JP2004115552A - One-pack liquid epoxy resin composition - Google Patents
One-pack liquid epoxy resin composition Download PDFInfo
- Publication number
- JP2004115552A JP2004115552A JP2002276446A JP2002276446A JP2004115552A JP 2004115552 A JP2004115552 A JP 2004115552A JP 2002276446 A JP2002276446 A JP 2002276446A JP 2002276446 A JP2002276446 A JP 2002276446A JP 2004115552 A JP2004115552 A JP 2004115552A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- curing agent
- group
- compound
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 title abstract description 5
- 239000003822 epoxy resin Substances 0.000 claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 imidazole compound Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 6
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 3
- 239000001257 hydrogen Substances 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000011342 resin composition Substances 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 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 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000010943 off-gassing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LYZFSSDDDMVLSX-UHFFFAOYSA-N 4-(2-aminoethyl)-6-(2-undecyl-1H-imidazol-5-yl)-1,3,5-triazin-2-amine Chemical compound NCCC1=NC(=NC(=N1)N)C=1N=C(NC1)CCCCCCCCCCC LYZFSSDDDMVLSX-UHFFFAOYSA-N 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 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
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 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
- 239000000463 material Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、小型電子部品又は電気部品さらに詳しくは、リレーの気密封止や絶縁封止用の一液型エポキシ樹脂に関するものである。
【０００２】
【従来の技術】
小型電子部品又は電気部品特にリレーは、エレクトニクス産業の発展とともに、その生産量も順調に伸びてきており、通信機器、ＯＡ機器、家電機器、自販器等使用される分野も多岐にわたっている。特にプリント配線基盤に搭載されるリレーが増加しつつある。その必要特性として、半田フラックスの侵入防止、部品の溶剤洗浄が可能であること等が挙げられ、樹脂等による完全気密封止型のリレーが多くなってきており、その信頼性要求は、ますます厳しくなっている。
【０００３】
この様に、リレーとして、その気密性が強く要求されることに伴い、優れた封止材料が必要とされており、従来から、この様な目的のための封止樹脂としては、エポキシ樹脂が用いられていた。エポキシ樹脂組成物としては、ポリアミドアミン、脂肪族アミン等の硬化剤とエポキシ樹脂とを使用直前に混合して使ういわゆる二液型エポキシ樹脂組成物と潜在性硬化剤として、ジシアンジアミド等を予めエポキシ樹脂組成物と混合しておく、いわゆる一液型エポキシ樹脂組成物がある。
【０００４】
一般に、二液型エポキシ樹脂組成物の欠点として、配合時の計量ミスによる硬化不良や配合後のポットライフが短い等が挙げられる。また、硬化剤にポリアミドアミン、脂肪族アミン等を用いた場合、硬化物の耐熱性が低く、封止後半田槽を通過後の気密不良が生じることが多い。一方、リレーの使用環境の多様化に伴い、封止剤の性能向上が要求されている。従って、最近では材料ロスの少なく生産性の高い一液型エポキシ樹脂組成物に移行している。
【０００５】
また、リレーに要求される性能として、接点間で数１００万回ものオン−オフ作動が繰返された後も接点が導電性の良好な状態が維持されていることが必要であるが、気密シールされたリレー内部で発生する有機ガス成分（以下アウトガスと称す）が多い場合、アウトガスが接点界面に吸着し、接点の作動に際してスパークを発生し、これに伴ない高熱を生じ、吸着したアウトガスが炭化し、導電性低下による接点不良が生じるといわれており、アウトガスの低減された一液型エポキシ樹脂組成物が求められていた。アウトガスの低減方法としては、芳香族系溶剤を含まないエポキシ樹脂を粉末状硬化剤と組み合わせた一液型液状エポキシ樹脂組成物が提案されている。（例えば、特許文献１参照）しかし、この方法は、アウトガスのうち、エポキシ樹脂や硬化剤に含まれている溶剤に起因するガス成分についてのみ着目し、エポキシ樹脂が含有している溶剤の低減について検討したものであり、硬化時に発生するエポキシ樹脂や硬化剤に含まれている溶剤に起因しないアウトガス、例えば、エポキシ樹脂や硬化剤や硬化物の分解により発生するアウトガスについては検討されていなかった。
【０００６】
【特許文献１】
特開昭６３−２６４６２４号公報
【０００７】
【発明が解決しようとする課題】
本発明は、小型電子部品又は電気部品、特にリレーにおいて性能低下の原因となる硬化時に発生するエポキシ樹脂や硬化剤に含まれている溶剤に起因しないアウトガスが低減された一液型液状エポキシ樹脂組成物を提供するものである。
【０００８】
【課題を解決するための手段】
本発明者らは、硬化時に発生するエポキシ樹脂や硬化剤に含まれている溶剤に起因しないアウトガス、例えば、エポキシ樹脂や硬化剤や硬化物の分解により発生するアウトガスが低減される一液型液状エポキシ樹脂を得るためにエポキシ樹脂と種々の硬化剤の組み合わせについて検討した結果、（Ａ）エポキシ樹脂、（Ｂ）潜在性硬化剤及び（Ｃ）イミダゾール化合物を必須成分として含有する一液型液状エポキシ樹脂組成物を用いることにより、硬化時に発生するエポキシ樹脂や硬化剤に含まれている溶剤に起因しないアウトガスについての発生が改善された硬化物が得られることが見出され、本発明を完成させた。
【０００９】
本発明において用いられる（Ａ）エポキシ樹脂としては、従来から一液型エポキシ樹脂組成物、好ましくはリレー封止用エポキシ樹脂組成物に使用されているエポキシ化合物であれば、特に限定なく使用することができる。エポキシ樹脂の具体例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、脂環式エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂等が挙げられ、これらのエポキシ樹脂単独あるいは混合で使用しても差し支えない。これらのエポキシ樹脂は、常温で液体でも固体でも使用できるが、好ましくは、常温で液状のものが使用される。
【００１０】
本発明において用いられる（Ｂ）潜在性硬化剤としては、ジシアンジアミド、エポキシ樹脂イミダゾールアダクト化合物、エポキシ樹脂アミンアダクト化合物、変性脂肪族ポリアミン化合物、ヒドラジド化合物等が挙げられる。エポキシ樹脂イミダゾールアダクト化合物としては、例えば、味の素テクノファイン社製アミキュアＰＮ−２３、アミキュアＰＮ−Ｒ等が挙げられ、エポキシ樹脂アミンアダクト化合物としては、例えば、味の素テクノファイン社製アミキュアＭＹ−２４、アミキュアＭＹ−Ｒや特開昭５７−１００１２７号公報に示されたアダクト系化合物等が挙げられる。変性脂肪族ポリアミン化合物としては、例えば、富士化成工業社製フジキュアーＦＸＥ−１０００等が挙げられ、ヒドラジド化合物としては、例えば、アジピン酸ジヒドラジドやセバシン酸ジヒドラジド等が挙げられる。以上の様な潜在性硬化剤を単独あるいは２種以上を併用することができ、硬化剤の使用量としては、エポキシ樹脂１００重量部に対して、通常、０．５重量部から３０重量部であり、好ましくは３重量部から２０重量部である。
【００１１】
本発明に用いられる（Ｃ）イミダゾール化合物は、硬化物の性能を低下させなければ、特に制限はないが、好ましくは一般式（１）で示されるイミダゾール化合物が用いられ、さらに好ましくは、２−フェニルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾールが用いられる。
【００１２】
本発明に用いる（Ｃ）イミダゾール化合物の使用量は、（Ｂ）潜在性硬化剤の使用量によって変化するが、エポキシ樹脂１００重量部に対して、０．１重量部から１０重量部であり、好ましくは０．３重量部から７重量部である。
【００１３】
本発明の一液型エポキシ樹脂組成物は、必要に応じて無機充填剤、カップリング剤、着色剤を配合することができる。無機充填剤として、例えば、炭酸カルシウム、硫酸バリウム、溶融シリカ、結晶シリカ、ガラスフィラー、水酸化アルミニウム、水酸化マグネシウム、アルミナ等が挙げられ、カップリング剤としては、例えば３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン等が挙げられ、着色剤としては、例えばカーボンブラック、酸化チタン等が挙げられる。
【００１４】
本発明の一液型エポキシ樹脂組成物の製造方法は、通常のエポキシ樹脂組成物の製造方法と同様の一般的な撹拌混合装置と混合条件が適用される。使用される装置としては、ミキシングロール、ディゾルバ、プラネタリミキサ、ニーダ、押出機等である。混合条件としてはエポキシ樹脂等を溶解および／または低粘度化し、撹拌混合効率を向上させるために加熱してもよい。また、摩擦発熱、反応発熱等を除去するために必要に応じて冷却してもよい。撹拌混合の時間は必要により定めればよく、特に制約されることはない。
【００１５】
【実施例】以下、実施例と比較例により本発明を具体的に説明する。
【００１６】
【発明の効果】
本発明の一液型エポキシ樹脂組成物を用いることにより、硬化物から発生するアウトガスのうち、硬化時に発生するエポキシ樹脂や硬化剤に含まれている溶剤に起因しないアウトガスが低減された硬化物が得られる。
【００１７】
【実施例】以下、実施例、比較例および参考例により本発明を具体的に説明する。
【００１８】
【実施例１】
エポキシ樹脂１００重量部、硬化剤Ａ９重量部およびジシアンジアミド３重量部、キュアゾール２Ｐ４ＭＨＺ ２重量部、アエロジル２００ １重量部、炭酸カルシウム１７重量部を混合し、ミキシングロールを使って混練し、一液型エポキシ樹脂組成物を調整した。
【００１９】
得られた一液型エポキシ樹脂組成物を以下の方法でアウトガスを測定した。
アウトガス測定：樹脂組成物１ｇを２０ｍｌバイアル瓶に秤量し密栓後、内部標準としてメチルエチルケトンを０．５ｍｇ添加し、１５０℃１時間加熱して硬化させ発生ガスをＧＣ装置（ＨＰ−５８９０−ＳＩＩ 検出器：ＦＩＤ）で測定を行った。
【００２０】
（実施例２〜８、比較例１〜２および参考例１）
表１および表２に示す割合で実施例１と同様にエポキシ樹脂組成物を調整したものにつき、実施例１と同様にアウトガスを測定した結果を表１および表２に示す。 尚、エポキシ樹脂のみについてアウトガスを測定した結果を参考例１として表１に示す。
【００２１】
表１〜３に記載されたジシアンジアミド以外の（Ａ）〜（Ｃ）成分は
以下のとおり。
Ｄ．Ｅ．Ｒ．３３１Ｊ：ビスフェノールＡ型エポキシ樹脂
（ダウ・ケミカルジャパン社製）
硬化剤Ａ：ジメチルアミンのエポキシ樹脂アダクト硬化剤（田岡化学社製）
硬化剤Ｂ：アミキュアＭＹ−Ｒ（味の素テクノファイン社製）
キュアゾール２Ｐ４ＭＨＺ：２−フェニル−４−メチル−５−ヒドロキシメチル−イミダゾール（四国化成工業社製）
キュアゾール２ＰＨＺ：２−フェニル−４，５−ジヒドロキシメチル−イミダゾール（四国化成工業社製）
キュアゾール２ＰＺ：２−フェニルイミダゾール（四国化成工業社製）
キュアゾールＣ１７Ｚ：２−ヘプタデシルイミダゾール（四国化成工業社製）
キュアゾールＣ１１Ｚ−Ａ：２，４−ジアミノ−６−（２´−ウンデシル−イミダゾリル）−エチル−ｓ−トリアジン （四国化成工業社製）
【００２２】
【表１】
表１
【表２】
表２
【表３】
表３
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a small electronic component or an electrical component, and more particularly, to a one-pack type epoxy resin for hermetically sealing or insulatingly sealing a relay.
[0002]
[Prior art]
With the development of the electronics industry, the production of small electronic components or electric components, particularly relays, has been steadily increasing, and the fields of use such as communication equipment, OA equipment, home electric appliances, vending machines, and the like are widespread. In particular, the number of relays mounted on printed wiring boards is increasing. Its required properties include prevention of solder flux intrusion and the ability to clean components with solvents, etc., and the number of fully hermetically sealed relays made of resin, etc. is increasing, and the reliability requirements are increasing. It's getting tougher.
[0003]
As described above, as the airtightness of the relay is strongly required, an excellent sealing material is required, and an epoxy resin has conventionally been used as a sealing resin for such a purpose. Was used. As the epoxy resin composition, a so-called two-pack type epoxy resin composition in which a curing agent such as polyamidoamine or an aliphatic amine and an epoxy resin are mixed immediately before use, and a dicyandiamide or the like as a latent curing agent are previously used as an epoxy resin. There is a so-called one-pack type epoxy resin composition which is mixed with the composition.
[0004]
In general, two-part epoxy resin compositions have drawbacks such as poor curing due to measurement errors during compounding and short pot life after compounding. In addition, when a polyamideamine, an aliphatic amine, or the like is used as a curing agent, the cured product has low heat resistance and often causes poor airtightness after passing through a solder bath after sealing. On the other hand, with the diversification of the use environment of the relay, the performance improvement of the sealant is required. Accordingly, recently, there has been a shift to a one-pack type epoxy resin composition with low material loss and high productivity.
[0005]
In addition, as a performance required for a relay, it is necessary that the contacts maintain a good conductive state even after several million on-off operations are repeated between the contacts. When there is a large amount of organic gas components (hereinafter referred to as outgas) generated inside the relay, the outgas is adsorbed at the contact interface, sparks are generated when the contacts operate, and high heat is generated due to this, and the adsorbed outgas is carbonized. However, it is said that a contact failure occurs due to a decrease in conductivity, and a one-pack type epoxy resin composition with reduced outgas has been demanded. As a method for reducing outgas, a one-part liquid epoxy resin composition in which an epoxy resin containing no aromatic solvent is combined with a powdery curing agent has been proposed. However, this method focuses only on a gas component resulting from a solvent contained in an epoxy resin or a curing agent in outgas, and reduces a solvent contained in the epoxy resin. Investigations have not been conducted on outgas generated at the time of curing and not caused by the solvent contained in the epoxy resin or the curing agent, for example, outgas generated by decomposition of the epoxy resin, the curing agent or the cured product.
[0006]
[Patent Document 1]
JP-A-63-264624
[Problems to be solved by the invention]
The present invention provides a one-part liquid epoxy resin composition in which outgassing not caused by a solvent contained in an epoxy resin or a curing agent generated at the time of curing which causes performance degradation in a small electronic component or electric component, particularly a relay, is reduced. It offers things.
[0008]
[Means for Solving the Problems]
The present inventors have found that a one-part liquid in which outgas not generated due to a solvent contained in an epoxy resin or a curing agent generated at the time of curing, for example, an outgas generated by decomposition of an epoxy resin, a curing agent or a cured product is reduced. As a result of studying the combination of the epoxy resin and various curing agents in order to obtain an epoxy resin, a one-part liquid epoxy containing (A) an epoxy resin, (B) a latent curing agent and (C) an imidazole compound as essential components. It has been found that by using the resin composition, it is possible to obtain a cured product in which the generation of outgas not caused by the solvent contained in the epoxy resin or the curing agent generated at the time of curing is improved, and the present invention has been completed. Was.
[0009]
The epoxy resin (A) used in the present invention is not particularly limited as long as it is an epoxy compound conventionally used in a one-pack type epoxy resin composition, preferably an epoxy resin composition for encapsulating a relay. Can be. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin, and dicyclo epoxy resin. Pentadiene-type epoxy resins, phenol novolak-type epoxy resins and the like can be mentioned, and these epoxy resins can be used alone or in combination. These epoxy resins can be used as liquid or solid at room temperature, but preferably used at room temperature.
[0010]
Examples of the latent curing agent (B) used in the present invention include dicyandiamide, an epoxy resin imidazole adduct compound, an epoxy resin amine adduct compound, a modified aliphatic polyamine compound, and a hydrazide compound. Examples of the epoxy resin imidazole adduct compound include Amicure PN-23 and Amicure PN-R manufactured by Ajinomoto Technofine Co., and examples of the epoxy resin amine adduct compound include Amicure MY-24 and Amicure manufactured by Ajinomoto Technofine Co. MY-R and adduct compounds disclosed in JP-A-57-100127. Examples of the modified aliphatic polyamine compound include Fujicure FXE-1000 manufactured by Fuji Kasei Kogyo Co., Ltd., and examples of the hydrazide compound include adipic dihydrazide and sebacic dihydrazide. These latent curing agents can be used alone or in combination of two or more, and the amount of the curing agent used is usually 0.5 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin. And preferably from 3 to 20 parts by weight.
[0011]
The imidazole compound (C) used in the present invention is not particularly limited as long as the performance of the cured product is not reduced, but an imidazole compound represented by the general formula (1) is preferably used, and more preferably, 2- Phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole are used.
[0012]
The amount of the (C) imidazole compound used in the present invention varies depending on the amount of the (B) latent curing agent used, but is from 0.1 part by weight to 10 parts by weight with respect to 100 parts by weight of the epoxy resin. Preferably it is from 0.3 to 7 parts by weight.
[0013]
The one-pack type epoxy resin composition of the present invention may optionally contain an inorganic filler, a coupling agent, and a coloring agent. Examples of the inorganic filler include calcium carbonate, barium sulfate, fused silica, crystalline silica, glass filler, aluminum hydroxide, magnesium hydroxide, and alumina. As the coupling agent, for example, 3-glycidoxypropyl tri Examples include methoxysilane and 3-glycidoxypropylmethyldiethoxysilane, and examples of the colorant include carbon black and titanium oxide.
[0014]
In the production method of the one-pack type epoxy resin composition of the present invention, the same general stirring and mixing apparatus and mixing conditions as in the production method of the ordinary epoxy resin composition are applied. Apparatuses used include mixing rolls, dissolvers, planetary mixers, kneaders, extruders and the like. As the mixing conditions, heating may be performed in order to dissolve and / or lower the viscosity of the epoxy resin or the like and to improve the stirring and mixing efficiency. Further, cooling may be performed as necessary to remove frictional heat, reaction heat, and the like. The time for stirring and mixing may be determined as needed, and is not particularly limited.
[0015]
The present invention will be specifically described below with reference to examples and comparative examples.
[0016]
【The invention's effect】
By using the one-pack type epoxy resin composition of the present invention, of the outgas generated from the cured product, the cured product in which the outgas not generated due to the solvent contained in the epoxy resin or the curing agent generated during curing is reduced. can get.
[0017]
The present invention will be specifically described below with reference to Examples, Comparative Examples and Reference Examples.
[0018]
Embodiment 1
100 parts by weight of an epoxy resin, 9 parts by weight of a curing agent A, 3 parts by weight of dicyandiamide, 2 parts by weight of Curazole 2P4MHZ, 1 part by weight of Aerosil 200, and 17 parts by weight of calcium carbonate are mixed and kneaded using a mixing roll. A resin composition was prepared.
[0019]
The outgassing of the obtained one-pack type epoxy resin composition was measured by the following method.
Outgas measurement: 1 g of the resin composition was weighed into a 20-ml vial, sealed, added with 0.5 mg of methyl ethyl ketone as an internal standard, heated at 150 ° C. for 1 hour, cured, and the generated gas was analyzed by a GC apparatus (HP-5890-SII detector). : FID).
[0020]
(Examples 2 to 8, Comparative Examples 1 and 2, and Reference Example 1)
Tables 1 and 2 show the results of measuring the outgassing in the same manner as in Example 1 for the epoxy resin compositions prepared in the same manner as in Example 1 at the ratios shown in Tables 1 and 2. Table 1 shows the results of measuring outgassing of only the epoxy resin as Reference Example 1.
[0021]
Components (A) to (C) other than dicyandiamide described in Tables 1 to 3 are as follows.
D. E. FIG. R. 331J: Bisphenol A type epoxy resin (manufactured by Dow Chemical Japan)
Curing agent A: dimethylamine epoxy resin adduct curing agent (manufactured by Taoka Chemical Co., Ltd.)
Curing agent B: AMICURE MY-R (manufactured by Ajinomoto Technofine)
Cureazole 2P4MHZ: 2-phenyl-4-methyl-5-hydroxymethyl-imidazole (Shikoku Chemicals)
Cureazole 2PHZ: 2-phenyl-4,5-dihydroxymethyl-imidazole (manufactured by Shikoku Chemicals)
Cureazole 2PZ: 2-phenylimidazole (manufactured by Shikoku Chemicals)
Cureazole C17Z: 2-heptadecyl imidazole (manufactured by Shikoku Chemicals)
Cureazole C11Z-A: 2,4-diamino-6- (2'-undecyl-imidazolyl) -ethyl-s-triazine (manufactured by Shikoku Chemicals)
[0022]
[Table 1]
Table 1
[Table 2]
Table 2
[Table 3]
Table 3
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002276446A JP2004115552A (en) | 2002-09-24 | 2002-09-24 | One-pack liquid epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002276446A JP2004115552A (en) | 2002-09-24 | 2002-09-24 | One-pack liquid epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004115552A true JP2004115552A (en) | 2004-04-15 |
Family
ID=32272315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002276446A Pending JP2004115552A (en) | 2002-09-24 | 2002-09-24 | One-pack liquid epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004115552A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005281513A (en) * | 2004-03-30 | 2005-10-13 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminate sheet |
| JP2007039543A (en) * | 2005-08-03 | 2007-02-15 | Taoka Chem Co Ltd | One part liquid epoxy resin composition |
| WO2010110433A1 (en) * | 2009-03-27 | 2010-09-30 | 日立化成工業株式会社 | Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same |
| JP2010248473A (en) * | 2009-03-27 | 2010-11-04 | Hitachi Chem Co Ltd | Thermosetting resin composition, and prepreg, laminate and multi-layered printed wiring board using same |
| EP2251369A4 (en) * | 2008-03-07 | 2011-03-16 | Omron Tateisi Electronics Co | COMPONENT-TYPE EPOXY RESIN COMPOSITION AND USE THEREOF |
| WO2014156926A1 (en) * | 2013-03-28 | 2014-10-02 | 日東電工株式会社 | Resin sheet for electronic device sealing and production method for electronic device package |
-
2002
- 2002-09-24 JP JP2002276446A patent/JP2004115552A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005281513A (en) * | 2004-03-30 | 2005-10-13 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminate sheet |
| JP2007039543A (en) * | 2005-08-03 | 2007-02-15 | Taoka Chem Co Ltd | One part liquid epoxy resin composition |
| EP2251369A4 (en) * | 2008-03-07 | 2011-03-16 | Omron Tateisi Electronics Co | COMPONENT-TYPE EPOXY RESIN COMPOSITION AND USE THEREOF |
| CN102365310B (en) * | 2009-03-27 | 2013-11-20 | 日立化成工业株式会社 | Thermosetting resin composition, prepreg using same, insulating film with support, laminate, and printed wiring board |
| JP2010248473A (en) * | 2009-03-27 | 2010-11-04 | Hitachi Chem Co Ltd | Thermosetting resin composition, and prepreg, laminate and multi-layered printed wiring board using same |
| CN102365310A (en) * | 2009-03-27 | 2012-02-29 | 日立化成工业株式会社 | Thermosetting resin composition, prepreg using same, insulating film with support, laminate, and printed wiring board |
| WO2010110433A1 (en) * | 2009-03-27 | 2010-09-30 | 日立化成工業株式会社 | Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same |
| US10119047B2 (en) | 2009-03-27 | 2018-11-06 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same |
| WO2014156926A1 (en) * | 2013-03-28 | 2014-10-02 | 日東電工株式会社 | Resin sheet for electronic device sealing and production method for electronic device package |
| JP2014194959A (en) * | 2013-03-28 | 2014-10-09 | Nitto Denko Corp | Resin sheet for electronic device sealing, and method for manufacturing electronic device package |
| CN105074905A (en) * | 2013-03-28 | 2015-11-18 | 日东电工株式会社 | Resin sheet for electronic device sealing and method for manufacturing electronic device package |
| TWI625832B (en) * | 2013-03-28 | 2018-06-01 | 日東電工股份有限公司 | Resin sheet for electronic component sealing and method of manufacturing electronic component package |
| CN105074905B (en) * | 2013-03-28 | 2018-11-30 | 日东电工株式会社 | Resin sheet for electronic device sealing and method for manufacturing electronic device package |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2251369A1 (en) | One-pack type epoxy resin composition and use thereof | |
| JP2010047717A (en) | One-part type liquid epoxy resin composition | |
| JP2010254951A (en) | Liquid resin composition for electronic part, and electronic part device | |
| JP2004115552A (en) | One-pack liquid epoxy resin composition | |
| JP2014173008A (en) | Curable resin composition | |
| JP2005239922A (en) | One-pack liquid epoxy resin composition | |
| WO2007075014A1 (en) | Epoxy resin composition | |
| JP4620531B2 (en) | Epoxy resin composition | |
| JP3797616B2 (en) | One-part liquid epoxy resin composition | |
| JP4090661B2 (en) | One-part liquid epoxy resin composition | |
| JP2005139274A (en) | Adhesive composition | |
| JP2009084384A (en) | One-component epoxy resin composition | |
| JP4707098B2 (en) | One-part liquid epoxy resin composition | |
| JP2001002893A (en) | One-part thermosetting resin composition | |
| JP2005239921A (en) | One-pack liquid epoxy resin composition | |
| JP4097798B2 (en) | One-part liquid epoxy resin composition | |
| JP2001207029A (en) | One-component liquid epoxy resin composition | |
| JP2007246713A (en) | One-pack type epoxy resin composition | |
| JP6057423B2 (en) | One-part liquid epoxy resin composition | |
| JP2006199818A (en) | One-pack liquid epoxy resin composition | |
| JP2004277437A (en) | Flame-retardant one-pack type liquid epoxy resin composition | |
| JP2004067963A (en) | One part liquid epoxy resin composition | |
| JP2005054060A (en) | Curing accelerator for thermosetting epoxy resin and latent epoxy resin composition for high temperature thermosetting | |
| JP2004123891A (en) | One-pack liquid epoxy resin composition | |
| JPH09194572A (en) | One liquid-type liquid epoxy resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050701 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20051109 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20051117 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A02 | Decision of refusal |
Effective date: 20060314 Free format text: JAPANESE INTERMEDIATE CODE: A02 |