JP2004099690A - Curing agent composition for epoxy compound - Google Patents
Curing agent composition for epoxy compound Download PDFInfo
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- JP2004099690A JP2004099690A JP2002261359A JP2002261359A JP2004099690A JP 2004099690 A JP2004099690 A JP 2004099690A JP 2002261359 A JP2002261359 A JP 2002261359A JP 2002261359 A JP2002261359 A JP 2002261359A JP 2004099690 A JP2004099690 A JP 2004099690A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000004593 Epoxy Substances 0.000 title claims abstract description 53
- 150000001875 compounds Chemical class 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 72
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000011256 inorganic filler Substances 0.000 claims abstract description 36
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 4
- 239000010419 fine particle Substances 0.000 claims description 24
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- 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 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 26
- 239000003822 epoxy resin Substances 0.000 description 24
- 229920000647 polyepoxide Polymers 0.000 description 24
- 239000000945 filler Substances 0.000 description 23
- 238000004062 sedimentation Methods 0.000 description 23
- 229910002012 Aerosil® Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、高電圧機器の絶縁構造用材料や航空宇宙機器の構造材料として好適なエポキシ化合物を硬化させるために用いられるエポキシ用硬化剤組成物に関するものである。
【０００２】
【従来の技術】
電気機器や部品の絶縁材料あるいは構造材料として用いられている樹脂の中で、エポキシ樹脂は、他の熱硬化性あるいは熱可塑性樹脂に比べて優れた絶縁特性、機械的特性を有しており、各種電気絶縁材料として幅広く用いられている。特に、平均エポキシ当量３５０〜５５０のビスフェノールＡジグリシジルエーテル（ＤＧＢＡ）型のエポキシ樹脂は、強靱で絶縁特性が優れていることから、大型の電気部品や構造物用の注型樹脂として長期の実績がある。
【０００３】
しかし、これらの樹脂は室温で固形であるため、硬化剤や充填剤を配合するためには加熱混合する必要があり、混合温度におけるポットライフが短いため、作業性が悪く、注型システムの自動化が困難である。このため、この分野の樹脂には、平均エポキシ当量１３５〜２５０の液状エポキシ樹脂の適用が試みられている。
【０００４】
このような液状エポキシ樹脂を用いる場合、（１）材料コストを下げる、（２）弾性率を上げて製品の剛性を増やす、（３）機械的強度を改善する、（４）線膨脹係数を下げて成形性を改善する等の目的のため、無機充填剤を充填することが一般的に行われている。
【０００５】
【発明が解決しようとする課題】
ところで、エポキシ樹脂用硬化剤としては、可使時間が長くとれることや、硬化反応時の発熱が小さいといった理由から、酸無水物を用いる場合が多いが、一般に酸無水物は低粘度であるため、無機充填剤を一旦均一に分散させたとしても、比較的短時間で沈降してしまうという欠点がある。このため、一般的に無機充填剤の配合は、エポキシ樹脂側のみに行なうことが多い。
【０００６】
しかし、無機充填剤をエポキシ樹脂側のみに配合すると、エポキシ樹脂側が高粘度になるため、作業性の面で好ましくなく、その結果、無機充填剤の配合割合を多くできないという問題点があった。さらに、主剤であるエポキシ樹脂側のみに無機充填剤を配合した系では、無機充填剤を含まない硬化剤との粘度差が大きく異なるため、ファイナルミキサーとしてスタティックミキサーを用いるタイプの樹脂自動混合注入装置においては、エポキシ樹脂と硬化剤とを十分に混合することができないという問題点があった。
【０００７】
また、エポキシ樹脂中に配合した無機充填剤の沈降防止には、有機ベントナイトや高温火炎加水分解法で製造される球状の二酸化ケイ素の添加が有効であることが知られ、前記の球状の二酸化ケイ素としては、平均一次粒子径が７ｎｍから数１０ｎｍのものが“ＡＥＲＯＳＩＬ”という商品名で市販されている。また、水、ジメチルスルフォキシド、ジメチルホルムアミドのように極性が強い液体中の沈降防止には、ＡＥＲＯＳＩＬと同じ気相法で作られた平均一次粒子径が約１０ｎｍの酸化アルミニウムと前記ＡＥＲＯＳＩＬとの１：５の混合物が有効とされ、“ＣＯＫ８４”の商品名で市販されている。
【０００８】
一方、エポキシ樹脂用硬化剤として用いられる酸無水物は、比較的極性の大きい液体であり、この酸無水物中の無機充填剤の沈降防止については報告例はなく、本発明者等の試験では、前記“ＣＯＫ８４（商品名）”の添加も有効でないことが明らかになった。
【０００９】
以上のように、エポキシ樹脂側に配合した無機充填剤の沈降を防止する技術としては、アエロジル等の無機微粒子の添加が有効であることは公知であるが、酸無水物中の無機充填剤の沈降防止に対する有効な技術は未だ見出されていない。
【００１０】
本発明は、上述したような従来技術の問題点を解決するために提案されたものであり、その目的は、酸無水物硬化剤中に配合した無機充填剤の沈降を防止することができるエポキシ用硬化剤組成物を提供することにある。
【００１１】
【課題を解決するための手段】
上記の目的を達成するため、本発明者等は、酸無水物硬化剤中に配合した無機充填剤の沈降を防止することができる物質について鋭意検討を重ねた結果、本発明を完成するに至ったものである。
【００１２】
（エポキシ用硬化剤組成物）
本発明に係るエポキシ用硬化剤組成物は、少なくとも１分子中に２つ以上のエポキシ基を有するエポキシ化合物を硬化させる酸無水物硬化剤と、主に無機充填剤よりなる第１の粒子と、球状の無機充填剤よりなる第２の粒子から構成されている。以下、エポキシ樹脂用硬化剤である酸無水物硬化剤、第１の粒子及び第２の粒子について詳述する。
【００１３】
（エポキシ樹脂用硬化剤）
エポキシ樹脂用硬化剤としては、室温で液状の酸無水物であれば、その種類は限定されるものではなく、これらの酸無水物硬化剤は、単一または混合して用いても良い。このエポキシ樹脂用硬化剤としては、例えば、ポリカルボン酸無水物または無水ナジック酸を用いることが好ましい。特に、メチル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、無水メチルナジック酸は硬化物の耐熱性、機械的特性が優れており、また、粘度が小さく、無機充填剤の分散性が優れている点から望ましい。
【００１４】
（第１の粒子…無機充填剤）
第１の粒子である無機充填剤としては、石英、溶融シリカのような平均粒子径が１０μｍ以上の注型樹脂用充填剤を、単独で、または２種類以上の混合物として用いることができる。例えば、平均粒子径が１５μｍを超えない破砕状のシリカを用いることが望ましい。前記シリカの平均粒子径が１５μｍを超えると、第２の粒子として微粒子球状アルミナを添加しても、有効な沈降防止効果が得られない。
【００１５】
また、破砕状シリカと球状アモルファスシリカとの混合物を用いても良い。前記シリカを破砕する過程で生じる平均粒子径が５０ｎｍを超えない微粒子シリカと、微粒子球状アルミナの存在により効果的な沈降防止効果が得られ、かつ球状アモルファスシリカの存在により、樹脂組成物の粘度を低減することができ、製造性を向上させることができる。
【００１６】
（第２の粒子…アルミナ等）
球状の無機充填剤よりなる第２の粒子としては、平均粒子径が約２０ｎｍ未満の微粒子球状アルミナを用いることが望ましい。第２の粒子として微粒子球状アルミナを用いた場合の沈降防止の作用機作は、以下の通りであると考えられる。すなわち、本発明のエポキシ用硬化剤組成物では、第１の粒子である無機充填剤として用いる石英、溶融シリカの表面は５０ｎｍ未満の無数の二酸化ケイ素粒子が付着している。酸無水物中における充填剤の機械的な混合過程で、前記第１の粒子の表面の二酸化ケイ素粒子が負に帯電し、正に帯電した前記第２の粒子であるアルミナとの相互作用で網目構造を形成し、チキソトロピー性が付与されるため、充填剤の沈降が極めて効果的に防止できると考えられる。
【００１７】
また、第２の粒子として、トリメチルシリル基で表面処理した微粒子球状アルミナ、あるいはジメチルシリコーンオイルで表面処理した微粒子球状アルミナを用いてもよい。いずれの場合でも、無処理の微粒子球状アルミナよりもより少量の添加で、酸無水物中の充填剤の沈降を効果的に防止できることが分かった。
【００１８】
また、第２の粒子として、微粒子球状アルミナとジメチルシリコーンオイルで表面処理した微粒子球状シリカを用いても良い。微粒子球状アルミナと微粒子球状シリカの混合物が酸無水物中の充填剤の沈降を防止する効果は、無処理の微粒子球状シリカを用いた場合は発揮されないが、表面がジメチルシリコーンオイルで処理された微粒子球状シリカを用いると効果的な沈降防止効果が得られることが分かった。
【００１９】
なお、上記第２の粒子は、その平均粒子径が上記第１の粒子の平均粒子径の１／５００以下であることが好ましい。その理由は、上記第２の粒子の平均粒子径が上記第１の粒子の平均粒子径の１／５００より大きいと、負に帯電した第１の粒子と、正に帯電した第２の粒子との相互作用に基づく網目構造の形成が十分に行われないため、充填剤の沈降を防止するために必要なチキソトロピー性を発現させることができないからである。
【００２０】
（エポキシ化合物）
本発明のエポキシ用硬化剤組成物を適用するのに適したエポキシ樹脂は、炭素原子２個と酸素原子１個からなる三員環を１分子中に２個以上持った硬化しうる化合物であり、かつ室温で液状のエポキシ樹脂であれば適宜使用可能であり、その種類は特に限定されるものではなく、前記液状エポキシ樹脂は単独または２種以上の混合物として使用される。
【００２１】
エポキシ化合物としては、例えば、ビスフェノールＡ型、ビスフェノールＦ型、又は脂環式ジグリシジル型等の室温で液状のエポキシ化合物が、電気的特性、耐熱性、機械的特性に優れ、かつ無機充填剤の分散性が優れている点や注型作業性の面から望ましい。なお、これらのエポキシ当量は１７０〜５００である。これらのエポキシ樹脂は、それぞれ単独で、もしくは２種以上併せて用いられる。
【００２２】
（効果）
本発明に係るエポキシ用硬化剤組成物を用いた場合には、酸無水物硬化剤に配合した無機充填剤の沈降を完全に防止することができる。その結果、予めエポキシ側のみだけではなく、酸無水物側にも無機充填剤を混合分散させておくことができるので、作業性を阻害することなく、エポキシ／酸無水物樹脂組成物中の無機充填剤を極めて高充填した、機械的、電気的特性に優れたエポキシ樹脂硬化物を得ることができる。
【００２３】
さらに、無機充填剤をエポキシ側と酸無水物硬化剤側にそれぞれ配合することにより、エポキシ側と硬化剤側の粘度を任意に調整することができるので、自動樹脂注入装置に適した、製造性が良好な樹脂組成物を得ることが可能になり、その工業的価値は極めて大きい。
【００２４】
【実施例】
以下、本発明に係るエポキシ用硬化剤組成物を使用して調製した実施例及び従来技術による比較例を用いて充填剤の沈降の程度を調べ、これらの実施例及び比較例で得られた充填剤沈降量の対照評価により、本発明の作用効果について詳細に説明する。
【００２５】
なお、以下に示した実施例及び比較例について行った沈降防止実験は、ガラス製スクリュー管（直径４０ｍｍ、高さ１２０ｍｍ）に所定の方法で調製したエポキシ用硬化剤組成物２００ｇを入れ、乾燥炉を用いて容器を８０℃で３Ｈ加熱した。次に、加熱後の容器底部に沈んだ充填剤とエポキシ用硬化剤組成物とを分離し、充填剤量を測定した。沈降した充填剤量の測定結果は、実施例を表１、比較例を表２に記載した。
【００２６】
（１）試料の調製
（実施例１）
メチルヘキサヒドロ無水フタル酸（商品名：ＭＨ７００，新日本理化社製）１０００ｇに対して、平均粒子径が１４μｍの破砕状アモルファスシリカ（商品名：ＲＤ８，龍森社製）２０００ｇと、沈降防止剤として平均粒子径が約１３ｎｍの高純度微粒子アルミナ（商品名：アルミニウムＣ，日本アエロジル社製）４ｇを添加し、室温にて万能混合機（ダルトン社製）を用いて真空で２Ｈ攪拌し、エポキシ用硬化剤組成物を得た。
【００２７】
（実施例２）
実施例１と同様の方法で、沈降防止剤のみ種類を変えてエポキシ用硬化剤組成物を得た。沈降防止剤としてトリメチルシリル基で表面処理した平均粒子径が約１３ｎｍの高純度微粒子アルミナ３ｇを用いた。
【００２８】
（実施例３）
実施例１と同様の方法で、沈降防止剤のみ種類を変えてエポキシ用硬化剤組成物を得た。沈降防止剤としてジメチルシリコーンオイルで表面処理した平均粒子径が約１３ｎｍの高純度微粒子アルミナ３ｇを用いた。
【００２９】
（実施例４）
実施例１と同様の方法で、沈降防止剤のみ種類を変えてエポキシ用硬化剤組成物を得た。沈降防止剤としてジメチルシリコーンオイルで表面処理した平均粒子径が約１２ｎｍの高純度微粒子シリカ（商品名：ＡＥＲＯＳＩＬ−ＲＹ２００Ｓ，日本アエロジル社製）２ｇと平均粒子径が約１３ｎｍの高純度微粒子アルミナ（商品名：アルミニウムＣ，日本アエロジル社製）２ｇを用いた。
【００３０】
（実施例５）
メチルテトラヒドロ無水フタル酸（商品名：ＱＨ２００，日本化薬社製）１０００ｇに対して、平均粒子径が１２μｍの結晶性シリカ（商品名：クリスタライトＡ−１，龍森社製）２０００ｇと、沈降防止剤として平均粒子径が約１３ｎｍの高純度微粒子アルミナ（商品名：アルミニウムＣ，日本アエロジル社製）４ｇを添加し、室温にて万能混合機（ダルトン社製）を用いて真空で２Ｈ攪拌し、エポキシ用硬化剤組成物を得た。
【００３１】
（実施例６）
メチルヘキサヒドロ無水フタル酸（商品名：ＭＨ７００，新日本理化社製）１０００ｇに対して、平均粒子径が１４μｍの球状アモルファスシリカ（商品名：ＦＢ４８，昭和電工社製）２０００ｇと、沈降防止剤として平均粒子径が約１３ｎｍの高純度微粒子アルミナ（商品名：アルミニウムＣ，日本アエロジル社製）４ｇを添加し、室温にて万能混合機（ダルトン社製）を用いて真空で２Ｈ攪拌し、エポキシ用硬化剤組成物を得た。
【００３２】
（実施例７）
メチルヘキサヒドロ無水フタル酸（商品名：ＭＨ７００，新日本理化社製）１０００ｇに対して、平均粒子径が１４μｍの破砕状アモルファスシリカ（商品名：ＲＤ８，龍森社製）１０００ｇと平均粒子径が１４μｍの球状アモルファスシリカ（商品名：ＦＢ４８，昭和電工社製）１０００ｇ、これに沈降防止剤として平均粒子径が約１３ｎｍの高純度微粒子アルミナ（商品名：アルミニウムＣ，日本アエロジル社製）４ｇを添加し、室温にて万能混合機（ダルトン社製）を用いて真空で２Ｈ攪拌し、エポキシ用硬化剤組成物を得た。
【００３３】
（比較例１）
本比較例は、上記実施例１〜４に対応するものであって、実施例１と同様の方法で、沈降防止剤のみ種類を変えてエポキシ用硬化剤組成物を得た。沈降防止剤としては、平均粒子径が約１２ｎｍの高純度微粒子シリカ（商品名：ＡＥＲＯＳＩＬ２００，日本アエロジル社製）４ｇを用いた。
【００３４】
（比較例２）
本比較例は、上記実施例１〜４に対応するものであって、実施例１と同様の方法で、沈降防止剤のみ種類を変えてエポキシ用硬化剤組成物を得た。沈降防止剤としては、平均粒子径が約１２ｎｍの高純度微粒子シリカ（商品名：ＡＥＲＯＳＩＬ−ＣＯＫ８４，日本アエロジル社製）４ｇを用いた。なお、ＡＥＲＯＳＩＬ−ＣＯＫ８４は、二酸化ケイ素とアルミナの５：１（重量比）の混合物である。
【００３５】
（比較例３）
本比較例は、上記実施例１〜４に対応するものであって、実施例１と同様の方法で、沈降防止剤のみ種類を変えてエポキシ用硬化剤組成物を得た。沈降防止剤としては、平均粒子径が約１２ｎｍの高純度微粒子シリカ（商品名：ＡＥＲＯＳＩＬ−ＲＹ２００Ｓ，日本アエロジル社製）４ｇを用いた。
【００３６】
（比較例４）
本比較例は、上記実施例１に対応するものであって、沈降防止剤を添加していない例である。すなわち、メチルヘキサヒドロ無水フタル酸（商品名：ＭＨ７００，新日本理化社製）１０００ｇに対して、平均粒子径が１４μｍの破砕状アモルファスシリカ（商品名：ＲＤ８，龍森社製）２０００ｇを添加し、室温にて万能混合機（ダルトン社製）を用いて真空で２Ｈ攪拌し、エポキシ用硬化剤組成物を得た。
【００３７】
（比較例５）
本比較例は、上記実施例６に対応するものであって、沈降防止剤を添加していない例である。すなわち、メチルヘキサヒドロ無水フタル酸（商品名：ＭＨ７００，新日本理化社製）１０００ｇに対して、平均粒子径が１４μｍの球状アモルファスシリカ（商品名：ＦＢ４８，昭和電工社製）２０００ｇを添加し、室温にて万能混合機（ダルトン社製）を用いて真空で２Ｈ攪拌し、エポキシ用硬化剤組成物を得た。
【００３８】
（比較例６）
本比較例は、上記実施例５に対応するものであって、沈降防止剤を添加していない例である。すなわち、メチルテトラヒドロ無水フタル酸（商品名：ＱＨ２００，日本化薬社製）１０００ｇに対して、平均粒子径が１２μｍの結晶性シリカ（商品名：クリスタライトＡ−１，龍森社製）２０００ｇを添加し、室温にて万能混合機（ダルトン社製）を用いて真空で２Ｈ攪拌し、エポキシ用硬化剤組成物を得た。
【００３９】
（比較例７）
本比較例は、上記実施例７に対応するものであって、沈降防止剤を添加していない例である。すなわち、メチルヘキサヒドロ無水フタル酸（商品名：ＭＨ７００，新日本理化社製）１０００ｇに対して、平均粒子径が１４μｍの破砕状アモルファスシリカ（商品名：ＲＤ８，龍森社製）１０００ｇと平均粒子径が１４μｍの球状アモルファスシリカ（商品名：ＦＢ４８，昭和電工社製）１０００ｇを添加し、室温にて万能混合機（ダルトン社製）を用いて真空で２Ｈ攪拌し、エポキシ用硬化剤組成物を得た。
【００４０】
（２）比較結果
沈降した充填剤量の測定結果は、表１及び表２に示す通りである。
【表１】
すなわち、表１に示したように、アルミナの球状超微粒子を沈降防止剤として用いた実施例１〜７においては、沈降した充填剤はほとんど認められず、エポキシ樹脂用硬化剤である酸無水物中の充填剤の沈降をほぼ完全に防止することができることがわかった。
また、前記アルミナの球状超微粒子は、非常に少量の添加量（全充填剤に対して、重量比で約０．２％）で充填剤の沈降を完全に防止することができ、硬化物の強度、破壊靭性等の機械的特性やエポキシ樹脂との反応性には全く影響しないことも確認された。
【００４２】
これに対して、比較例１〜３は、実施例１〜４の沈降防止剤を変更したものであるが、表２に示したように、比較例１〜３では、沈降した充填剤は１１〜２１ｇと多かった。
また、比較例４は、実施例１と同様の酸無水物と無機充填剤に沈降防止剤を用いていない例であり、比較例５は、実施例６と同様の酸無水物と無機充填剤に沈降防止剤を用いていない例である。さらに、比較例６は、実施例５と同様の酸無水物と無機充填剤に沈降防止剤を用いていない例であり、比較例７は、実施例７と同様の酸無水物と無機充填剤に沈降防止剤を用いていない例である。表２に示したように、これら比較例４〜７においても、沈降した充填剤は２０．５〜２５ｇと多かった。
【００４３】
表２に示した比較例のように、従来技術では酸無水物硬化剤中の充填剤の沈降を防止することは困難である。これに対して、アルミナの球状超微粒子を沈降防止剤として用いた各実施例では、エポキシ樹脂用硬化剤である酸無水物中の充填剤の沈降をほぼ完全に防止することができることが示された。また、前記アルミナの球状超微粒子は、非常に少量の添加量（全充填剤に対して重量比で約０．２％）で充填剤の沈降を完全に防止でき、硬化物の強度、破壊靭性等の機械的特性やエポキシ樹脂との反応性には全く影響しない。
【００４４】
【発明の効果】
以上説明したように、本発明によれば、酸無水物硬化剤中に配合した無機充填剤の沈降を防止することができるエポキシ用硬化剤組成物を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to an epoxy curing agent composition used for curing an epoxy compound suitable as a material for insulating structures of high-voltage equipment or a structural material of aerospace equipment.
[0002]
[Prior art]
Among resins used as insulating or structural materials for electrical equipment and components, epoxy resins have superior insulating and mechanical properties compared to other thermosetting or thermoplastic resins. Widely used as various electrical insulating materials. Particularly, bisphenol A diglycidyl ether (DGBA) type epoxy resin having an average epoxy equivalent of 350 to 550 has a long-term performance as a casting resin for large electric parts and structures because of its toughness and excellent insulating properties. There is.
[0003]
However, since these resins are solid at room temperature, they need to be heated and mixed to mix the curing agent and filler, and the pot life at the mixing temperature is short, resulting in poor workability and automation of the casting system. Is difficult. For this reason, liquid epoxy resins having an average epoxy equivalent of 135 to 250 have been applied to resins in this field.
[0004]
When such a liquid epoxy resin is used, (1) lower the material cost, (2) increase the rigidity of the product by increasing the elastic modulus, (3) improve the mechanical strength, and (4) lower the linear expansion coefficient. Filling with an inorganic filler is generally performed for the purpose of improving the moldability.
[0005]
[Problems to be solved by the invention]
By the way, as a curing agent for an epoxy resin, an acid anhydride is often used for reasons such as a long pot life and a small amount of heat generated during a curing reaction, but generally, an acid anhydride has a low viscosity. Even if the inorganic filler is once dispersed uniformly, there is a disadvantage that the inorganic filler settles out in a relatively short time. Therefore, in general, the mixing of the inorganic filler is often performed only on the epoxy resin side.
[0006]
However, when the inorganic filler is mixed only with the epoxy resin, the viscosity of the epoxy resin becomes high, which is not preferable in terms of workability. As a result, there is a problem that the mixing ratio of the inorganic filler cannot be increased. Furthermore, in a system in which an inorganic filler is blended only on the epoxy resin side, which is the main component, the difference in viscosity from a curing agent that does not contain an inorganic filler is significantly different, so a type of resin automatic mixing and injection device that uses a static mixer as the final mixer However, there is a problem that the epoxy resin and the curing agent cannot be sufficiently mixed.
[0007]
Further, it is known that the addition of organic bentonite or spherical silicon dioxide produced by a high-temperature flame hydrolysis method is effective in preventing the sedimentation of the inorganic filler compounded in the epoxy resin, and the spherical silicon dioxide described above is effective. The one having an average primary particle diameter of 7 nm to several tens nm is commercially available under the trade name "AEROSIL". Further, in order to prevent sedimentation in a liquid having a strong polarity such as water, dimethyl sulfoxide, and dimethylformamide, aluminum oxide having an average primary particle diameter of about 10 nm produced by the same gas phase method as AEROSIL and aluminum oxide and the AEROSIL are used. A 1: 5 mixture is considered effective and is marketed under the trade name "COK84".
[0008]
On the other hand, acid anhydrides used as curing agents for epoxy resins are relatively large liquids, and there are no reports on the prevention of sedimentation of inorganic fillers in this acid anhydride. It was also found that the addition of "COK84 (trade name)" was not effective.
[0009]
As described above, as a technique for preventing sedimentation of the inorganic filler compounded on the epoxy resin side, it is known that the addition of inorganic fine particles such as Aerosil is effective. No effective technique for preventing settling has yet been found.
[0010]
The present invention has been proposed to solve the problems of the prior art as described above, and an object of the present invention is to provide an epoxy that can prevent the sedimentation of the inorganic filler blended in the acid anhydride curing agent. To provide a curing agent composition for use.
[0011]
[Means for Solving the Problems]
In order to achieve the above object, the present inventors have conducted intensive studies on substances capable of preventing the sedimentation of the inorganic filler compounded in the acid anhydride curing agent, and as a result, have completed the present invention. It is a thing.
[0012]
(Curing agent composition for epoxy)
The epoxy curing agent composition according to the present invention is an acid anhydride curing agent for curing an epoxy compound having two or more epoxy groups in at least one molecule, and first particles mainly composed of an inorganic filler, The second particles are made of a spherical inorganic filler. Hereinafter, the acid anhydride curing agent as the curing agent for the epoxy resin, the first particles, and the second particles will be described in detail.
[0013]
(Curing agent for epoxy resin)
The type of the epoxy resin curing agent is not limited as long as it is a liquid anhydride at room temperature, and these acid anhydride curing agents may be used alone or as a mixture. As the curing agent for the epoxy resin, for example, it is preferable to use polycarboxylic anhydride or nadic anhydride. In particular, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic anhydride have excellent heat resistance and mechanical properties of the cured product, and also have low viscosity and excellent dispersibility of the inorganic filler. Desirable from the point.
[0014]
(First particle: inorganic filler)
As the inorganic filler as the first particle, a filler for a casting resin having an average particle diameter of 10 μm or more, such as quartz or fused silica, can be used alone or as a mixture of two or more kinds. For example, it is desirable to use crushed silica having an average particle size not exceeding 15 μm. If the average particle diameter of the silica exceeds 15 μm, an effective effect of preventing sedimentation cannot be obtained even if spherical alumina fine particles are added as the second particles.
[0015]
Further, a mixture of crushed silica and spherical amorphous silica may be used. The fine silica particles having an average particle diameter not exceeding 50 nm generated in the process of crushing the silica, and an effective anti-settling effect are obtained by the presence of the spherical alumina particles, and the presence of the spherical amorphous silica reduces the viscosity of the resin composition. It can be reduced and manufacturability can be improved.
[0016]
(Second particles: alumina, etc.)
As the second particles made of a spherical inorganic filler, it is desirable to use fine-particle spherical alumina having an average particle diameter of less than about 20 nm. The mechanism of action for preventing sedimentation when using fine-grained spherical alumina as the second particles is considered to be as follows. That is, in the epoxy curing agent composition of the present invention, countless silicon dioxide particles of less than 50 nm adhere to the surface of quartz and fused silica used as the inorganic filler as the first particles. During the mechanical mixing process of the filler in the acid anhydride, the silicon dioxide particles on the surface of the first particles are negatively charged, and interact with the positively charged second particles of alumina to form a network. It is thought that the formation of a structure and the addition of thixotropy can prevent the sedimentation of the filler very effectively.
[0017]
Further, as the second particles, fine-particle spherical alumina surface-treated with trimethylsilyl groups or fine-particle spherical alumina surface-treated with dimethyl silicone oil may be used. In any case, it was found that the addition of a smaller amount than the untreated fine particle spherical alumina can effectively prevent the sedimentation of the filler in the acid anhydride.
[0018]
Further, as the second particles, fine particle spherical silica which has been surface-treated with fine particle spherical alumina and dimethyl silicone oil may be used. The effect of the mixture of fine-grained spherical alumina and fine-grained silica to prevent the sedimentation of the filler in the acid anhydride is not exhibited when untreated fine-grained silica is used, but the fine particles whose surface is treated with dimethyl silicone oil are not exhibited. It has been found that the use of spherical silica provides an effective effect of preventing sedimentation.
[0019]
It is preferable that the second particles have an average particle diameter of 1/500 or less of the average particle diameter of the first particles. The reason is that when the average particle diameter of the second particles is larger than 1/500 of the average particle diameter of the first particles, the first particles that are negatively charged, the second particles that are positively charged, This is because the formation of a network structure based on the interaction of the phenomena is not sufficiently performed, and the thixotropic property required to prevent the sedimentation of the filler cannot be exhibited.
[0020]
(Epoxy compound)
An epoxy resin suitable for applying the epoxy curing agent composition of the present invention is a curable compound having two or more three-membered rings composed of two carbon atoms and one oxygen atom in one molecule. Any type of epoxy resin that is liquid at room temperature can be used as appropriate, and the type thereof is not particularly limited. The liquid epoxy resin is used alone or as a mixture of two or more.
[0021]
As the epoxy compound, for example, an epoxy compound which is liquid at room temperature such as bisphenol A type, bisphenol F type, or alicyclic diglycidyl type has excellent electrical properties, heat resistance, mechanical properties, and dispersion of inorganic filler. It is desirable from the viewpoint of excellent workability and casting workability. In addition, these epoxy equivalents are 170-500. These epoxy resins are used alone or in combination of two or more.
[0022]
(effect)
When the epoxy curing agent composition according to the present invention is used, sedimentation of the inorganic filler compounded in the acid anhydride curing agent can be completely prevented. As a result, the inorganic filler can be mixed and dispersed not only on the epoxy side but also on the acid anhydride side in advance, so that the workability is not impaired and the inorganic filler in the epoxy / acid anhydride resin composition can be reduced. It is possible to obtain an epoxy resin cured product excellent in mechanical and electrical properties, which is very highly filled with a filler.
[0023]
Furthermore, by blending the inorganic filler into the epoxy side and the acid anhydride curing agent side, respectively, the viscosity of the epoxy side and the curing agent side can be adjusted arbitrarily. It is possible to obtain a good resin composition, and its industrial value is extremely large.
[0024]
【Example】
Hereinafter, the degree of sedimentation of the filler was examined using Examples prepared using the epoxy curing agent composition according to the present invention and Comparative Examples according to the prior art, and the filling obtained in these Examples and Comparative Examples was examined. The action and effect of the present invention will be described in detail by a control evaluation of the amount of the agent settled.
[0025]
The sedimentation prevention experiment performed on the following Examples and Comparative Examples was conducted by placing 200 g of the epoxy curing agent composition prepared by a predetermined method in a glass screw tube (40 mm in diameter and 120 mm in height), and drying oven. The vessel was heated at 80 ° C. for 3 H using Next, the filler settled at the bottom of the heated container and the curing agent composition for epoxy were separated, and the amount of the filler was measured. The measurement results of the amount of the settled filler are shown in Table 1 for Examples and Table 2 for Comparative Examples.
[0026]
(1) Preparation of sample (Example 1)
For 1000 g of methylhexahydrophthalic anhydride (trade name: MH700, manufactured by Shin Nippon Rika Co., Ltd.), 2000 g of crushed amorphous silica (trade name: RD8, manufactured by Tatsumori Co.) having an average particle diameter of 14 μm, and an antisettling agent 4 g of high-purity fine-particle alumina (trade name: Aluminum C, manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of about 13 nm was added thereto, and the mixture was stirred at room temperature for 2 hours in a vacuum using a universal mixer (manufactured by Dalton), and epoxy was added. A curing agent composition was obtained.
[0027]
(Example 2)
A curing agent composition for epoxy was obtained in the same manner as in Example 1 except that only the anti-settling agent was changed. As an anti-settling agent, 3 g of high-purity fine-particle alumina having a mean particle diameter of about 13 nm and surface-treated with a trimethylsilyl group was used.
[0028]
(Example 3)
A curing agent composition for epoxy was obtained in the same manner as in Example 1 except that only the anti-settling agent was changed. As an anti-settling agent, 3 g of high-purity fine-particle alumina having a mean particle diameter of about 13 nm and surface-treated with dimethyl silicone oil was used.
[0029]
(Example 4)
A curing agent composition for epoxy was obtained in the same manner as in Example 1 except that only the anti-settling agent was changed. 2 g of high-purity fine-particle silica having an average particle diameter of about 12 nm (trade name: AEROSIL-RY200S, manufactured by Nippon Aerosil Co., Ltd.) surface-treated with dimethyl silicone oil as an anti-settling agent and high-purity fine-particle alumina having an average particle diameter of about 13 nm (product (Name: Aluminum C, manufactured by Nippon Aerosil Co., Ltd.) 2 g was used.
[0030]
(Example 5)
For 1000 g of methyltetrahydrophthalic anhydride (trade name: QH200, manufactured by Nippon Kayaku Co., Ltd.), 2000 g of crystalline silica (trade name: Crystallite A-1, manufactured by Tatsumori Co.) having an average particle diameter of 12 μm, and sedimentation 4 g of high-purity fine-particle alumina having an average particle diameter of about 13 nm (trade name: Aluminum C, manufactured by Nippon Aerosil Co., Ltd.) is added as an inhibitor, and the mixture is stirred at room temperature in a vacuum for 2 hours using a universal mixer (manufactured by Dalton). Thus, a curing agent composition for epoxy was obtained.
[0031]
(Example 6)
2000 g of spherical amorphous silica (trade name: FB48, manufactured by Showa Denko KK) having an average particle diameter of 14 μm per 1000 g of methyl hexahydrophthalic anhydride (trade name: MH700, manufactured by Shin Nippon Rika Co., Ltd.) 4 g of high-purity fine-particle alumina having an average particle diameter of about 13 nm (trade name: Aluminum C, manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was stirred at room temperature for 2 H under vacuum using a universal mixer (manufactured by Dalton) to obtain epoxy resin. A curing agent composition was obtained.
[0032]
(Example 7)
For 1000 g of methylhexahydrophthalic anhydride (trade name: MH700, manufactured by Shin Nippon Rika Co., Ltd.), 1000 g of crushed amorphous silica (trade name: RD8, manufactured by Tatsumori Co.) having an average particle diameter of 14 μm was obtained. 1000 g of 14 μm spherical amorphous silica (trade name: FB48, manufactured by Showa Denko KK) and 4 g of high-purity fine-particle alumina (trade name: aluminum C, manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of about 13 nm were added to this as an anti-settling agent. Then, the mixture was stirred at room temperature for 2H under vacuum using a universal mixer (manufactured by Dalton) to obtain a curing agent composition for epoxy.
[0033]
(Comparative Example 1)
This comparative example corresponds to Examples 1 to 4 described above, and a curing agent composition for epoxy was obtained in the same manner as in Example 1, except that only the anti-settling agent was changed. As the anti-settling agent, 4 g of high-purity fine-particle silica having an average particle diameter of about 12 nm (trade name: AEROSIL200, manufactured by Nippon Aerosil Co., Ltd.) was used.
[0034]
(Comparative Example 2)
This comparative example corresponds to Examples 1 to 4 described above, and a curing agent composition for epoxy was obtained in the same manner as in Example 1, except that only the anti-settling agent was changed. As the anti-settling agent, 4 g of high-purity fine-particle silica having an average particle diameter of about 12 nm (trade name: AEROSIL-COK84, manufactured by Nippon Aerosil Co., Ltd.) was used. AEROSIL-COK84 is a 5: 1 (weight ratio) mixture of silicon dioxide and alumina.
[0035]
(Comparative Example 3)
This comparative example corresponds to Examples 1 to 4 described above, and a curing agent composition for epoxy was obtained in the same manner as in Example 1, except that only the anti-settling agent was changed. As the anti-settling agent, 4 g of high-purity fine-particle silica having an average particle diameter of about 12 nm (trade name: AEROSIL-RY200S, manufactured by Nippon Aerosil Co., Ltd.) was used.
[0036]
(Comparative Example 4)
This comparative example corresponds to Example 1 described above, and is an example in which the anti-settling agent is not added. That is, 2000 g of crushed amorphous silica (trade name: RD8, manufactured by Tatsumori) having an average particle diameter of 14 μm is added to 1000 g of methyl hexahydrophthalic anhydride (trade name: MH700, manufactured by Shin Nippon Rika Co., Ltd.). The mixture was stirred at room temperature under vacuum for 2 hours using a universal mixer (manufactured by Dalton) to obtain a curing agent composition for epoxy.
[0037]
(Comparative Example 5)
This comparative example corresponds to Example 6 described above, and is an example in which the anti-settling agent was not added. That is, 2000 g of spherical amorphous silica (trade name: FB48, manufactured by Showa Denko KK) having an average particle diameter of 14 μm was added to 1000 g of methyl hexahydrophthalic anhydride (trade name: MH700, manufactured by Shin Nippon Rika Co., Ltd.). The mixture was stirred in a vacuum at room temperature for 2H using a universal mixer (manufactured by Dalton) to obtain a curing agent composition for epoxy.
[0038]
(Comparative Example 6)
This comparative example corresponds to Example 5 described above, and is an example in which the anti-settling agent is not added. That is, for 1000 g of methyltetrahydrophthalic anhydride (trade name: QH200, manufactured by Nippon Kayaku Co., Ltd.), 2000 g of crystalline silica (trade name: Crystallite A-1, manufactured by Tatsumori Co., Ltd.) having an average particle diameter of 12 μm is used. The mixture was stirred at room temperature for 2H under vacuum using a universal mixer (manufactured by Dalton) to obtain a curing agent composition for epoxy.
[0039]
(Comparative Example 7)
This comparative example corresponds to Example 7 described above, and is an example in which the anti-settling agent is not added. That is, with respect to 1000 g of methyl hexahydrophthalic anhydride (trade name: MH700, manufactured by Shin Nippon Rika Co., Ltd.), 1000 g of crushed amorphous silica (trade name: RD8, manufactured by Tatsumori Co.) having an average particle diameter of 14 μm and average particle 1000 g of spherical amorphous silica having a diameter of 14 μm (trade name: FB48, manufactured by Showa Denko KK) was added, and the mixture was stirred at room temperature for 2 hours in a vacuum using a universal mixer (manufactured by Dalton) to obtain a curing agent composition for epoxy. Obtained.
[0040]
(2) Comparison result The measurement results of the amount of the settled filler are as shown in Tables 1 and 2.
[Table 1]
That is, as shown in Table 1, in Examples 1 to 7 in which spherical ultrafine particles of alumina were used as an anti-settling agent, almost no settled filler was observed, and the acid anhydride as a curing agent for epoxy resin was used. It has been found that sedimentation of the filler therein can be almost completely prevented.
In addition, the ultrafine spherical particles of alumina can completely prevent the sedimentation of the filler with a very small amount of addition (about 0.2% by weight based on the total filler), and can harden the cured product. It was also confirmed that it had no effect on mechanical properties such as strength and fracture toughness and reactivity with epoxy resin.
[0042]
On the other hand, in Comparative Examples 1 to 3, the anti-settling agents of Examples 1 to 4 were changed, but as shown in Table 2, in Comparative Examples 1 to 3, the settled filler was 11 It was as large as ~ 21g.
Comparative Example 4 is an example in which the same acid anhydride and inorganic filler as in Example 1 were not used with the sedimentation inhibitor, and Comparative Example 5 was the same acid anhydride and inorganic filler as in Example 6. This is an example in which no anti-settling agent is used. Further, Comparative Example 6 is an example in which the same acid anhydride and inorganic filler as in Example 5 were not used with the sedimentation inhibitor, and Comparative Example 7 was the same acid anhydride and inorganic filler as in Example 7. This is an example in which no anti-settling agent is used. As shown in Table 2, in these Comparative Examples 4 to 7, the amount of the settled filler was as large as 20.5 to 25 g.
[0043]
As in the comparative examples shown in Table 2, it is difficult to prevent the settling of the filler in the acid anhydride curing agent by the conventional technology. On the other hand, in each of the examples in which spherical ultrafine particles of alumina were used as the anti-settling agent, it was shown that the settling of the filler in the acid anhydride, which is a curing agent for epoxy resin, could be almost completely prevented. Was. Also, the ultrafine spherical particles of alumina can completely prevent the sedimentation of the filler with a very small amount of addition (about 0.2% by weight based on the total filler), and can improve the strength and fracture toughness of the cured product. It has no effect on the mechanical properties such as the above and the reactivity with the epoxy resin.
[0044]
【The invention's effect】
As described above, according to the present invention, it is possible to provide a curing agent composition for epoxy which can prevent sedimentation of an inorganic filler compounded in an acid anhydride curing agent.
Claims (9)
前記第２の粒子が、その平均粒子径が前記第１の粒子の平均粒子径の１／５００以下である球状の無機充填剤よりなることを特徴とするエポキシ用硬化剤組成物。An acid anhydride curing agent for curing an epoxy compound, first particles composed of an inorganic filler, and a curing agent composition for epoxy composed of second particles composed of a spherical inorganic filler,
A curing agent composition for epoxy, wherein the second particles comprise a spherical inorganic filler having an average particle size of 1/500 or less of the average particle size of the first particles.
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| JP2002261359A JP4053849B2 (en) | 2002-09-06 | 2002-09-06 | Epoxy curing agent composition |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008094902A (en) * | 2006-10-10 | 2008-04-24 | Shin Etsu Chem Co Ltd | Thixotropic sealant |
| JP2009203431A (en) * | 2008-02-29 | 2009-09-10 | Kyocera Chemical Corp | Epoxy resin composition for casting and highly heat conductive coil |
| JP2011079973A (en) * | 2009-10-07 | 2011-04-21 | Hitachi Chem Co Ltd | Method for producing and method for adjusting liquid resin composition for sealing and method for sealing semiconductor device and semiconductor element using the same |
| JP2014129466A (en) * | 2012-12-28 | 2014-07-10 | Hitachi Industrial Equipment Systems Co Ltd | Insulation resin material for high voltage equipment, and high voltage equipment using the same |
| CN104448717A (en) * | 2014-11-28 | 2015-03-25 | 桂林电器科学研究院有限公司 | Low-viscosity heat-conducting casting rubber and preparation method thereof |
| WO2018184486A1 (en) | 2017-04-07 | 2018-10-11 | 株式会社德山 | Silicone oil-treated fumed silica, manufacturing method and application thereof |
| JP7494703B2 (en) | 2019-10-30 | 2024-06-04 | 日産化学株式会社 | Acid anhydride-dispersed alumina sol, its uses and its manufacturing method |
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2002
- 2002-09-06 JP JP2002261359A patent/JP4053849B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008094902A (en) * | 2006-10-10 | 2008-04-24 | Shin Etsu Chem Co Ltd | Thixotropic sealant |
| JP2009203431A (en) * | 2008-02-29 | 2009-09-10 | Kyocera Chemical Corp | Epoxy resin composition for casting and highly heat conductive coil |
| JP2011079973A (en) * | 2009-10-07 | 2011-04-21 | Hitachi Chem Co Ltd | Method for producing and method for adjusting liquid resin composition for sealing and method for sealing semiconductor device and semiconductor element using the same |
| JP2014129466A (en) * | 2012-12-28 | 2014-07-10 | Hitachi Industrial Equipment Systems Co Ltd | Insulation resin material for high voltage equipment, and high voltage equipment using the same |
| CN104448717A (en) * | 2014-11-28 | 2015-03-25 | 桂林电器科学研究院有限公司 | Low-viscosity heat-conducting casting rubber and preparation method thereof |
| WO2018184486A1 (en) | 2017-04-07 | 2018-10-11 | 株式会社德山 | Silicone oil-treated fumed silica, manufacturing method and application thereof |
| US11254821B2 (en) | 2017-04-07 | 2022-02-22 | Tokuyama Corporation | Silicone oil-treated fumed silica, manufacturing method and application thereof |
| JP7494703B2 (en) | 2019-10-30 | 2024-06-04 | 日産化学株式会社 | Acid anhydride-dispersed alumina sol, its uses and its manufacturing method |
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