en) * | 2017-07-11 | 2018-05-09 | 群栄化学工業株式会社 | Propenyl group-containing resin, resin composition, resin varnish, laminate manufacturing method, thermosetting molding material and sealing material |
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| JP2570923B2 (en) * | 1991-06-07 | 1997-01-16 | 信越化学工業株式会社 | Thermosetting resin composition |
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| JPH05239155A (en) * | 1992-02-28 | 1993-09-17 | Toagosei Chem Ind Co Ltd | Low viscousity thermosetting resin composition |
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