JP4535214B2 - Flame retardant liquid epoxy resin composition - Google Patents
Flame retardant liquid epoxy resin composition Download PDFInfo
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- JP4535214B2 JP4535214B2 JP28821499A JP28821499A JP4535214B2 JP 4535214 B2 JP4535214 B2 JP 4535214B2 JP 28821499 A JP28821499 A JP 28821499A JP 28821499 A JP28821499 A JP 28821499A JP 4535214 B2 JP4535214 B2 JP 4535214B2
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- epoxy resin
- resin composition
- liquid epoxy
- retardant liquid
- flame
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- 239000000203 mixture Substances 0.000 title claims description 24
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 title claims description 23
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 17
- 239000003063 flame retardant Substances 0.000 title claims description 17
- 239000003822 epoxy resin Substances 0.000 claims description 37
- 229920000647 polyepoxide Polymers 0.000 claims description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- HYYJOCXNESGFSB-UHFFFAOYSA-N 1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CNCC1CO1 HYYJOCXNESGFSB-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- KZJBHSXMURQXRM-UHFFFAOYSA-N CP1(Oc2ccccc2-c2ccccc12)=O Chemical compound CP1(Oc2ccccc2-c2ccccc12)=O KZJBHSXMURQXRM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 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
- 150000001412 amines Chemical class 0.000 description 1
- -1 aniline diglycidylamine Chemical compound 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、液状エポキシ樹脂組成物に関し、好適には、半導体チップを液状封止する際に利用される難燃性液状エポキシ樹脂組成物に関するものである。
【０００２】
【従来技術】
半導体封止用材料としては従来から、プラスチックパッケージ用としてモールディングコンパウンドが多く使用されている。しかし、近年は半導体パッケージの小型・軽量化が進む中、さまざまなパッケージ形態が提案されている。例えば、従来のＱＦＰ（クアッドフラットパッケ−ジ）やＴＳＯＰ（チンスモ−ルアウトラインパッケ−ジ）といったパッケージから、ＴＣＰ（テープキャリアパッケージ）、ＢＧＡ（ボールグリッドアレイ）、ＣＳＰ（チップスケールパッケージ）、ＭＣＭ（マルチチップモジュール）などへと変化してきている。これらのパッケージに使用される材料として、液状封止材料が次第に使用されるようになってきている。
【０００３】
液状封止材料には液状エポキシ樹脂が使用されているが、これらの液状エポキシ樹脂に対する要求性能として、低粘度であることと、難燃性の付与がなされていることが挙げられる。エポキシ樹脂の難燃化に対しては従来から、臭素化エポキシ樹脂が使用されてきたが、これらを分解・燃焼するとハロゲン化物、特にダイオキシン類の発生の懸念が最近では問題視されており、ハロゲン化物を使用せずに難燃性をいかにエポキシ樹脂に付与するかが大きな問題となっている。
【０００４】
【本発明が解決しようとする課題】
本発明者は、上記の問題点を解決すべく、低粘度であり、燃焼時にハロゲン及びハロゲン化物を発生せずに難燃性を示すエポキシ樹脂を得るため種々研究した結果、本発明を完成したもので、本発明の目的はハロゲン化化合物を使用せずに低粘度で、難燃性を付与し、分解・燃焼時にハロゲン及びハロゲン化物の発生のないリンを含有するエポキシ樹脂を必須の構成成分とする難燃性液状エポキシ樹脂組成物を提供することにある。
【０００５】
【課題を解決するための手段】
即ち、本発明の要旨は、エポキシ樹脂、硬化剤、反応性希釈剤を必須の成分とする難燃性液状エポキシ樹脂組成物において、一般式〔１〕で表される液状のリン含有エポキシ樹脂を含有し、２５℃における粘度が５，０００ｍＰａ・ｓ以下であり、且つ反応性希釈剤がトリメチロールプロパンのトリグリシジルメタクリレートであることを特徴とする難燃性液状エポキシ樹脂組成物である。
【０００６】
【化２】
（式中Ｒは水素又はメチル基を表す）
本発明においては一般式〔１〕で表されるリン含有エポキシ樹脂（Ａ）（なお、このリン含有エポキシ樹脂を他のエポキシ樹脂と区別するためリン含有エポキシ樹脂（Ａ）と称する場合がある）の含有量の割合は、難燃性液状エポキシ樹脂組成物中の全エポキシ樹脂に対して５〜９５重量％であることが好ましく、また、反応性希釈剤としてトリメチロールプロパンのトリグリシジルエーテルを用いることが好ましい。
そして、本発明の難燃性液状エポキシ樹脂組成物は、２５℃における粘度が５，０００ｍＰａ・ｓ以下であることが各種半導体パッケージを液状封止する際の作業性の安定維持の面から好ましい。
【０００８】
【発明の実施の形態】
以下に、本発明について詳細に説明する。
本発明における難燃性液状エポキシ樹脂組成物のエポキシ樹脂としては、１分子中に２個以上のエポキシ基を有するエポキシ樹脂であって、例えば、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、ノボラック型エポキシ樹脂、オルトトルイジンのジグリシジルアミン型、アニリンのジグリシジルアミン、パラアミノフェノールを出発原料とした三官能エポキシ樹脂、メタアミノフェノールを出発原料とした三官能エポキシ樹脂及びレゾルシンのジグリシジルエーテルなどが挙げられる。これらのうち好ましいものは、液状のビスフェノールＡ型エポキシ樹脂およびビスフェノールＦ型エポキシ樹脂であり、特に好ましいものはこれらの分子蒸留品であり、例えば、東都化成（株）エポトートＹＤ−８１２５およびＹＤ−８１７０等である。
【０００９】
そして、エポキシ樹脂に難燃剤としてリン含有エポキシ樹脂（Ａ）が含有されるのであって、該リン含有エポキシ樹脂（Ａ）は、下記一般式〔１〕で表される
【００１０】
【化３】
（式中Ｒは水素又はメチル基を表す。）
で表れるものであり、該化合物は、下記式〔２〕
【００１２】
【化４】
で表されるリン化合物とグリシジルメタクリレートまたはグリシジルアクリレートとを、例えば、特開昭５４−１５３８４７号に開示された方法等により、加熱付加せしめる事により製造することができる。この付加反応は一般に無触媒又はアルカリ性触媒の存在下で５０℃〜１８０℃で行うことができるが、非反応性の有機溶媒（キシレン等）を反応溶媒として用いることもできる。
【００１４】
本発明で用いる一般式〔１〕で表されるリン含有エポキシ樹脂（Ａ）の割合は、これ以外に用いられるエポキシ樹脂との合計量に対して５〜９５重量％が好ましく、より好ましくは１５〜８０重量％である。５重量％以下では難燃性が不十分であり、９５重量％以上ではエポキシ樹脂硬化物の耐水性及び接着性が著しく低下して好ましくない。
【００１５】
本発明に用いられる硬化剤としては、各種フェノール類およびこれらの誘導体、酸無水物、アミン類、ヒドラジド類及び酸性ポリエステル等の従来公知の硬化剤を用いることができるが、より好ましくは可使時間の長いものおよび一液性エポキシ樹脂組成物が得やすい各種フェノール類およびこれらの誘導体、酸無水物、ヒドラジド類であり、特に好ましいものは各種フェノール類およびこれらの誘導体であり、ビスフェノールＡ、ビスフェノールＦ、フェノールノボラック、ビスフェノールＡノボラック、キシレノールノボラック、アラルキル型ノボラック、ポリパラヒドロキシスチレン、アリル化フェノールノボラック等が挙げられる。
本発明においては硬化促進剤を添加しても良い。硬化促進剤としては、第３級アミン、第４アンモニウム塩、ホスフィン類、イミダゾール類、いずれでも良いが、特にホスフィン類が好ましく、その中でもトリフェニルホスフィンが好ましい。
また、各種の市販されている潜在性硬化剤を用いることができ、これらを用いて一液性液状エポキシ樹脂組成物とすることができる。
【００１６】
本発明に用いられる反応性希釈剤としては、トリメチロールプロパントリグリシジルエーテルである。
【００１７】
上記反応性希釈剤は低塩素含有量のものが好ましいが、その中でもトリメチロールプロパントリグリシジルエーテルの全塩素含有量は０．１ｗｔ％以下であることが特に好ましい。全塩素含有量は０．１ｗｔ％以上の場合、ＩＣ封止剤として用いる場合に、これに付属している配線の腐食等が発生し易くなり好ましくない。全塩素含有量０．１ｗｔ％以下のトリメチロールプロパントリグリシジルエーテルの製造方法の一つとして、通常の市販品（例えば、東都化成（株）商品名：ＹＨ−３００）を分子蒸留する方法等が挙げられる。
【００１８】
本発明の難燃性液状エポキシ樹脂組成物には通常のエポキシ樹脂に配合される配合剤、例えば充填剤、天然ワックス、パラフィン類、直鎖状脂肪酸の金属塩類などの離型剤、チタンホワイト、カーボンブラック、ベンガラ等の着色剤、シランカップリング剤などを配合してもよい。本発明の難燃性液状エポキシ樹脂組成物に用いられる充填剤としては、シリカ粉末、アルミナ、三酸化アンチモン、タルク、炭酸カルシウムの粉末状のものなどが挙げられる。
本発明の難燃性液状エポキシ樹脂組成物の粘度は２５℃において５、０００ｍＰａ・ｓ以下が好ましく、より好ましくは３、０００ｍＰａ・ｓ以下であり、特に好ましくは１、０００ｍＰａ・ｓ以下である。粘度が５、０００ｍＰａ・ｓを越える場合には液状封止材料として高粘性となるところから各種半導体パッケージを液状封止する際の作業性が困難となることから好ましくない。
【００１９】
【実施例】
以下、本発明を実施例によって具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。尚、参考例、実施例及び比較例において「部」とは特に説明のない限り「重量部」を意味する。
参考例１
リン含有液状エポキシ樹脂（Ａ）の製造
９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド（三光化学（株）製商品名：ＨＣＡ）１００部とキシレン１００部を４つ口セパラブルフラスコに仕込み、窒素ガス雰囲気中、撹拌しながら１４０℃に昇温した。同温度を保持しながら、これにグリシジルメタクリレート６５．７部を１時間で滴下し、滴下終了後１４０℃にて３時間保った後、１０ｔｏｒｒ、１４０℃にてキシレンを留去することにより、淡黄色の液体１６５部を得た。このもののエポキシ当量は３７５ｇ／ｅｑ、５０℃における粘度は１５０ｍＰａ・ｓであった。
【００２０】
実施例例１〜３、比較例１〜３
表１の配合量に基づいて材料の配合を行い、次いで三本ロールにて混練と脱泡を行って液状エポキシ樹脂組成物を得た。リン含有エポキシ樹脂としては、参考例１で得られたものを使用し、その他のエポキシ樹脂としては、ビスフェノールＦ型エポキシ樹脂（東都化成（株）製商品名：ＹＤＦ−８１７０、エポキシ当量１６０ｇ／ｅｑ、粘度１３００ｍＰａ・ｓ ａｔ２５℃）を使用した。硬化剤としては、水酸基当量１０７ｇ／ｅｑのフェノールノボラック樹脂（昭和高分子（株）製商品名：ＢＲＧ−５５６）を使用した。硬化促進剤としては、トリフェニルホスフィンを使用した。反応性希釈剤としては、エポキシ当量１２０ｇ／ｅｑ、粘度７０ｍＰａ・ｓ ａｔ２５℃、全塩素含有量７５０ｐｐｍ（０．０７５ｗｔ％）のトリメチロールプロパントリグリシジルエーテル（東都化成（株）製：ＺＸ−１５４２）を使用した。カップリング剤としてはγ−グリシドキシプロピルトリメトキシシランを使用した、充填剤としては、溶融シリカ（平均粒径５μｍ）を使用した。
以上から得られた液状エポキシ樹脂組成物を金型に注型し、１３０℃×１０分、１５０℃×８時間なる条件で硬化させ、物性測定用の試験片を作成し、その物性を測定した。その結果を表１に示す。
【００２１】
【表１】
【発明の効果】
本発明の液状エポキシ樹脂組成物は、低粘度であり、難燃性を示すという効果がある。また、本リン含有エポキシ樹脂はハロゲン化物を含んでいないところから、分解燃焼時にハロゲン及びハロゲン化物の発生する恐れがない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid epoxy resin composition, and preferably relates to a flame retardant liquid epoxy resin composition used when a semiconductor chip is liquid-sealed.
[0002]
[Prior art]
Conventionally, many molding compounds have been used as a semiconductor sealing material for plastic packages. However, in recent years, various package forms have been proposed as semiconductor packages are becoming smaller and lighter. For example, conventional packages such as QFP (quad flat package) and TSOP (chinsmol outline package), TCP (tape carrier package), BGA (ball grid array), CSP (chip scale package), MCM ( Multi-chip module). As materials used for these packages, liquid sealing materials are gradually being used.
[0003]
A liquid epoxy resin is used for the liquid sealing material, and the required performance for these liquid epoxy resins includes low viscosity and imparted flame retardancy. Brominated epoxy resins have traditionally been used to make epoxy resins flame-retardant. However, there is a recent concern about the occurrence of halides, especially dioxins, when they are decomposed and burned. A major problem is how to impart flame retardancy to epoxy resins without using chemicals.
[0004]
[Problems to be solved by the present invention]
In order to solve the above problems, the inventor has completed the present invention as a result of various studies to obtain an epoxy resin that has low viscosity and exhibits flame retardancy without generating halogen and halide during combustion. Therefore, the object of the present invention is to use an epoxy resin containing phosphorus which has low viscosity without using a halogenated compound, imparts flame retardancy, and does not generate halogens and halides during decomposition and combustion. And providing a flame retardant liquid epoxy resin composition.
[0005]
[Means for Solving the Problems]
That is, the gist of the present invention is to provide a liquid phosphorus-containing epoxy resin represented by the general formula [1] in a flame retardant liquid epoxy resin composition containing an epoxy resin, a curing agent, and a reactive diluent as essential components. A flame retardant liquid epoxy resin composition comprising: a viscosity of 5,000 mPa · s or less at 25 ° C .; and a reactive diluent being triglycidyl methacrylate of trimethylolpropane .
[0006]
[Chemical 2]
(Wherein R represents hydrogen or a methyl group)
In the present invention, the phosphorus-containing epoxy resin (A) represented by the general formula [1] (Note that this phosphorus-containing epoxy resin may be referred to as a phosphorus-containing epoxy resin (A) in order to distinguish this phosphorus-containing epoxy resin from other epoxy resins) The content ratio is preferably 5 to 95% by weight based on the total epoxy resin in the flame retardant liquid epoxy resin composition, and triglycidyl ether of trimethylolpropane is used as the reactive diluent. It is preferable.
The flame-retardant liquid epoxy resin composition of the present invention preferably has a viscosity at 25 ° C. of 5,000 mPa · s or less from the viewpoint of stably maintaining workability when liquid-sealing various semiconductor packages.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The epoxy resin of the flame retardant liquid epoxy resin composition in the present invention is an epoxy resin having two or more epoxy groups in one molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolak. Epoxy resin, orthotoluidine diglycidylamine type, aniline diglycidylamine, trifunctional epoxy resin starting from paraaminophenol, trifunctional epoxy resin starting from metaaminophenol, and resorcin diglycidyl ether Can be mentioned. Among these, preferred are liquid bisphenol A type epoxy resin and bisphenol F type epoxy resin, and particularly preferred are these molecularly distilled products, for example, Toto Kasei Co., Ltd. Epototo YD-8125 and YD-8170. Etc.
[0009]
The epoxy resin contains a phosphorus-containing epoxy resin (A) as a flame retardant, and the phosphorus-containing epoxy resin (A) is represented by the following general formula [1].
[Chemical 3]
(In the formula, R represents hydrogen or a methyl group.)
The compound is represented by the following formula [2]
[0012]
[Formula 4]
And a glycidyl methacrylate or a glycidyl acrylate can be produced by, for example, heating and adding by the method disclosed in JP-A No. 54-153847. This addition reaction can be generally performed at 50 ° C. to 180 ° C. in the presence of a non-catalyst or an alkaline catalyst, but a non-reactive organic solvent (such as xylene) can also be used as a reaction solvent.
[0014]
The proportion of the phosphorus-containing epoxy resin (A) represented by the general formula [1] used in the present invention is preferably 5 to 95% by weight, more preferably 15%, based on the total amount with the epoxy resin used other than this. ~ 80% by weight. If it is 5% by weight or less, the flame retardancy is insufficient, and if it is 95% by weight or more, the water resistance and adhesiveness of the cured epoxy resin are remarkably lowered.
[0015]
As the curing agent used in the present invention, conventionally known curing agents such as various phenols and derivatives thereof, acid anhydrides, amines, hydrazides, and acidic polyesters can be used, but the pot life is more preferable. Are various phenols and their derivatives, acid anhydrides and hydrazides that are easy to obtain a one-component epoxy resin composition, and particularly preferred are various phenols and their derivatives, bisphenol A and bisphenol F. Phenol novolak, bisphenol A novolak, xylenol novolak, aralkyl novolak, polyparahydroxystyrene, allylated phenol novolak, and the like.
In the present invention, a curing accelerator may be added. As the curing accelerator, any of tertiary amines, quaternary ammonium salts, phosphines, and imidazoles may be used, and phosphines are particularly preferred, and among them, triphenylphosphine is preferred.
Various commercially available latent curing agents can be used, and these can be used to form a one-component liquid epoxy resin composition.
[0016]
The reactive diluents used in the present invention, a preparative trimethylolpropane triglycidyl ether.
[0017]
Although the said reactive diluent has a preferable low chlorine content, it is especially preferable that the total chlorine content of trimethylolpropane triglycidyl ether is 0.1 wt% or less. When the total chlorine content is 0.1 wt% or more, when used as an IC sealant, corrosion of wiring attached thereto is likely to occur, which is not preferable. As one method for producing trimethylolpropane triglycidyl ether having a total chlorine content of 0.1 wt% or less, there is a method of molecularly distilling a commercially available product (for example, Tohto Kasei Co., Ltd., trade name: YH-300). Can be mentioned.
[0018]
In the flame-retardant liquid epoxy resin composition of the present invention, a compounding agent blended in a normal epoxy resin, for example, a release agent such as a filler, natural wax, paraffins, metal salts of linear fatty acids, titanium white, You may mix | blend coloring agents, such as carbon black and bengara, a silane coupling agent. Examples of the filler used in the flame-retardant liquid epoxy resin composition of the present invention include silica powder, alumina, antimony trioxide, talc, and calcium carbonate powder.
The viscosity of the flame retardant liquid epoxy resin composition of the present invention is preferably 5,000 mPa · s or less at 25 ° C., more preferably 3,000 mPa · s or less, and particularly preferably 1,000 mPa · s or less. When the viscosity exceeds 5,000 mPa · s, it is not preferable because workability when liquid-sealing various semiconductor packages becomes difficult because the liquid sealing material is highly viscous.
[0019]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the reference examples, examples and comparative examples, “parts” means “parts by weight” unless otherwise specified.
Reference example 1
Production of Phosphorus-Containing Liquid Epoxy Resin (A) 100 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name: HCA manufactured by Sanko Chemical Co., Ltd.) and 100 parts of xylene A four-neck separable flask was charged and heated to 140 ° C. with stirring in a nitrogen gas atmosphere. While maintaining the same temperature, 65.7 parts of glycidyl methacrylate was added dropwise over 1 hour. After completion of the addition, the mixture was kept at 140 ° C. for 3 hours, and then xylene was distilled off at 10 torr and 140 ° C. 165 parts of a yellow liquid were obtained. The epoxy equivalent of this product was 375 g / eq, and the viscosity at 50 ° C. was 150 mPa · s.
[0020]
Examples 1 to 3 and Comparative Examples 1 to 3
The materials were blended based on the blending amounts shown in Table 1, and then kneaded and defoamed with a three roll to obtain a liquid epoxy resin composition. As the phosphorus-containing epoxy resin, the one obtained in Reference Example 1 was used, and as the other epoxy resin, bisphenol F type epoxy resin (trade name: YDF-8170, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 160 g / eq) And a viscosity of 1300 mPa · s at 25 ° C.). As the curing agent, a phenol novolak resin (trade name: BRG-556 manufactured by Showa High Polymer Co., Ltd.) having a hydroxyl group equivalent of 107 g / eq was used. Triphenylphosphine was used as a curing accelerator. As a reactive diluent, an epoxy equivalent of 120 g / eq, a viscosity of 70 mPa · s at 25 ° C., and a total chlorine content of 750 ppm (0.075 wt%), trimethylolpropane triglycidyl ether (manufactured by Toto Kasei Co., Ltd .: ZX-1542) It was used. As a coupling agent, γ-glycidoxypropyltrimethoxysilane was used, and as a filler, fused silica (average particle size 5 μm) was used.
The liquid epoxy resin composition obtained from the above was poured into a mold and cured under conditions of 130 ° C. × 10 minutes, 150 ° C. × 8 hours, a test piece for measuring physical properties was prepared, and the physical properties were measured. . The results are shown in Table 1.
[0021]
[Table 1]
【The invention's effect】
The liquid epoxy resin composition of the present invention has a low viscosity and an effect of exhibiting flame retardancy. In addition, since the present phosphorus-containing epoxy resin does not contain a halide, there is no possibility of generation of halogen and halide during decomposition combustion.
Claims (2)
一般式
General formula
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| JP28821499A JP4535214B2 (en) | 1999-10-08 | 1999-10-08 | Flame retardant liquid epoxy resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE60023752T2 (en) * | 1999-12-13 | 2006-04-20 | Dow Global Technologies, Inc., Midland | FIRE-RESISTANT PHOSPHORUS-BASED EPOXY RESIN COMPOSITION |
| JP5000053B2 (en) * | 2001-09-05 | 2012-08-15 | 三菱化学株式会社 | Liquid epoxy resin composition and cured epoxy resin |
| JP4553734B2 (en) * | 2002-12-10 | 2010-09-29 | 東レ・ダウコーニング株式会社 | Phosphorus-containing organosilicon compound, method for producing the same, and resin composition or coating composition containing the same |
| JP2004231787A (en) * | 2003-01-30 | 2004-08-19 | Nippon Steel Chem Co Ltd | Epoxy resin diluent, epoxy resin composition and epoxy resin cured product |
| JP2006332163A (en) * | 2005-05-24 | 2006-12-07 | Rohm Co Ltd | White light emitting device |
| JP2008222677A (en) | 2007-03-15 | 2008-09-25 | Chisso Corp | Flame retardant, polymer composition using the same |
| JP2011178816A (en) * | 2009-07-01 | 2011-09-15 | Sakamoto Yakuhin Kogyo Co Ltd | Specific trimethylolpropane polyglycidyl ether and epoxy resin composition containing the compound |
| JP5744010B2 (en) * | 2010-03-31 | 2015-07-01 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product thereof |
| JP6125775B2 (en) * | 2012-08-23 | 2017-05-10 | 旭化成株式会社 | Liquid sealing epoxy resin composition, cured product and electronic member |
| FR3040059B1 (en) | 2015-08-13 | 2019-05-17 | Roquette Freres | USE OF A LOW VISCOSITY BIS-ANHYDROHEXITOL ETHERS COMPOSITION AS A REACTIVE DILUENT FOR CROSS-LINKABLE COMPOSITIONS OF RESINS, ADHESIVES, COATINGS AND COMPOSITE MATRIXES |
| CN111665685A (en) * | 2019-03-08 | 2020-09-15 | 株式会社田村制作所 | Photosensitive resin composition |
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|---|---|---|---|---|
| JPS60161993A (en) * | 1984-02-01 | 1985-08-23 | Sanko Kagaku Kk | Phosphorus-containing epoxy compound and preparation thereof |
| JPH08245763A (en) * | 1995-03-13 | 1996-09-24 | Toshiba Chem Corp | Liquid resin sealing compound and sealed semiconductor device |
| JPH11166035A (en) * | 1997-09-09 | 1999-06-22 | Toto Kasei Co Ltd | Epoxy resin composition including phosphorus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS612726A (en) * | 1984-06-14 | 1986-01-08 | Sumitomo Bakelite Co Ltd | Liquid epoxy resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60161993A (en) * | 1984-02-01 | 1985-08-23 | Sanko Kagaku Kk | Phosphorus-containing epoxy compound and preparation thereof |
| JPH08245763A (en) * | 1995-03-13 | 1996-09-24 | Toshiba Chem Corp | Liquid resin sealing compound and sealed semiconductor device |
| JPH11166035A (en) * | 1997-09-09 | 1999-06-22 | Toto Kasei Co Ltd | Epoxy resin composition including phosphorus |
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