JP2004155865A - Modified polysiloxane and curable resin composition using the same - Google Patents
Modified polysiloxane and curable resin composition using the same Download PDFInfo
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- JP2004155865A JP2004155865A JP2002321566A JP2002321566A JP2004155865A JP 2004155865 A JP2004155865 A JP 2004155865A JP 2002321566 A JP2002321566 A JP 2002321566A JP 2002321566 A JP2002321566 A JP 2002321566A JP 2004155865 A JP2004155865 A JP 2004155865A
- Authority
- JP
- Japan
- Prior art keywords
- modified polysiloxane
- group
- resin composition
- curable resin
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polysiloxane Polymers 0.000 title claims abstract description 35
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 31
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims description 20
- 229920000647 polyepoxide Polymers 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 125000004018 acid anhydride group Chemical group 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- DKFHWNGVMWFBJE-UHFFFAOYSA-N 1-ethynylcyclohexene Chemical compound C#CC1=CCCCC1 DKFHWNGVMWFBJE-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 2
- LQOPXMZSGSTGMF-UHFFFAOYSA-N 6004-79-1 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C2 LQOPXMZSGSTGMF-UHFFFAOYSA-N 0.000 description 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000005593 norbornanyl group Chemical group 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- IUFCMMBNTGYIJU-UHFFFAOYSA-N 1-ethenyl-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1CCCC2C(C=C)CCCC21 IUFCMMBNTGYIJU-UHFFFAOYSA-N 0.000 description 1
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
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- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、発光ダイオード、フォトダイオード等の光半導体の封止剤、電子部品用の接着剤、シール剤等として有用な硬化性樹脂組成物及びそれを調製する為の変性ポリシロキサンに関するものである。
【０００２】
【従来の技術】
一般に、光半導体装置は発光ダイオード、フォトダイオード等の光半導体素子をエポキシ樹脂組成物によって樹脂封止することにより構成されている。一方、近年注目されている青色ＬＥＤや白色ＬＥＤの場合、封止剤として従来のエポキシ組成物を用いると耐光性が不充分であり、短期間に輝度の低下が起こる。耐光性を向上させる手段として脂環式のエポキシ樹脂を用いる検討が、例えば特開２００１−１９７４２号公報等に開示されているが、未だ不充分であり、更なる耐光性の向上が強く求められている。
【０００３】
一方、エポキシ基を有するシリコーン樹脂を含有するエポキシ樹脂組成物を光半導体の封止剤として用いる検討が、例えば特開平６−２４０００１号公報等に開示されている。しかしながら、一般にエポキシ基を有するシリコーン樹脂はガラス転移温度が低く、それを用いた組成物で青色ＬＥＤや白色ＬＥＤを封止すると通電による発熱により封止剤が軟化すると言う課題を有し、耐熱性の向上が強く求められている。
【０００４】
【特許文献１】
特開２００１−１９７４２号公報
【特許文献２】
特開平６−２４０００１号公報
【０００５】
【発明が解決しようとする課題】
本発明は、高い耐光性と耐熱性を有する硬化物を与える変性ポリシロキサンおよび硬化性樹脂組成物を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、脂環式炭化水素基と架橋点となる置換基を特定割合で導入した変性ポリシロキサンを硬化性樹脂組成物の一成分として使用することにより、上記の目的が達成されることを見出し、本発明を完成した。
即ち、本発明は下記の通りである。
１）平均組成式（１）
【０００７】
【化４】
（但し、Ｒ１は水素基あるいは炭素数が１〜６の脂肪族炭化水素基、Ｒ２は化学式（２）あるいは化学式（３）で示される置換基、Ｒ３は炭素数が５〜２０の脂環式炭化水素基である。Ｒ４はＲ１〜Ｒ３の何れかの基である。ｘ，ｙ，ｚはそれぞれ、０≦ｘ≦５０，１≦ｙ≦５０，１≦ｚ≦５０の整数である。）
化学式（２）
【０００９】
【化５】
化学式（３）
【００１１】
【化６】
（但しＲ５は炭素数が１〜１０，酸素数が０〜２の２価の有機基）
で示される変性ポリシロキサン。
【００１３】
２）ｘ、ｙ、ｚの合計に対するｙの比率が５〜８０％である上記１）記載の変性ポリシロキサン。
３）ｘ、ｙ、ｚの合計に対するｚの比率が５〜５０％である上記１）記載の変性ポリシロキサン。
４）Ｒ３が多環脂環式炭化水素基である上記１）〜３）記載の変性ポリシロキサン。
５）上記１）〜４）に記載の変性ポリシロキサンとエポキシ樹脂用硬化剤を含有する硬化性樹脂組成物。
６）さらに芳香環を有さないエポキシ樹脂を含有する上記５）記載の硬化性樹脂組成物。
７）硬化剤が酸無水物系硬化剤である上記５），６）記載の硬化性樹脂組成物。
【００１４】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の変性ポリシロキサンは、平均組成式（１）に示す構造を有する。
【００１５】
【化７】
（但し、Ｒ１は水素基あるいは炭素数が１〜６の脂肪族炭化水素基、Ｒ２は化学式（２）あるいは化学式（３）で示される置換基、Ｒ３は炭素数が５〜２０の脂環式炭化水素基である。Ｒ４はＲ１〜Ｒ３の何れかの基である。ｘ，ｙ，ｚはそれぞれ、０≦ｘ≦５０，１≦ｙ≦５０，１≦ｚ≦５０の整数である。）
化学式（２）
【００１７】
【化８】
化学式（３）
【００１９】
【化９】
（但しＲ５は炭素数が１〜１０，酸素数が０〜２の２価の有機基）
Ｒ１は具体的には水素基、メチル基、エチル基、プロピル基、ブチル基等があげられる。好ましくはメチル基である。該置換基は１種類でも数種の混合でも良い。
Ｒ２は反応して架橋点となる置換基であり、具体的にはグリシジル基、エチニルグリシジルエーテル基、プロピレニルグリシジルエーテル基、エチニルシクロヘキセンオキシド基等があげられる。特にエチニルシクロヘキセンオキシド基が好ましい。該置換基は１種類でも数種の混合でも良い。ｙは硬化が十分にできる量あればよく２以上である事が好ましい。ｘ、ｙ、ｚの合計に対するｙの比率は好ましくは５〜８０％である。更に好ましくは１０〜６０％、一層好ましくは１５〜５０％、更に一層好ましくは２０〜４０％である。ｙの比率が５％以上有する事で、十分な低吸水性が得られ、また、硬化剤等との高い相溶性が得られる。一方、ｙの比率が８０％以下で、高い耐クラック性が得られる。
【００２１】
Ｒ３は耐熱性を付与する置換基であり、具体的には、シクロヘキシル基、ノルボルナニル基、ノルボルネニル基、ジシクロペンタジエニル基、エチニルシクロヘキサン基、エチニルシクロヘキセン基、エチニルデカヒドロナフタレン基等があげられる。特にノルボルナニル基が好ましい。該置換基は１種類でも数種の混合でも良い。ｚは耐熱性を向上させる効果が発現できる量あればよい。ｘ、ｙ、ｚの合計に対するｚの比率は好ましくは５〜５０％であり、更に好ましくは１０〜４０％一層好ましくは１５〜３０％である。ｚの比率が５％以上で高い耐熱性が得られ、一方、ｚの比率が５０％以下で、高い耐光性が得られる。
【００２２】
Ｒ５は、具体的には−ＣＨ２−、−ＣＨ２−ＣＨ２−、−Ｏ−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ２−Ｏ−、−ＣＨ２−ＣＨ２−ＣＨ２−Ｏ−等が挙げられる。
本発明の変性ポリシロキサンは従来周知の方法で合成する事ができる。具体的には、ＳｉＨ基を含有するオルガノポリシロキサンにハイドロシリレーション反応によって置換基を導入する方法、オルガノハロシラン及びオルガノアルコキシシランを単独にあるいは混合して加水分解する方法や、さらに再平衡化重合する方法、環状オルガノシロキサンを開環重合する方法等があげられる。なかでもＳｉＨ基を含有するオルガノポリシロキサンにハイドロシリレーション反応によって置換基を導入する方法が簡便であり好ましい。以下、具体的にこの方法について述べる。
【００２３】
ハイドロシリレーション反応は、必要に応じて触媒の存在下、ＳｉＨ基含有オルガノポリシロキサンに置換基となるビニル基を含有する不飽和化合物を段階的にあるいは一度に反応させる方法である。
置換基となるビニル基を含有する不飽和化合物としては以下のものが挙げられる。
反応してＲ２になる化合物としては、ビニルグリシジルエーテル、アリルグリシジルエーテル、ビニルシクロヘキセンオキシド等が挙げられる。
反応してＲ３になる化合物としては、ノルボルネン、ノルボルナジエン、ジシクロペンタジエン、ビニルシクロヘキサン、ビニルシクロヘキセン、ビニルデカヒドロナフタレン等があげられる。
反応温度は特に制限はないが、反応の速度と収率の観点から１０〜２００℃、好ましくは３０〜１５０℃、特に好ましくは、５０〜１２０℃である。反応は無溶媒下でも進行するが溶媒を使用しても良い。溶媒として、ジオキサン、メチルイソブチルケトン、トルエン、キシレン、酢酸ブチル等が使用される。
【００２４】
シロキサン骨格は本質的に耐光性を有する。しかしながら耐熱性をあげるために一般的に用いられるフェニル基を置換基として用いると、このフェニル基が耐光性を低下させてしまう。よって、これまでに耐光性と耐熱性に優れたポリシロキサンは提供されていなかった。本発明者らは、脂環式炭化水素基とエポキシ基を特定割合で導入した変性ポリシロキサンを硬化性樹脂組成物の一成分として使用することにより、上記の目的が達成されることを見出し本発明を完成した。
【００２５】
本発明で使用されるエポキシ樹脂用硬化剤は、例えば、エチレンジアミン、トリエチレンペンタミン、ヘキサメチレンジアミン、ダイマー酸変性エチレンジアミン、Ｎ−エチルアミノピペラジン、イソホロンジアミン等の脂肪族アミン類、メタフェニレンジアミン、パラフェニレンジアミン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェノルスルホン、４，４’−ジアミノジフェノルメタン、４，４’−ジアミノジフェノルエーテル等の芳香族アミン類、メルカプトプロピオン酸エステル、エポキシ樹脂の末端メルカプト化合物等のメルカプタン類、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、ビスフェノールＳ、テトラメチルビスフェノールＡ、テトラメチルビスフェノールＦ、テトラメチルビスフェノールＡＤ、テトラメチルビスフェノールＳ、テトラブロモビスフェノールＡ、テトラクロロビスフェノールＡ、テトラフルオロビスフェノールＡ、ビフェノール、ジヒドロキシナフタレン、１，１，１−トリス（４−ヒドロキシフェニル）メタン、４，４−（１−（４−（１−（４−ヒドロキシフェニル）−１−メチルエチル）フェニル）エチリデン）ビスフェノール、フェノールノボラック、クレゾールノボラック、ビスフェノールＡノボラック、臭素化フェノールノボラック、臭素化ビスフェノールＡノボラック等のフェノール樹脂類、これらフェノール樹脂類芳香環を水素化したポリオール類、ポリアゼライン酸無水物、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、５−ノルボルネン−２，３−ジカルボン酸無水物、ノルボルナン−２，３−ジカルボン酸無水物、メチル−５−ノルボルネン−２，３−ジカルボン酸無水物、メチル−ノルボルナン−２，３−ジカルボン酸無水物等の脂環式酸無水物類、無水フタル酸、無水トリメリット酸、無水ピロメリット酸等の芳香族酸無水物類、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール等のイミダゾール類およびその塩類、上記脂肪族アミン類、芳香族アミン類、及び／またはイミダゾール類とエポキシ樹脂との反応により得られるアミンアダクト類、アジピン酸ジヒドラジド等のヒドラジン類、ジメチルベンジルアミン、１，８−ジアザビシクロ［５．４．０］ウンデセン−７等の第３級アミン類、トリフェニルホスフィン等の有機ホスフィン類、ジシアンジアミド等が挙げられる。中でも酸無水物類が好ましく、より好ましくは、脂環式酸無水物類であり、特に好ましくは、メチルヘキサヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、ノルボルナン−２，３−ジカルボン酸無水物、メチル−ノルボルナン−２，３−ジカルボン酸無水物である。
【００２６】
硬化剤の使用量は変性ポリシロキサン１００部に対して、任意に選択できるが、好ましくは、０．１〜２００質量部である。より好ましくは０．２〜１００質量部である。これらの硬化剤は単独で用いても良く、２種以上を併用しても良い。
本発明の芳香環を有さないエポキシ樹脂とは、脂環式エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＦ型エポキシ樹脂等が挙げられる。芳香環を水添したエポキシ樹脂では、本質的に芳香環を有していない事が必須であり、このエポキシ樹脂の組成物への添加量にもよるが、その水添率が好ましくは９０モル％以上、さらに好ましくは９５モル％以上である。また、その添加量は本発明の変性ポリシロキサン１００質量部に対して芳香環を有さないエポキシ樹脂を好ましくは１００質量部以下であり、より好ましくは５０質量部以下である。
【００２７】
本発明の硬化性樹脂組成物は、上記成分以外に必要に応じて、硬化促進剤、染料、変性剤、変色防止剤等の従来公知の添加剤を適宜配合することができる。
硬化促進剤としては、例えば、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類、１，８−ジアザビシクロ（５，４，０）ウンデセン−７等の第３級アミン類、トリフェニルホスフィン等のホスフィン類、トリフェニルホスホニウムブロマイド等のホスホニウム塩類、アミノトリアゾール類、オクチル酸錫、ジブチル錫ジラウレート等の錫系、オクチル酸亜鉛等の亜鉛系、アルミニウム、クロム、コバルト、ジルコニウム等のアセチルアセトナート等の金属触媒類等が用いられる。これらの硬化促進剤は単独で用いても良く、２種以上を併用しても良い。
本発明のエポキシ樹脂組成物を用いての光半導体素子の封止は、特に限定されることなく、通常の注型等の公知のモールド方法により行うことができる。
【００２８】
【実施例】
本発明を実施例に基づいて説明する。
評価方法は以下の通りとする。
（１） 透過率
厚さ２ｍｍの硬化物を用いて、（株）島津製作所のＵＶ−２５００ＰＣを用いて４３０ｎｍの光透過率を測定した。
（２） 透過率保持率
厚さ２ｍｍの硬化物に、高圧水銀ランプを用いて５００時間紫外線を照射する。紫外線照射前後の４３０ｎｍの光透過率を（株）島津製作所のＵＶ−２５００ＰＣを用いて測定し、その保持率が８０％以上を○とし、６０〜８０％を△、それ以下を×とした。
（３） 耐熱性
厚さ２ｍｍの硬化物を１５０℃で１０時間保持した時に軟化しないものを○とした。
【００２９】
［合成例］
還流冷却器、温度計及び撹拌装置を有する１Ｌの反応器にメチルハイドロジェンシロキサン−ジメチルシロキサンコポリマー（旭化成ワッカーシリコーン社製：Ｖ５８）１００ｇ、ジオキサン１００ｇを入れ、撹拌下６０℃に加熱した。これにジシクロペンタジエニル白金ジクロライドの０．５質量％ジオキサン溶液を０．４５ｇ添加した後、ノルボルネン（和光純薬株式会社製：試薬特級）の２０質量％ジオキサン溶液１６５ｇを１２０分かけて滴下し、さらに６０℃で１時間撹拌を続けた。これにジシクロペンタジエニル白金ジクロライドの０．５質量％ジオキサン溶液を０．２ｇ追加添加した後、続けてビニルシクロヘキセンオキシド（ダイセル化学工業株式会社製：セロキサイド２０００）の２０質量％ジオキサン溶液２１７ｇを１２０分かけて滴下し、さらに６０℃で１時間撹拌を続けた。
この反応液を加熱減圧下、溶媒等を留去することにより本発明の変性ポリシロキサン１６８ｇを得た。なお、各ステップで反応液をサンプリングし、アルカリで分解して水素ガスの発生を確認することにより、反応が定量的に進行している事を確認した。
【００３０】
［実施例１］
合成例で得られた変性ポリシロキサンとメチルヘキサヒドロ無水フタル酸をエポキシ基と無水カルボン酸が当量となるように混合し、変性ポリシロキサンに対して０．５質量％のナフテン酸コバルトを混合し、全体が均一になるまで撹拌して硬化性樹脂組成物を得た。この組成物を深さ２ｍｍの型に流し込み、１２０℃で２時間、更に１５０℃で６時間硬化反応を行い、硬化物を得た。物性を表１に示す。
【００３１】
［実施例２］
変性ポリシロキサンに対して１０質量％の脂環式エポキシ樹脂である３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート（東京化成株式会社製）を添加し、両方のエポキシ基に対して無水カルボン酸が当量となるように混合した以外は実施例１と同様にして硬化物を得た。物性を表１に示す。
【００３２】
［比較例１］
３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートのみを用いて、このエポキシ基に対して無水カルボン酸が当量となるように混合した以外は実施例１と同様にして硬化物を得た。物性を表１に示す。
【００３３】
【表１】
【発明の効果】本発明の硬化性樹脂組成物は、エポキシ基を含有する置換基と脂環式炭化水素を含有する置換基の両方を有する変性ポリシロキサンを用いているため、耐光性に優れると共に高い耐熱性を有する。これを封止剤として用いて得られる光半導体装置は、半導体素子の特性低下が少なく信頼性が高い。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a curable resin composition useful as a sealant for optical semiconductors such as light-emitting diodes and photodiodes, an adhesive for electronic components, a sealant, and the like, and a modified polysiloxane for preparing the same. .
[0002]
[Prior art]
Generally, an optical semiconductor device is configured by resin-sealing an optical semiconductor element such as a light emitting diode and a photodiode with an epoxy resin composition. On the other hand, in the case of a blue LED or a white LED, which has been attracting attention in recent years, if a conventional epoxy composition is used as a sealant, light resistance is insufficient, and the luminance is reduced in a short time. The use of an alicyclic epoxy resin as a means for improving light resistance is disclosed in, for example, JP-A-2001-19742, but is still insufficient, and further improvement in light resistance is strongly demanded. ing.
[0003]
On the other hand, the use of an epoxy resin composition containing a silicone resin having an epoxy group as an encapsulant for an optical semiconductor is disclosed in, for example, JP-A-6-240001. However, a silicone resin having an epoxy group generally has a low glass transition temperature, and has a problem that when a blue LED or a white LED is sealed with a composition using the same, the sealing agent is softened by heat generation due to energization. There is a strong demand for improvement.
[0004]
[Patent Document 1]
JP 2001-19742 A [Patent Document 2]
JP-A-6-240001
[Problems to be solved by the invention]
An object of the present invention is to provide a modified polysiloxane and a curable resin composition that give a cured product having high light resistance and heat resistance.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, modified polysiloxane in which alicyclic hydrocarbon groups and substituents serving as crosslinking points are introduced at a specific ratio is one component of the curable resin composition. It has been found that the above object can be achieved by using the present invention, and the present invention has been completed.
That is, the present invention is as follows.
1) Average composition formula (1)
[0007]
Embedded image
(However, R 1 is a hydrogen group or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, R 2 is a substituent represented by the chemical formula (2) or (3), and R 3 is a C 5-20 carbon atom.) R 4 is any group of R 1 to R 3 , x, y, and z are respectively 0 ≦ x ≦ 50, 1 ≦ y ≦ 50, and 1 ≦ z ≦ 50. Is an integer.)
Chemical formula (2)
[0009]
Embedded image
Chemical formula (3)
[0011]
Embedded image
(However, R 5 is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen atoms)
A modified polysiloxane represented by the formula:
[0013]
2) The modified polysiloxane according to 1), wherein the ratio of y to the total of x, y, and z is 5 to 80%.
3) The modified polysiloxane according to 1), wherein the ratio of z to the total of x, y, and z is 5 to 50%.
4) The modified polysiloxane according to 1) to 3) above, wherein R 3 is a polycyclic alicyclic hydrocarbon group.
5) A curable resin composition containing the modified polysiloxane described in 1) to 4) above and a curing agent for an epoxy resin.
6) The curable resin composition according to 5), further containing an epoxy resin having no aromatic ring.
7) The curable resin composition according to 5) or 6) above, wherein the curing agent is an acid anhydride curing agent.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The modified polysiloxane of the present invention has a structure represented by the average composition formula (1).
[0015]
Embedded image
(However, R 1 is a hydrogen group or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, R 2 is a substituent represented by the chemical formula (2) or (3), and R 3 is a C 5-20 carbon atom.) R 4 is any group of R 1 to R 3 , x, y, and z are respectively 0 ≦ x ≦ 50, 1 ≦ y ≦ 50, and 1 ≦ z ≦ 50. Is an integer.)
Chemical formula (2)
[0017]
Embedded image
Chemical formula (3)
[0019]
Embedded image
(However, R 5 is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen atoms)
Specific examples of R 1 include a hydrogen group, a methyl group, an ethyl group, a propyl group, and a butyl group. Preferably it is a methyl group. The substituent may be one kind or a mixture of several kinds.
R 2 is a substituent that becomes a cross-linking point upon reaction, and specific examples thereof include a glycidyl group, an ethynyl glycidyl ether group, a propylenyl glycidyl ether group, and an ethynylcyclohexene oxide group. Particularly, an ethynylcyclohexene oxide group is preferable. The substituent may be one kind or a mixture of several kinds. It is sufficient that y is sufficient to cure, and it is preferable that y is 2 or more. The ratio of y to the sum of x, y and z is preferably from 5 to 80%. It is more preferably 10 to 60%, more preferably 15 to 50%, and still more preferably 20 to 40%. When the ratio of y is 5% or more, sufficient low water absorption is obtained, and high compatibility with a curing agent or the like is obtained. On the other hand, when the ratio of y is 80% or less, high crack resistance is obtained.
[0021]
R 3 is a substituent that imparts heat resistance, and specific examples thereof include a cyclohexyl group, a norbornanyl group, a norbornenyl group, a dicyclopentadienyl group, an ethynylcyclohexane group, an ethynylcyclohexene group, and an ethynyldecahydronaphthalene group. Can be Particularly, a norbornanyl group is preferable. The substituent may be one kind or a mixture of several kinds. z should just be the quantity which can exhibit the effect which improves heat resistance. The ratio of z to the total of x, y, and z is preferably 5 to 50%, more preferably 10 to 40%, and even more preferably 15 to 30%. When the ratio of z is 5% or more, high heat resistance is obtained. On the other hand, when the ratio of z is 50% or less, high light resistance is obtained.
[0022]
R 5 is specifically -CH 2 -, - CH 2 -CH 2 -, - O-CH 2 -CH 2 -, - CH 2 -CH 2 -O -, - CH 2 -CH 2 -CH 2 —O— and the like.
The modified polysiloxane of the present invention can be synthesized by a conventionally known method. Specifically, a method of introducing a substituent into an organopolysiloxane containing a SiH group by a hydrosilylation reaction, a method of hydrolyzing an organohalosilane and an organoalkoxysilane singly or in combination, and a method of further equilibration. Examples thereof include a method of polymerizing and a method of ring-opening polymerization of a cyclic organosiloxane. Above all, a method of introducing a substituent into an organopolysiloxane containing a SiH group by a hydrosilylation reaction is simple and preferred. Hereinafter, this method will be specifically described.
[0023]
The hydrosilylation reaction is a method in which an unsaturated compound having a vinyl group as a substituent is reacted with an SiH group-containing organopolysiloxane stepwise or at once in the presence of a catalyst, if necessary.
Examples of the unsaturated compound containing a vinyl group serving as a substituent include the following.
Examples of the compound capable of reacting with becomes R 2, vinyl glycidyl ether, allyl glycidyl ether, and vinyl cyclohexene oxide and the like.
Examples of the compound that reacts to R 3 include norbornene, norbornadiene, dicyclopentadiene, vinylcyclohexane, vinylcyclohexene, and vinyldecahydronaphthalene.
Although the reaction temperature is not particularly limited, it is 10 to 200 ° C, preferably 30 to 150 ° C, particularly preferably 50 to 120 ° C from the viewpoint of the reaction rate and the yield. The reaction proceeds even without solvent, but a solvent may be used. As the solvent, dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate and the like are used.
[0024]
The siloxane skeleton is inherently lightfast. However, when a generally used phenyl group is used as a substituent to increase heat resistance, the phenyl group lowers light resistance. Therefore, a polysiloxane excellent in light resistance and heat resistance has not been provided so far. The present inventors have found that the above object is achieved by using a modified polysiloxane in which an alicyclic hydrocarbon group and an epoxy group are introduced at a specific ratio as one component of a curable resin composition. Completed the invention.
[0025]
The curing agent for the epoxy resin used in the present invention includes, for example, ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, aliphatic amines such as isophoronediamine, metaphenylenediamine, Aromatic amines such as paraphenylenediamine, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenolsulfone, 4,4'-diaminodiphenolmethane, and 4,4'-diaminodiphenol ether , Mercapto propionates, mercaptans such as terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1 -(4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) phenolic resins such as bisphenol, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, and brominated bisphenol A novolak These phenolic resins, polyols obtained by hydrogenating aromatic rings, polyazeleic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydro Water phthalic acid, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, methyl-norbornane-2,3 Alicyclic acid anhydrides such as dicarboxylic anhydride, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, 2-methylimidazole, 2-ethyl-4-methylimidazole , 2-phenylimidazoles and other imidazoles and salts thereof, aliphatic amines, aromatic amines, and / or amine adducts obtained by reaction of imidazoles with epoxy resins, hydrazines such as adipic dihydrazide, Tertiary amines such as dimethylbenzylamine and 1,8-diazabicyclo [5.4.0] undecene-7 Organic phosphines such as triphenylphosphine, dicyandiamide, and the like. Among them, acid anhydrides are preferable, and alicyclic acid anhydrides are more preferable. Particularly preferable are methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl -Norbornane-2,3-dicarboxylic anhydride.
[0026]
The amount of the curing agent used can be arbitrarily selected with respect to 100 parts of the modified polysiloxane, but is preferably 0.1 to 200 parts by mass. More preferably, it is 0.2 to 100 parts by mass. These curing agents may be used alone or in combination of two or more.
The epoxy resin having no aromatic ring of the present invention includes an alicyclic epoxy resin, a hydrogenated bisphenol A type epoxy resin, a hydrogenated bisphenol F type epoxy resin and the like. In an epoxy resin in which an aromatic ring is hydrogenated, it is essential that the epoxy resin has essentially no aromatic ring, and the hydrogenation rate is preferably 90 mol, although it depends on the amount of the epoxy resin added to the composition. % Or more, more preferably 95 mol% or more. The amount of the epoxy resin having no aromatic ring is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the modified polysiloxane of the present invention.
[0027]
In the curable resin composition of the present invention, conventionally known additives such as a curing accelerator, a dye, a denaturant, and a discoloration inhibitor can be appropriately compounded, if necessary, in addition to the above components.
Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7; Phosphines such as phenylphosphine, phosphonium salts such as triphenylphosphonium bromide, aminotriazoles, tin-based such as tin octylate and dibutyltin dilaurate, zinc-based such as zinc octylate, and acetyl such as aluminum, chromium, cobalt, and zirconium. Metal catalysts such as acetonate are used. These curing accelerators may be used alone or in combination of two or more.
The sealing of the optical semiconductor device using the epoxy resin composition of the present invention is not particularly limited, and can be performed by a known molding method such as ordinary casting.
[0028]
【Example】
The present invention will be described based on examples.
The evaluation method is as follows.
(1) Transmittance Using a cured product having a thickness of 2 mm, the light transmittance at 430 nm was measured using UV-2500PC manufactured by Shimadzu Corporation.
(2) Transmittance retention The cured product having a thickness of 2 mm is irradiated with ultraviolet rays for 500 hours using a high-pressure mercury lamp. The light transmittance at 430 nm before and after ultraviolet irradiation was measured using a UV-2500PC manufactured by Shimadzu Corporation. The retention was evaluated as ○ when the retention was 80% or more, Δ when 60 to 80%, and × when the retention was less than 80%.
(3) Heat resistance A cured product having a thickness of 2 mm that did not soften when held at 150 ° C. for 10 hours was evaluated as ○.
[0029]
[Synthesis example]
100 g of methylhydrogensiloxane-dimethylsiloxane copolymer (V58, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and 100 g of dioxane were charged into a 1 L reactor having a reflux condenser, a thermometer and a stirrer, and heated to 60 ° C. with stirring. After adding 0.45 g of a 0.5% by mass dioxane solution of dicyclopentadienylplatinum dichloride thereto, 165 g of a 20% by mass dioxane solution of norbornene (manufactured by Wako Pure Chemical Industries, Ltd .: special grade) was added dropwise over 120 minutes. Then, stirring was further continued at 60 ° C. for 1 hour. After adding 0.2 g of a 0.5% by mass dioxane solution of dicyclopentadienylplatinum dichloride thereto, 217 g of a 20% by mass dioxane solution of vinylcyclohexene oxide (Celoxide 2000, manufactured by Daicel Chemical Industries, Ltd.) was added. The mixture was added dropwise over 120 minutes, and stirring was further continued at 60 ° C. for 1 hour.
The reaction solution was heated under reduced pressure to remove the solvent and the like, thereby obtaining 168 g of the modified polysiloxane of the present invention. In each step, the reaction solution was sampled and decomposed with an alkali to confirm generation of hydrogen gas, thereby confirming that the reaction had progressed quantitatively.
[0030]
[Example 1]
The modified polysiloxane obtained in the synthesis example and methylhexahydrophthalic anhydride are mixed so that the epoxy group and the carboxylic anhydride become equivalent, and 0.5% by mass of cobalt naphthenate is mixed with the modified polysiloxane. Then, the mixture was stirred until the whole became uniform to obtain a curable resin composition. This composition was poured into a mold having a depth of 2 mm, and a curing reaction was performed at 120 ° C. for 2 hours and further at 150 ° C. for 6 hours to obtain a cured product. Table 1 shows the physical properties.
[0031]
[Example 2]
To the modified polysiloxane, 10% by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is an alicyclic epoxy resin, was added. A cured product was obtained in the same manner as in Example 1 except that the carboxylic anhydride was mixed so as to be equivalent. Table 1 shows the physical properties.
[0032]
[Comparative Example 1]
A cured product was obtained in the same manner as in Example 1 except that only 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate was used and carboxylic anhydride was mixed with the epoxy group in an equivalent amount. Obtained. Table 1 shows the physical properties.
[0033]
[Table 1]
The curable resin composition of the present invention is excellent in light resistance because it uses a modified polysiloxane having both an epoxy group-containing substituent and an alicyclic hydrocarbon-containing substituent. Also has high heat resistance. The optical semiconductor device obtained by using this as a sealing agent has high reliability with little deterioration of the characteristics of the semiconductor element.
Claims (7)
化学式（２）
で示される変性ポリシロキサン。Average composition formula (1)
Chemical formula (2)
A modified polysiloxane represented by the formula:
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