JP2009059753A - Flame-retardant noise suppressing sheet - Google Patents
Flame-retardant noise suppressing sheet Download PDFInfo
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- JP2009059753A JP2009059753A JP2007223619A JP2007223619A JP2009059753A JP 2009059753 A JP2009059753 A JP 2009059753A JP 2007223619 A JP2007223619 A JP 2007223619A JP 2007223619 A JP2007223619 A JP 2007223619A JP 2009059753 A JP2009059753 A JP 2009059753A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
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- Epoxy Resins (AREA)
- Powder Metallurgy (AREA)
- Hard Magnetic Materials (AREA)
- Soft Magnetic Materials (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、不要電磁波の干渉を抑制するノイズ抑制シートに関し、特に高環境信頼性を有する難燃化ノイズ抑制シートに関する。 The present invention relates to a noise suppression sheet that suppresses interference of unnecessary electromagnetic waves, and particularly relates to a flame retardant noise suppression sheet having high environmental reliability.
従来から、電子装置からの電磁波漏洩、外部環境からの電子装置への電磁波の進入、筐体金属による電子装置内での電磁波の反射が電磁ノイズとなり、電子装置の誤動作や生体への影響が懸念されている。そのため、様々な電磁波吸収機能を有する材料の開発が進められてきた。特に、扁平磁性粉を添加した材料は、その磁性損失の特性から電磁波を吸収する特性に優れている。一方で、近年、携帯電話やノートパソコンに代表されるモバイル機器の普及が進み、薄型化、小型化、軽量化、高速・高周波化が急速に進んでいる。また、モバイル機器の開発においては、短期間での製品設計・特性検証が重要になっている。そのような背景から、設計段階では把握できなかった電磁ノイズに対して、短期間で対処できる電磁波吸収機能を有する薄物のノイズ抑制シートが普及しつつある。ノイズ抑制シートは、発熱する電子装置の近傍に用いられるため、難燃性が要求される。また、熱による機械的強度などの劣化も回避しなければならない。 Conventionally, leakage of electromagnetic waves from electronic devices, invasion of electromagnetic waves from the outside environment into electronic devices, and reflection of electromagnetic waves inside electronic devices by housing metal have become electromagnetic noise, and there are concerns about malfunctions of electronic devices and effects on living organisms. Has been. Therefore, development of materials having various electromagnetic wave absorbing functions has been advanced. In particular, the material to which the flat magnetic powder is added is excellent in the property of absorbing electromagnetic waves from the property of magnetic loss. On the other hand, in recent years, mobile devices typified by mobile phones and notebook personal computers have been widely used, and thinning, miniaturization, weight reduction, and high speed / high frequency have been rapidly advanced. In the development of mobile devices, product design and characteristic verification in a short period are important. From such a background, thin noise suppression sheets having an electromagnetic wave absorbing function capable of dealing with electromagnetic noise that could not be grasped at the design stage are becoming widespread. Since the noise suppression sheet is used in the vicinity of an electronic device that generates heat, flame resistance is required. In addition, deterioration of mechanical strength due to heat must be avoided.
難燃性の付与に関しては、これまでに多くの方法が開示されている（例えば、特許文献１、特許文献２、特許文献３、特許文献４）。これらは難燃性成分をマトリクス樹脂（結合剤）中に配合することにより、所望の難燃性を得ている。例えば、特許文献１は、ハロゲン系難燃剤と三酸化アンチモンを代表とする難燃助剤の他に、無機水酸化物、無機化合物の水和物のような高温で水を分離する物質を添加して難燃性を向上したノイズ抑制シートを提供する。また、特許文献２は、エチレンアクリルゴムを必須成分としたマトリクス樹脂中に軟磁性材料粉末を分散させ、加硫工程を省いても十分な強度を有するノイズ抑制シートを得て、さらに臭素化難燃剤を添加することによって難燃規格に合格するノイズ抑制シートを提供する。特許文献３は、アクリルゴムのマトリクス樹脂中に軟磁性材料粉末を分散させ、メラミンおよびメラミン誘導体を必須として配合し、難燃性を有するノイズ抑制シートを提供する。特許文献４は、亜鉛系難燃剤、窒素系難燃剤、水酸化物系難燃剤から選ばれる少なくとも２種を合計で１５〜３０体積％含有するノイズ抑制シートを提供する。
しかし、これまで開示されているノイズ抑制シートを達成する方法は難燃性に主眼が置かれているために、厳しい環境下での信頼性の検討がされてこなかった。今後、ノイズ抑制シートが自動車内の電子機器のノイズ対策などに用いられていくためには、高温高湿などの環境に耐えられる信頼性が望まれる。特許文献３中では、高温放置後の特性劣化が少ないことが開示されているが、高温高湿などの厳しい環境試験の信頼性は解決すべき課題である。本発明は、難燃性を有し、かつ厳しい環境でも信頼性を有するノイズ抑制シートを提供することを目的とする。 However, the methods for achieving the noise suppression sheet disclosed so far have focused on flame retardancy, and thus have not been studied for reliability in harsh environments. In the future, in order for noise suppression sheets to be used for noise countermeasures for electronic devices in automobiles, reliability that can withstand environments such as high temperature and high humidity is desired. Patent Document 3 discloses that there is little characteristic deterioration after being left at high temperature, but the reliability of severe environmental tests such as high temperature and high humidity is a problem to be solved. An object of this invention is to provide the noise suppression sheet | seat which has a flame retardance and has reliability also in a severe environment.
本発明は、（Ａ）扁平軟磁性材料粉末１０００重量部、（Ｂ）エポキシ樹脂３０〜４０重量部、（Ｃ）臭素化フェノール樹脂３０〜８０重量部、（Ｄ）硬化促進剤０．０３〜１．５重量部、（Ｅ）グリシジル（メタ）アクリレート２〜６重量％を含むＴｇ（ガラス転移温度）が−１０℃以上でかつ重量平均分子量が８０万以上であるエポキシ基含有アクリル系共重合体４５〜２００重量部、（Ｆ）アンチモン酸化物３〜３０重量部、及び（Ｇ）分散剤３〜２０重量部を含有する難燃化ノイズ抑制シートである。 The present invention includes (A) 1000 parts by weight of a flat soft magnetic material powder, (B) 30 to 40 parts by weight of an epoxy resin, (C) 30 to 80 parts by weight of a brominated phenol resin, (D) 0.03 to 0.03 of a curing accelerator. Epoxy group-containing acrylic copolymer having a Tg (glass transition temperature) of -10 ° C or higher and a weight average molecular weight of 800,000 or higher, containing 1.5 parts by weight and 2 to 6% by weight of (E) glycidyl (meth) acrylate It is a flame retardant noise suppressing sheet containing 45 to 200 parts by weight of coal, (F) 3 to 30 parts by weight of antimony oxide, and (G) 3 to 20 parts by weight of a dispersant.
また、本発明は、（Ａ）扁平軟磁性材料粉末が、（１）Ｆｅ−Ａｌ系合金、Ｆｅ−Ｓｉ系合金、又はＦｅ−Ａｌ−Ｓｉ系合金からなる群から選択される１種以上の粉末、（２）Ｆｅ−Ｚｒ−Ｂ系合金、Ｆｅ−Ｈｆ−Ｂ系合金、Ｆｅ−Ｎｂ−Ｂ系合金、Ｆｅ−Ｚｒ−Ｎｂ−Ｂ系合金、Ｆｅ−Ｚｒ−Ｃｕ−ＢまたはＦｅ−Ｓｉ−Ｂ−Ｎｂ−Ｃｕ系合金、Ｆｅ−Ｃｏ−Ｓｉ−Ｂ−Ｎｂ−Ｃｕ系合金からなる群から選択される１種以上の粉末、（３）Ｆｅ−Ｂ−Ｓｉ系合金、Ｆｅ−Ｃｏ−Ｓｉ−Ｂ系合金、Ｆｅ−Ｂ−Ｓｉ−Ｃ系合金、またはＦｅ−Ｃｏ−Ｎｉ−Ｓｉ−Ｂ系合金からなる群から選択される１種以上の粉末、（４）Ｆｅ−Ｎｉ系合金、Ｆｅ−Ｎｉ−Ｍｏ系合金、Ｆｅ−Ｎｉ−Ｍｏ−Ｃｕ系合金、またはＦｅ−Ｎｉ−Ｍｏ−Ｍｎ系合金からなる群から選択される１種以上の粉末、のいずれかである難燃化ノイズ抑制シートである。 Further, the present invention provides (A) one or more flat soft magnetic material powders selected from the group consisting of (1) an Fe—Al alloy, an Fe—Si alloy, or an Fe—Al—Si alloy. Powder, (2) Fe-Zr-B alloy, Fe-Hf-B alloy, Fe-Nb-B alloy, Fe-Zr-Nb-B alloy, Fe-Zr-Cu-B or Fe-Si One or more powders selected from the group consisting of -B-Nb-Cu alloys, Fe-Co-Si-B-Nb-Cu alloys, (3) Fe-B-Si alloys, Fe-Co- One or more powders selected from the group consisting of an Si-B alloy, an Fe-B-Si-C alloy, or an Fe-Co-Ni-Si-B alloy, (4) an Fe-Ni alloy, From Fe-Ni-Mo alloy, Fe-Ni-Mo-Cu alloy, or Fe-Ni-Mo-Mn alloy One or more powder selected from that group, a flame retardant noise suppression sheet which is either a.
また、本発明は、扁平軟磁性材料粉末のアスペクト比が１０〜１００であり、かつ面方向の平均粒子径が４０〜１００μｍである前記の難燃化ノイズ抑制シートである。 Moreover, this invention is the said flame-retardant noise suppression sheet | seat whose aspect-ratio of flat soft magnetic material powder is 10-100, and the average particle diameter of a surface direction is 40-100 micrometers.
また、本発明は、（Ｇ）分散剤が、カルボキシル基又はスルホン基を有するアニオン性高分子を主成分とする難燃化ノイズ抑制シートである。 Moreover, this invention is a flame-retardant noise suppression sheet | seat which (G) a dispersing agent has as a main component the anionic polymer which has a carboxyl group or a sulfone group.
さらに本発明は、難燃化ノイズ抑制シートの厚みが、２０〜５０μｍである難燃化ノイズ抑制シート、難燃化ノイズ抑制シートの厚み方向に扁平軟磁性材料粉末の粒子が３〜１０枚重なって配向されている難燃化ノイズ抑制シートである。 Furthermore, the present invention provides a flame retardant noise suppression sheet having a thickness of 20 to 50 μm, and 3 to 10 particles of flat soft magnetic material powder in the thickness direction of the flame retardant noise suppression sheet. It is a flame retardant noise suppression sheet that is oriented.
本発明によれば、難燃性を有し、かつ高環境信頼性を有するノイズ抑制シートを提供することが可能となる。 According to the present invention, it is possible to provide a noise suppression sheet having flame retardancy and high environmental reliability.
本発明の難燃化ノイズ抑制シートは、（Ａ）扁平軟磁性材料粉末１０００重量部、（Ｂ）エポキシ樹脂３０〜４０重量部、（Ｃ）臭素化フェノール樹脂３０〜８０重量部、（Ｄ）硬化促進剤０．０３〜１．５重量部、（Ｅ）グリシジル（メタ）アクリレート２〜６重量％を含むＴｇ（ガラス転移温度）が−１０℃以上でかつ重量平均分子量が８０万以上であるエポキシ基含有アクリル系共重合体４５〜２００重量部、（Ｆ）アンチモン酸化物３〜３０重量部、及び（Ｇ）分散剤３〜２０重量部を含有する。 The flame retardant noise suppression sheet of the present invention includes (A) 1000 parts by weight of a flat soft magnetic material powder, (B) 30 to 40 parts by weight of an epoxy resin, (C) 30 to 80 parts by weight of a brominated phenol resin, (D) Tg (glass transition temperature) containing 0.03 to 1.5 parts by weight of a curing accelerator and 2 to 6% by weight of (E) glycidyl (meth) acrylate is −10 ° C. or higher and the weight average molecular weight is 800,000 or higher. It contains 45 to 200 parts by weight of an epoxy group-containing acrylic copolymer, (F) 3 to 30 parts by weight of antimony oxide, and (G) 3 to 20 parts by weight of a dispersant.
本発明における（Ａ）扁平軟磁性材料粉末は、軟磁性材料として高透磁率を示すものであれば限定されることなく好適に使用することができる。Ｆｅ−Ａｌ系合金、例えばアルパーム、Ｆｅ−Ｓｉ系合金、例えばケイ素鋼、又はＦｅ−Ａｌ−Ｓｉ系合金、例えばセンダストのいずれか、またそれらの混合粉末を用いることが出来る。また、ナノ結晶材料で高透磁率を発現するＦｅ−Ｚｒ−Ｂ系合金、例えばＦｅ９１Ｚｒ７Ｂ２、Ｆｅ−Ｈｆ−Ｂ系合金、例えばＦｅ８９Ｈｆ７Ｂ４、Ｆｅ−Ｎｂ−Ｂ系合金、例えばＦｅ８４Ｎｂ７Ｂ９、Ｆｅ−Ｚｒ−Ｎｂ−Ｂ系合金、例えばＦｅ８９Ｚｒ６Ｎｂ１Ｂ４、Ｆｅ−Ｚｒ−Ｃｕ−Ｂ系合金、例えばＦｅ８８Ｚｒ７Ｃｕ１Ｂ４、Ｆｅ−Ｓｉ−Ｂ−Ｎｂ−Ｃｕ系合金、例えばＦｅ７３．５Ｓｉ１３．５Ｂ９Ｎｂ３Ｃｕ１、又はＦｅ−Ｃｏ−Ｓｉ−Ｂ−Ｎｂ−Ｃｕ系合金、例えばＦｅ１８．８Ｃｏ６０Ｓｉ９Ｂ９Ｎｂ２．６Ｃｕ０．６のいずれか、またそれらの混合粉末を用いることが出来る。また、アモルファス合金であるＦｅ−Ｂ−Ｓｉ系合金、例えばＦｅ７８Ｂ１０Ｓｉ１２、Ｆｅ−Ｃｏ−Ｓｉ−Ｂ系合金、例えばＦｅ５Ｃｏ７０Ｓｉ１５Ｂ１０、Ｆｅ−Ｂ−Ｓｉ−Ｃ系合金、例えばＦｅ９４．４Ｂ３Ｓｉ２．１Ｃ０．５、又はＦｅ−Ｃｏ−Ｎｉ−Ｓｉ−Ｂ系合金、例えばＦｅ２４Ｃｏ１２．５Ｎｉ４５．５Ｓｉ２Ｂ１６のいずれか、またそれらの混合粉末を用いることが出来る。また、パーマロイ系合金であるＦｅ−Ｎｉ系合金、Ｆｅ−Ｎｉ−Ｍｏ系合金、Ｆｅ−Ｎｉ−Ｍｏ−Ｃｕ系合金、又はＦｅ−Ｎｉ−Ｍｏ−Ｍｎ系合金（スーパーマロイ）のいずれか、またそれらの混合粉末を用いることが出来る。 The (A) flat soft magnetic material powder in the present invention can be suitably used without limitation as long as it exhibits a high magnetic permeability as a soft magnetic material. Any of Fe-Al based alloys such as Alpalm, Fe-Si based alloys such as silicon steel, or Fe-Al-Si based alloys such as Sendust, and mixed powders thereof can be used. In addition, Fe—Zr—B based alloys that exhibit high magnetic permeability in nanocrystalline materials, such as Fe 91 Zr 7 B 2 , Fe—Hf—B based alloys, such as Fe 89 Hf 7 B 4 , Fe—Nb—B based, etc. alloys such as Fe 84 Nb 7 B 9, Fe -Zr-Nb-B -based alloy, for example, Fe 89 Zr 6 Nb 1 B 4 , Fe-Zr-Cu-B alloy, for example, Fe 88 Zr 7 Cu 1 B 4 , Fe-Si-B-Nb-Cu-based alloys such as Fe 73.5 Si 13.5 B 9 Nb 3 Cu 1 , or Fe-Co-Si-B-Nb-Cu-based alloys such as Fe 18.8 Co 60 Any of Si 9 B 9 Nb 2.6 Cu 0.6 or a mixed powder thereof can be used. Also, Fe-B-Si alloys that are amorphous alloys, such as Fe 78 B 10 Si 12 , Fe-Co-Si-B alloys, such as Fe 5 Co 70 Si 15 B 10 , Fe-B-Si-C, are used. Either an alloy, such as Fe 94.4 B 3 Si 2.1 C 0.5 , or an Fe—Co—Ni—Si—B based alloy, such as Fe 24 Co 12.5 Ni 45.5 Si 2 B 16 , Moreover, those mixed powders can be used. Also, any one of Fe-Ni alloy, Fe-Ni-Mo alloy, Fe-Ni-Mo-Cu alloy, or Fe-Ni-Mo-Mn alloy (supermalloy), which is a permalloy alloy, Those mixed powders can be used.
また、扁平軟磁性材料粉末は、金属軟磁性材料を粉砕、延伸・引張り加工や溶湯アトマイズ法などにより粉末化し、アトライタやボールミルによる扁平化処理を行うことにより得ることが出来る。扁平軟磁性材料粉末の扁平度は１０〜３０であり、かつ面方向の平均粒子径が４０〜１００μｍであることが好ましい。ここで扁平度とは、扁平度＝粉末粒子の平均粒子径／粒子の平均厚みで表されるものである。扁平度が１０未満であると、分散したシートの透磁率が低くノイズ抑制効果が低い。扁平度が３０を超えると分散性が低下する。また、平均粒子径が４０μｍ未満であっても、分散したシートの透磁率が低くノイズ抑制効果が低い。平均粒子径が１００μｍを超えても分散性が低下する。 The flat soft magnetic material powder can be obtained by pulverizing, stretching and pulling a metal soft magnetic material by a melt atomizing method or the like, and performing a flattening treatment using an attritor or a ball mill. The flatness of the flat soft magnetic material powder is preferably 10 to 30, and the average particle size in the plane direction is preferably 40 to 100 μm. Here, flatness is expressed by flatness = average particle diameter of powder particles / average thickness of particles. When the flatness is less than 10, the magnetic permeability of the dispersed sheet is low and the noise suppression effect is low. If the flatness exceeds 30, the dispersibility decreases. Even if the average particle size is less than 40 μm, the magnetic permeability of the dispersed sheet is low and the noise suppression effect is low. Even if the average particle diameter exceeds 100 μm, the dispersibility decreases.
本発明における（Ｂ）エポキシ樹脂は、硬化した後に高温放置試験や高温高湿放置試験などで特性が劣化しないものであれば限定されることなく好適に使用することができる。具体的には、架橋点間分子量が小さい２官能エポキシ樹脂や多官能エポキシ樹脂を用いることが好ましい。２官能エポキシ樹脂としては、ビスフェノールＡ型又はビスフェノールＦ型液状樹脂等を使用できる。多官能エポキシ樹脂としては、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等を使用できる。また、難燃化を効果的にするために臭素化エポキシ樹脂を用いてもよい。臭素化エポキシ樹脂としては、ビスフェノールＡ型やノボラック型のものを使用できる。エポキシ樹脂は、扁平軟磁性材料粉末１０００重量部に対して３０〜４０重量部用いる。エポキシ樹脂が３０重量部未満では、十分な機械的な強度が得られず、４０重量部を超えると、シートを製造する際の取り扱い性が低下する。扁平軟磁性材料粉末１０００重量部に対して、（Ｂ）エポキシ樹脂、（Ｃ）臭素化フェノール樹脂、（Ｄ）硬化促進剤、（Ｅ）エポキシ基含有アクリル系共重合体、及び（Ｇ）分散剤の樹脂合計量が、１００〜３５０重量部であることが好ましい。１００重量部未満では、マトリクス樹脂量の低下により、ボイドの発生や機械的強度の低下が起こる。３５０重量部を超えると、扁平軟磁性材料粉末量が相対的に低下し、ノイズ抑制効果が低下する。マトリクス樹脂を形成するエポキシ樹脂、臭素化フェノール樹脂、硬化促進剤、エポキシ基含有アクリル系共重合体、分散剤の比率は、機械的な強度、取り扱い性や信頼性などから決められる。 The (B) epoxy resin in the present invention can be suitably used without being limited as long as it does not deteriorate in properties after being cured, such as a high temperature storage test or a high temperature high humidity storage test. Specifically, it is preferable to use a bifunctional epoxy resin or a polyfunctional epoxy resin having a small molecular weight between crosslinking points. As the bifunctional epoxy resin, bisphenol A type or bisphenol F type liquid resin or the like can be used. As the polyfunctional epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, or the like can be used. Further, a brominated epoxy resin may be used in order to make flame retardancy effective. As the brominated epoxy resin, bisphenol A type or novolac type resin can be used. The epoxy resin is used in an amount of 30 to 40 parts by weight with respect to 1000 parts by weight of the flat soft magnetic material powder. If the epoxy resin is less than 30 parts by weight, sufficient mechanical strength cannot be obtained, and if it exceeds 40 parts by weight, the handleability when producing a sheet is lowered. (B) Epoxy resin, (C) Brominated phenol resin, (D) Curing accelerator, (E) Epoxy group-containing acrylic copolymer, and (G) Dispersion with respect to 1000 parts by weight of flat soft magnetic material powder The total resin amount of the agent is preferably 100 to 350 parts by weight. If the amount is less than 100 parts by weight, voids and mechanical strength are reduced due to a decrease in the amount of matrix resin. If it exceeds 350 parts by weight, the amount of the flat soft magnetic material powder is relatively lowered, and the noise suppression effect is lowered. The ratios of the epoxy resin, brominated phenol resin, curing accelerator, epoxy group-containing acrylic copolymer and dispersant forming the matrix resin are determined from mechanical strength, handleability and reliability.
本発明における（Ｃ）エポキシ樹脂の硬化剤は、難燃化のためにフェノール性水酸基を１分子中に２個以上有する臭素化フェノール樹脂を用いる。臭素化フェノール樹脂は、エポキシ樹脂１００重量部に対し、１００〜２００重量部用いる。したがって、扁平軟磁性材料粉末１０００重量部に対して、３０〜８０重量部とする。臭素化フェノール樹脂の配合量は、その水酸基当量とエポキシ樹脂のエポキシ当量から未反応官能基が少なくなるように決めることが好ましい。未反応官能基が多い場合には、耐熱性の低下等が現われる。臭素化フェノール樹脂としては、テトラブロモビスフェノールＡを用いることが好ましい。 As the curing agent for the epoxy resin (C) in the present invention, a brominated phenol resin having two or more phenolic hydroxyl groups in one molecule is used for flame retardancy. The brominated phenol resin is used in an amount of 100 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin. Therefore, it is 30 to 80 parts by weight with respect to 1000 parts by weight of the flat soft magnetic material powder. The blending amount of the brominated phenol resin is preferably determined so that the number of unreacted functional groups decreases from the hydroxyl equivalent and the epoxy equivalent of the epoxy resin. When there are many unreacted functional groups, a heat resistant fall etc. appear. Tetrabromobisphenol A is preferably used as the brominated phenol resin.
本発明においては、硬化剤とともに（Ｄ）硬化促進剤を用いる。硬化促進剤としては、各種イミダゾール類を用いるのが好ましい。イミダゾールとしては、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−フェニルイミダゾリウムトリメリテート等を使用できる。硬化促進剤量は、０．０３〜１．５重量部とする。０．０３重量部未満の場合には、硬化促進作用が現れない。１．５重量部を超えると、硬化反応が進みやすく、硬化前の保存管理が難しくなる。 In the present invention, (D) a curing accelerator is used together with the curing agent. As the curing accelerator, various imidazoles are preferably used. As imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate and the like can be used. The amount of curing accelerator is 0.03 to 1.5 parts by weight. In the case of less than 0.03 parts by weight, the curing accelerating action does not appear. If it exceeds 1.5 parts by weight, the curing reaction tends to proceed, and storage management before curing becomes difficult.
本発明における（Ｅ）グリシジル（メタ）アクリレート２〜６重量％を含むＴｇが−１０℃以上でかつ重量平均分子量が８０万以上であるエポキシ基含有アクリル系共重合体は、エチル（メタ）アクリレートやブチル（メタ）アクリレート又は両者のユニットを有する共重合体を使用することができる。官能基モノマーが、グリシジル（メタ）アクリレートでなく、カルボン酸タイプのアクリル酸や、水酸基タイプのヒドロキシメチル（メタ）アクリレートを用いると、架橋反応が進行しやすく、ワニス状態でのゲル化が起こりやすく好ましくない。また、グリシジル（メタ）アクリレートの量は、２〜６重量％の共重合体比とする。架橋反応による耐熱性向上を図るため、２重量％以上とし、ゴムのゲル化を防止するために６重量％以下とする。エチル（メタ）アクリレートやブチル（メタ）アクリレートとの比率は、共重合体のＴｇを考慮して決定する。Ｔｇが−１０℃未満であるとＢステージ状態での接着フィルムのタック性が大きくなり取扱性が悪化するので、−１０℃以上とする。重合方法はパール重合、溶液重合等が挙げられ、これらにより得ることができる。エポキシ基含有アクリル系共重合体の重量平均分子量は、シート状、フィルム状での強度や可撓性の低下が少ない８０万以上とする。エポキシ基含有アクリル系共重合体の添加量は、４５〜２００重量部とする。４５重量部未満では、シート状、フィルム状での強度や可撓性が低下する。また、エポキシ基含有アクリル系共重合体の添加量が増えると、ゴム成分の相が多くなりエポキシ樹脂相が少なくなるため、高温での取扱い性の低下が起こるため、２００重量部以下とする。 In the present invention, an epoxy group-containing acrylic copolymer having a Tg containing 2 to 6% by weight of (E) glycidyl (meth) acrylate is -10 ° C. or more and a weight average molecular weight is 800,000 or more is ethyl (meth) acrylate. Or a butyl (meth) acrylate or a copolymer having both units. When the functional group monomer is not glycidyl (meth) acrylate but carboxylic acid type acrylic acid or hydroxyl group type hydroxymethyl (meth) acrylate, the crosslinking reaction is likely to proceed and gelation in the varnish state is likely to occur. It is not preferable. The amount of glycidyl (meth) acrylate is 2 to 6% by weight of the copolymer. In order to improve the heat resistance by the crosslinking reaction, the content is made 2% by weight or more, and in order to prevent rubber gelation, the content is made 6% by weight or less. The ratio of ethyl (meth) acrylate or butyl (meth) acrylate is determined in consideration of the Tg of the copolymer. When Tg is less than −10 ° C., the tackiness of the adhesive film in the B-stage state is increased and the handleability is deteriorated. Examples of the polymerization method include pearl polymerization and solution polymerization, and these can be obtained. The weight average molecular weight of the epoxy group-containing acrylic copolymer is set to 800,000 or more with little decrease in strength and flexibility in sheet form and film form. The addition amount of the epoxy group-containing acrylic copolymer is 45 to 200 parts by weight. If it is less than 45 weight part, the intensity | strength and flexibility in a sheet form and a film form will fall. Further, when the addition amount of the epoxy group-containing acrylic copolymer is increased, the phase of the rubber component is increased and the epoxy resin phase is decreased.
本発明における（Ｆ）アンチモン酸化物は、三酸化二アンチモン、五酸化二アンチモンを用いることができる。難燃性を発現させるために、アンチモン酸化物の添加量は３〜３０重量部である。この範囲であると、難燃性が付与でき、添加フィラー増大によるボイドなどの欠陥発生を抑制することができる。 As the antimony oxide (F) in the present invention, diantimony trioxide and diantimony pentoxide can be used. In order to express flame retardancy, the amount of antimony oxide added is 3 to 30 parts by weight. Within this range, flame retardancy can be imparted and the occurrence of defects such as voids due to an increase in added filler can be suppressed.
本発明においては、扁平軟磁性材料粉末の分散性を向上させるために（Ｇ）分散剤を加える。分散剤としては、アニオン性高分子を主成分としたものがより好ましい。アニオン性高分子を主成分とした分散剤としては、アクリル酸重合物、アクリル−マレイン酸共重合物、アクリル酸−アクリル酸エステル共重合物、カルボキシメチルセルロースなどのカルボキシル基をもつ高分子や、２−アクリルアミド−２−メチルプロパンスルホン酸、ナフタリンスルホン酸ホルマリン縮合物などのスルホン基をもつ高分子が挙げられる。分散剤の添加量は、３〜２０重量部である。３重量部未満では、分散性の向上の効果が薄く、２０重量部を超えると樹脂材料の特性に悪影響を及ぼし、耐熱性低下などの原因となる。 In the present invention, (G) a dispersant is added in order to improve the dispersibility of the flat soft magnetic material powder. As the dispersant, those having an anionic polymer as a main component are more preferable. Examples of the dispersant mainly composed of an anionic polymer include polymers having a carboxyl group such as acrylic acid polymer, acrylic-maleic acid copolymer, acrylic acid-acrylic acid ester copolymer, carboxymethyl cellulose, and 2 -Polymers having a sulfonic group such as acrylamido-2-methylpropane sulfonic acid, naphthalene sulfonic acid formalin condensate and the like. The addition amount of a dispersing agent is 3-20 weight part. If the amount is less than 3 parts by weight, the effect of improving dispersibility is thin. If the amount exceeds 20 parts by weight, the properties of the resin material are adversely affected, leading to a decrease in heat resistance.
また、扁平軟磁性材料粉末表面の濡れ性を上げるためにカップリング剤を併用しても良い。カップリング剤としては、シランカップリング剤、チタネートカップリング剤を用いることができる。添加量は、扁平軟磁性材料粉末と分散剤の添加量を考慮し、特性低下を起こさない範囲とすることが好ましい。 Further, a coupling agent may be used in combination in order to increase the wettability of the flat soft magnetic material powder surface. As the coupling agent, a silane coupling agent or a titanate coupling agent can be used. The addition amount is preferably set in a range that does not cause deterioration of characteristics in consideration of the addition amount of the flat soft magnetic material powder and the dispersant.
難燃化ノイズ抑制シートの厚みは、２０〜５０μｍであることが好ましい。２０μｍ未満であると、ノイズ抑制効果が低くシートの取り扱い性も困難である。５０μｍを超えると、薄型電子機器で用いるメリットが低下してしまう。 The thickness of the flame retardant noise suppression sheet is preferably 20 to 50 μm. If it is less than 20 μm, the noise suppressing effect is low, and the sheet is difficult to handle. When it exceeds 50 μm, the merit to be used in a thin electronic device is lowered.
シートの製造は、（１）ワニスの製造、（２）キャリアフィルムへの塗布、（３）溶剤除去・硬化の工程を通すことで製造することができる。 The sheet can be produced by (1) production of varnish, (2) application to a carrier film, and (3) solvent removal / curing process.
ワニスの製造に関して、ワニス化に溶剤は、比較的低沸点の、メチルエチルケトン、アセトン、メチルイソブチルケトン、２−エトキシエタノール、トルエン、ブチルセルソルブ、メタノール、エタノール、２−メトキシエタノールなどを用いるのが好ましい。また、塗膜性を向上するなどの目的で、高沸点溶剤を加えても良い。高沸点溶剤としては、ジメチルアセトアミド、ジメチルホルムアミド、メチルピロリドン、シクロヘキサノンなどが挙げられる。ワニスの製造は、扁平軟磁性材料粉末の分散を考慮した場合には、らいかい機、３本ロール、ホモミクサー、ビーズミル、ジェットミル、ナノマイザー等により、またこれらを組み合わせて行なうことができる。扁平軟磁性材料粉末と低分子量物をあらかじめ混合した後、高分子量物を配合することにより、混合に要する時間を短縮することも可能となる。また、ワニスとした後、真空脱気によりワニス中の気泡を除去することが好ましい。 Regarding the production of varnish, it is preferable to use a solvent having a relatively low boiling point such as methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol, etc. . Moreover, you may add a high boiling point solvent for the purpose of improving coating-film property. Examples of the high boiling point solvent include dimethylacetamide, dimethylformamide, methylpyrrolidone, and cyclohexanone. In consideration of the dispersion of the flat soft magnetic material powder, the varnish can be produced by a raking machine, three rolls, a homomixer, a bead mill, a jet mill, a nanomizer or the like, or a combination thereof. By mixing the flat soft magnetic material powder and the low molecular weight material in advance and then blending the high molecular weight material, the time required for mixing can be shortened. In addition, after forming the varnish, it is preferable to remove bubbles in the varnish by vacuum degassing.
キャリアフィルムへの塗布に関しては、一般的なドクターブレード法を用いることができる。また、バーコーター，コンマコーター，ダイコーターなどの装置も使用できる。キャリアフィルムとしては、ポリテトラフルオロエチレンフィルム、ポリエチレンテレフタレートフィルム、離型処理したポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルムなどのプラスチックフィルムが使用できる。 For application to the carrier film, a general doctor blade method can be used. Devices such as bar coaters, comma coaters, and die coaters can also be used. As the carrier film, a plastic film such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a release-treated polyethylene terephthalate film, a polyethylene film, or a polypropylene film can be used.
溶剤の除去・硬化に関しては、防爆型の加熱乾燥機，加熱乾燥炉を用いることができる。また、溶剤の除去に伴って、シート中に気泡ができたり、シート中で扁平軟磁性材料粉末が十分に行われなかったりする場合がある。そのようなことを防ぐためには、溶剤除去した半硬化状態のシートを加熱加圧して、充填性と配向性を向上することが好ましい。 For removal and curing of the solvent, an explosion-proof heating dryer and heating drying furnace can be used. Further, with removal of the solvent, bubbles may be formed in the sheet, or the flat soft magnetic material powder may not be sufficiently performed in the sheet. In order to prevent such a situation, it is preferable to heat and press the semi-cured sheet from which the solvent is removed to improve the filling property and orientation.
次に実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these.
（実施例１）
扁平軟磁性材料粉末として、Ｆｅ−Ａｌ−Ｓｉ合金であるＦｅ８５Ａｌ５．５Ｓｉ９．５の溶湯を水噴霧し、得られた粉末をアトライタで処理して、扁平粉末（平均粒子径６０μｍ、平均厚み３μｍ）としたもの１０００重量部、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５）２０重量部、クレゾールノボラック型エポキシ樹脂（東都化成株式会社製、ＹＤＣＮ−７０３）１５重量部、臭素化フェノール樹脂（帝人化成株式会社製、ファイヤーガードＦG２０００）５０重量部、硬化促進剤として１−シアノエチル−２−フェニルイミダゾール（キュアゾール２ＰＺ−ＣＮ、四国化成株式会社製を使用）０．４重量部、エポキシ基含有アクリル系共重合体としてエポキシ基含有アクリルゴム（分子量１００万、ナガセケムテックス株式会社製、ＨＴＲ−８６０Ｐ−３）７０重量部、アンチモン酸化物として三酸化二アンチモン（日本精鉱株式会社製、ＰＡＴＯＸ−Ｕ）８重量部、分散剤としてカルボキシル基を含む共重合体（ビックケミー・ジャパン株式会社製、Ｄｉｓｐｅｒｂｙｋ１１１）８重量部からなる組成物に、メチルエチルケトンを加えて撹拌混合し、さらにビーズミルを用いて混練し、真空脱気した。
このワニスを、厚み５０μｍの離型処理したポリエチレンテレフタレートフィルム上にドクターブレードを用いて塗布し、温度１５０℃で５分間加熱乾燥して、半硬化状態のノイズ抑制シートを形成した。このシートの表面に、さらに厚み５０μｍの離型処理したポリエチレンテレフタレートフィルムを離型面がノイズ抑制シート表面に接するように重ね合わせ、温度１７０℃、圧力４ＭＰａ、３０分間、加熱加圧硬化した。硬化したノイズ抑制シート単体の厚みを測定したところ、４０μｍであった。
(Example 1)
As a flat soft magnetic material powder, a Fe 85 Al 5.5 Si 9.5 molten metal, which is an Fe—Al—Si alloy, is sprayed with water, and the obtained powder is treated with an attritor to obtain a flat powder (average particle diameter of 60 μm). , Average thickness 3 μm) 1000 parts by weight, epoxy resin bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., YD-8125), cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDCN-703) ) 15 parts by weight, brominated phenolic resin (manufactured by Teijin Chemicals Ltd., Fireguard FG2000), 1-cyanoethyl-2-phenylimidazole (Cureazole 2PZ-CN, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator 0.4 parts by weight, epoxy group-containing acrylic rubber as epoxy group-containing acrylic copolymer ( Molecular weight 1 million, manufactured by Nagase ChemteX Corp., 70 parts by weight of HTR-860P-3), antimony oxide as antimony trioxide (manufactured by Nippon Seiko Co., Ltd., PATOX-U), 8 parts by weight, and a carboxyl group as a dispersant Methyl ethyl ketone was added to a composition comprising 8 parts by weight of a copolymer (Disperbyk 111, manufactured by Big Chemie Japan Co., Ltd.), stirred and mixed, kneaded using a bead mill, and vacuum degassed.
This varnish was applied onto a 50 μm-thick polyethylene terephthalate film subjected to a release treatment using a doctor blade and dried by heating at a temperature of 150 ° C. for 5 minutes to form a semi-cured noise suppression sheet. On the surface of this sheet, a polyethylene terephthalate film having a release treatment of 50 μm in thickness was superposed so that the release surface was in contact with the surface of the noise suppression sheet, and cured by heating and pressing at a temperature of 170 ° C. and a pressure of 4 MPa for 30 minutes. It was 40 micrometers when the thickness of the hardening noise suppression sheet single-piece | unit was measured.
（実施例２）
扁平軟磁性材料粉末とし、Ｆｅ−Ｓｉ−Ｂ−Ｎｂ−Ｃｕ系合金であるＦｅ７３．５Ｓｉ１３．５Ｂ９Ｎｂ３Ｃｕ１の溶湯を水噴霧し、得られた粉末をアトライタで処理して、扁平粉末（平均粒子径６０μｍ、平均厚み３μｍ）としたもの１０００重量部、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５）２０重量部、クレゾールノボラック型エポキシ樹脂（東都化成株式会社製、ＹＤＣＮ−７０３）１５重量部、臭素化フェノール樹脂（帝人化成株式会社製、ファイヤーガードＦＧ２０００）５０重量部、硬化促進剤として硬化促進剤１−シアノエチル−２−フェニルイミダゾール（キュアゾール２ＰＺ−ＣＮ、四国化成株式会社製を使用）０．４重量部、エポキシ基含有アクリル系共重合体としてエポキシ基含有アクリルゴム（分子量１００万、ナガセケムテックス株式会社製、ＨＴＲ−８６０Ｐ−３）１００重量部、アンチモン酸化物として三酸化二アンチモン（日本精鉱株式会社製、ＰＡＴＯＸ−Ｕ）１０重量部、分散剤としてカルボキシル基を含む共重合体（ビックケミー・ジャパン株式会社製、Ｄｉｓｐｅｒｂｙｋ１１１）８重量部からなる組成物に、メチルエチルケトンを加えて撹拌混合し、さらにビーズミルを用いて混練し、真空脱気した。
このワニスを、厚み５０μｍの離型処理したポリエチレンテレフタレートフィルム上にドクターブレードを用いて塗布し、温度１５０℃で５分間加熱乾燥して、半硬化状態のノイズ抑制シートを形成した。このシートの表面に、さらに厚み５０μｍの離型処理したポリエチレンテレフタレートフィルムを離型面がノイズ抑制シート表面に接するように重ね合わせ、温度１７０℃、圧力４ＭＰａ、３０分間、加熱加圧硬化した。硬化したノイズ抑制シート単体の厚みを測定したところ、４０μｍであった。
(Example 2)
A flat soft magnetic material powder, Fe 73.5 Si 13.5 B 9 Nb 3 Cu 1 molten metal, which is an Fe—Si—B—Nb—Cu alloy, is sprayed with water, and the obtained powder is treated with an attritor. 1000 parts by weight of a flat powder (average particle size 60 μm, average thickness 3 μm), 20 parts by weight of bisphenol A type epoxy resin (YD-8125, manufactured by Tohto Kasei Co., Ltd.) as an epoxy resin, cresol novolac type epoxy resin ( Toto Kasei Co., Ltd., YDCN-703) 15 parts by weight, brominated phenol resin (Teijin Kasei Co., Ltd., Fireguard FG2000) 50 parts by weight, curing accelerator 1-cyanoethyl-2-phenylimidazole (Cureazole) as a curing accelerator 2PZ-CN, made by Shikoku Kasei Co., Ltd.) 0.4 parts by weight, epoxy group-containing acrylic copolymer Epoxy group-containing acrylic rubber (molecular weight 1 million, manufactured by Nagase ChemteX Corporation, HTR-860P-3) as a body, and antimony trioxide (Nippon Seiko Co., Ltd., PATOX-U) 10 as antimony oxide Methyl ethyl ketone is added to a composition comprising 8 parts by weight of a copolymer containing a carboxyl group as a dispersant (Disperbyk 111, manufactured by Big Chemie Japan Co., Ltd.), and the mixture is stirred and mixed. I worried.
This varnish was applied onto a 50 μm-thick polyethylene terephthalate film subjected to a release treatment using a doctor blade and dried by heating at a temperature of 150 ° C. for 5 minutes to form a semi-cured noise suppression sheet. On the surface of this sheet, a polyethylene terephthalate film having a release treatment of 50 μm in thickness was superposed so that the release surface was in contact with the surface of the noise suppression sheet, and cured by heating and pressing at a temperature of 170 ° C. and a pressure of 4 MPa for 30 minutes. It was 40 micrometers when the thickness of the hardening noise suppression sheet single-piece | unit was measured.
（実施例３）
扁平軟磁性材料粉末とし、Ｆｅ−Ｃｏ−Ｎｉ−Ｓｉ−Ｂ系合金であるＦｅ２４Ｃｏ１２．５Ｎｉ４５．５Ｓｉ２Ｂ１６の溶湯を水噴霧し、得られた粉末をアトライタで処理して、扁平粉末（平均粒子径５０μｍ、平均厚み３μｍ）としたもの１０００重量部、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５）２０重量部、クレゾールノボラック型エポキシ樹脂（東都化成株式会社製、ＹＤＣＮ−７０３）１５重量部、臭素化フェノール樹脂（帝人化成株式会社製、ファイヤーガードＦG２０００）５０重量部、硬化促進剤として硬化促進剤１−シアノエチル−２−フェニルイミダゾール（キュアゾール２ＰＺ−ＣＮ、四国化成株式会社製を使用）０．４重量部、エポキシ基含有アクリル系共重合体としてエポキシ基含有アクリルゴム（分子量１００万、ナガセケムテックス株式会社製、ＨＴＲ−８６０Ｐ−３）１００重量部、アンチモン酸化物として三酸化二アンチモン（日本精鉱株式会社製、ＰＡＴＯＸ−Ｕ）１０重量部、分散剤としてカルボキシル基を含む共重合体（ビックケミー・ジャパン株式会社製、Ｄｉｓｐｅｒｂｙｋ１１１）８重量部からなる組成物に、メチルエチルケトンを加えて撹拌混合し、さらにビーズミルを用いて混練し、真空脱気した。
このワニスを、厚み５０μｍの離型処理したポリエチレンテレフタレートフィルム上にドクターブレードを用いて塗布し、温度１５０℃で５分間加熱乾燥して、半硬化状態のノイズ抑制シートを形成した。このシートの表面に、さらに厚み５０μｍの離型処理したポリエチレンテレフタレートフィルムを離型面がノイズ抑制シート表面に接するように重ね合わせ、温度１７０℃、圧力４ＭＰａ、３０分間、加熱加圧硬化した。硬化したノイズ抑制シート単体の厚みを測定したところ、４０μｍであった。
(Example 3)
As a flat soft magnetic material powder, Fe 24 Co 12.5 Ni 45.5 Si 2 B 16 melt, which is an Fe—Co—Ni—Si—B alloy, is sprayed with water, and the obtained powder is treated with an attritor. 1000 parts by weight of a flat powder (average particle size 50 μm, average thickness 3 μm), 20 parts by weight of a bisphenol A type epoxy resin (manufactured by Tohto Kasei Co., Ltd., YD-8125) as an epoxy resin, a cresol novolac type epoxy resin ( Toto Kasei Co., Ltd., YDCN-703) 15 parts by weight, brominated phenol resin (Teijin Kasei Co., Ltd., Fireguard FG2000) 50 parts by weight, curing accelerator 1-cyanoethyl-2-phenylimidazole (Cureazole) as a curing accelerator 2PZ-CN, manufactured by Shikoku Kasei Co., Ltd.) 0.4 parts by weight, epoxy group-containing acrylic Epoxy group-containing acrylic rubber (molecular weight: 1,000,000, manufactured by Nagase ChemteX Corporation, HTR-860P-3) as a coalescence, antimony trioxide (Nippon Seiko Co., Ltd., PATOX-U) as antimony oxide 10 Methyl ethyl ketone is added to a composition consisting of 8 parts by weight of a copolymer containing a carboxyl group as a dispersant (Disperbyk 111, manufactured by Big Chemie Japan Co., Ltd.), and the mixture is stirred and mixed. I worried.
This varnish was applied onto a 50 μm-thick polyethylene terephthalate film subjected to a release treatment using a doctor blade and dried by heating at a temperature of 150 ° C. for 5 minutes to form a semi-cured noise suppression sheet. On the surface of this sheet, a polyethylene terephthalate film having a release treatment of 50 μm in thickness was superposed so that the release surface was in contact with the surface of the noise suppression sheet, and cured by heating and pressing at a temperature of 170 ° C. and a pressure of 4 MPa for 30 minutes. It was 40 micrometers when the thickness of the hardening noise suppression sheet single-piece | unit was measured.
（実施例４）
扁平軟磁性材料粉末とし、Ｆｅ−Ｎｉ−Ｍｏ系合金であるＦｅ１６Ｎｉ７９Ｍｏ５の溶湯を水噴霧し、得られた粉末をアトライタで処理して、扁平粉末（平均粒子径５０μｍ、平均厚み３μｍ）としたもの１０００重量部、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５）２０重量部、クレゾールノボラック型エポキシ樹脂（東都化成株式会社製、ＹＤＣＮ−７０３）１５重量部、臭素化フェノール樹脂（帝人化成株式会社製、ファイヤーガードＦG２０００）５０重量部、硬化促進剤として硬化促進剤１−シアノエチル−２−フェニルイミダゾール（キュアゾール２ＰＺ−ＣＮ、四国化成株式会社製を使用）０．４重量部、エポキシ基含有アクリル系共重合体としてエポキシ基含有アクリルゴム（分子量１００万、ナガセケムテックス株式会社製、ＨＴＲ−８６０Ｐ−３）１００重量部、アンチモン酸化物として三酸化二アンチモン（日本精鉱株式会社製、ＰＡＴＯＸ−Ｕ）１０重量部、分散剤としてカルボキシル基を含む共重合体（ビックケミー・ジャパン株式会社製、Ｄｉｓｐｅｒｂｙｋ１１１）８重量部からなる組成物に、メチルエチルケトンを加えて撹拌混合し、さらにビーズミルを用いて混練し、真空脱気した。
このワニスを、厚み５０μｍの離型処理したポリエチレンテレフタレートフィルム上にドクターブレードを用いて塗布し、温度１５０℃で５分間加熱乾燥して、半硬化状態のノイズ抑制シートを形成した。このシートの表面に、さらに厚み５０μｍの離型処理したポリエチレンテレフタレートフィルムを離型面がノイズ抑制シート表面に接するように重ね合わせ、温度１７０℃、圧力４ＭＰａ、３０分間、加熱加圧硬化した。硬化したノイズ抑制シート単体の厚みを測定したところ、４０μｍであった。
Example 4
A flat soft magnetic material powder, Fe 16 Ni 79 Mo 5 , which is an Fe—Ni—Mo alloy, is sprayed with water, and the resulting powder is treated with an attritor to obtain a flat powder (average particle size 50 μm, average thickness). 3 μm) 1000 parts by weight, 20 parts by weight of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., YD-8125) as epoxy resin, 15 parts by weight of cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDCN-703) Part, 50 parts by weight of brominated phenolic resin (manufactured by Teijin Chemicals Ltd., Fireguard FG2000), curing accelerator 1-cyanoethyl-2-phenylimidazole (curazole 2PZ-CN, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator 0.4 part by weight, epoxy group-containing acrylic copolymer as epoxy group-containing acrylic copolymer 100 parts by weight (molecular weight 1,000,000, manufactured by Nagase ChemteX Corporation, HTR-860P-3), 10 parts by weight of antimony trioxide (made by Nippon Seiko Co., Ltd., PATOX-U) as an antimony oxide, as a dispersant Methyl ethyl ketone was added to a composition comprising 8 parts by weight of a copolymer containing a carboxyl group (manufactured by Big Chemie Japan Co., Ltd., Disperbyk111), stirred and mixed, kneaded using a bead mill, and vacuum degassed.
This varnish was applied onto a 50 μm-thick polyethylene terephthalate film subjected to a release treatment using a doctor blade and dried by heating at a temperature of 150 ° C. for 5 minutes to form a semi-cured noise suppression sheet. On the surface of this sheet, a polyethylene terephthalate film having a release treatment of 50 μm in thickness was superposed so that the release surface was in contact with the surface of the noise suppression sheet, and cured by heating and pressing at a temperature of 170 ° C. and a pressure of 4 MPa for 30 minutes. It was 40 micrometers when the thickness of the hardening noise suppression sheet single-piece | unit was measured.
（実施例５）
扁平軟磁性材料粉末とし、Ｆｅ−Ａｌ−Ｓｉ合金であるＦｅ８５Ａｌ５．５Ｓｉ９．５の溶湯を水噴霧し、得られた粉末をアトライタで処理して、扁平粉末（平均粒子径６０μｍ、平均厚み３μｍ）としたもの１０００重量部、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５）１２重量部、クレゾールノボラック型エポキシ樹脂（東都化成株式会社製、ＹＤＣＮ−７０３）９重量部、臭素化フェノール樹脂（帝人化成株式会社製、ファイヤーガードＦG２０００）３０重量部、硬化促進剤として硬化促進剤１−シアノエチル−２−フェニルイミダゾール（キュアゾール２ＰＺ−ＣＮ、四国化成株式会社製を使用）０．２４重量部、エポキシ基含有アクリル系共重合体としてエポキシ基含有アクリルゴム（分子量１００万、ナガセケムテックス株式会社製、ＨＴＲ−８６０Ｐ−３）６０重量部、アンチモン酸化物として三酸化二アンチモン（日本精鉱株式会社製、ＰＡＴＯＸ−Ｕ）７重量部、分散剤としてカルボキシル基を含む共重合体（ビックケミー・ジャパン株式会社製、Ｄｉｓｐｅｒｂｙｋ１１１）８重量部からなる組成物に、メチルエチルケトンを加えて撹拌混合し、さらにビーズミルを用いて混練し、真空脱気した。
このワニスを、厚み５０μｍの離型処理したポリエチレンテレフタレートフィルム上にドクターブレードを用いて塗布し、温度１５０℃で５分間加熱乾燥して、半硬化状態のノイズ抑制シートを形成した。このシートの表面に、さらに厚み５０μｍの離型処理したポリエチレンテレフタレートフィルムを離型面がノイズ抑制シート表面に接するように重ね合わせ、温度１７０℃、圧力４ＭＰａ、３０分間、加熱加圧硬化した。硬化したノイズ抑制シート単体の厚みを測定したところ、４０μｍであった。
(Example 5)
A flat soft magnetic material powder, Fe 85 Al 5.5 Si 9.5 , which is an Fe—Al—Si alloy, is sprayed with water, and the obtained powder is treated with an attritor to obtain a flat powder (average particle size 60 μm). , Average thickness 3 μm) 1000 parts by weight, epoxy resin as bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., YD-8125), cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDCN-703) ) 9 parts by weight, 30 parts by weight of brominated phenolic resin (manufactured by Teijin Chemicals Ltd., Fireguard FG2000), curing accelerator 1-cyanoethyl-2-phenylimidazole (Cureazole 2PZ-CN, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator 0.24 parts by weight, epoxy group-containing acrylic as an epoxy group-containing acrylic copolymer 60 parts by weight of rubum (molecular weight 1 million, manufactured by Nagase ChemteX Corporation, HTR-860P-3), 7 parts by weight of antimony trioxide (manufactured by Nippon Seiko Co., Ltd., PATOX-U) as an antimony oxide, as a dispersant Methyl ethyl ketone was added to a composition comprising 8 parts by weight of a copolymer containing a carboxyl group (manufactured by Big Chemie Japan Co., Ltd., Disperbyk 111), mixed with stirring, kneaded using a bead mill, and vacuum degassed.
This varnish was applied onto a 50 μm-thick polyethylene terephthalate film subjected to a release treatment using a doctor blade and dried by heating at a temperature of 150 ° C. for 5 minutes to form a semi-cured noise suppression sheet. On the surface of this sheet, a polyethylene terephthalate film having a release treatment of 50 μm in thickness was superposed so that the release surface was in contact with the surface of the noise suppression sheet, and cured by heating and pressing at a temperature of 170 ° C. and a pressure of 4 MPa for 30 minutes. It was 40 micrometers when the thickness of the hardening noise suppression sheet single-piece | unit was measured.
（比較例１）
扁平軟磁性材料粉末とし、Ｆｅ−Ａｌ−Ｓｉ合金であるＦｅ８５Ａｌ５．５Ｓｉ９．５の溶湯を水噴霧し、得られた粉末をアトライタで処理して、扁平粉末（平均粒子径６０μｍ、平均厚み３μｍ）としたもの１０００重量部、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５）６０重量部、クレゾールノボラック型エポキシ樹脂（東都化成株式会社製、ＹＤＣＮ−７０３）４５重量部、臭素化フェノール樹脂（帝人化成株式会社製、ファイヤーガードＦG２０００）１５０重量部、硬化促進剤として硬化促進剤１−シアノエチル−２−フェニルイミダゾール（キュアゾール２ＰＺ−ＣＮ、四国化成株式会社製を使用）１．２重量部、エポキシ基含有アクリル系共重合体としてエポキシ基含有アクリルゴム（分子量１００万、ナガセケムテックス株式会社製、ＨＴＲ−８６０Ｐ−３）２１０重量部、アンチモン酸化物として三酸化二アンチモン（日本精鉱株式会社製、ＰＡＴＯＸ−Ｕ）２４重量部、分散剤としてカルボキシル基を含む共重合体（ビックケミー・ジャパン株式会社製、Ｄｉｓｐｅｒｂｙｋ１１１）８重量部からなる組成物に、メチルエチルケトンを加えて撹拌混合し、さらにビーズミルを用いて混練し、真空脱気した。
このワニスを、厚み５０μｍの離型処理したポリエチレンテレフタレートフィルム上にドクターブレードを用いて塗布し、温度１５０℃で５分間加熱乾燥して、半硬化状態のノイズ抑制シートを形成した。このシートの表面に、さらに厚み５０μｍの離型処理したポリエチレンテレフタレートフィルムを離型面がノイズ抑制シート表面に接するように重ね合わせ、温度１７０℃、圧力４ＭＰａ、３０分間、加熱加圧硬化した。硬化したノイズ抑制シート単体の厚みを測定したところ、４０μｍであった。
(Comparative Example 1)
A flat soft magnetic material powder, Fe 85 Al 5.5 Si 9.5 , which is an Fe—Al—Si alloy, is sprayed with water, and the obtained powder is treated with an attritor to obtain a flat powder (average particle size 60 μm). 1000 parts by weight of an average thickness of 3 μm), 60 parts by weight of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., YD-8125) as an epoxy resin, cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDCN-703) ) 45 parts by weight, 150 parts by weight of a brominated phenolic resin (manufactured by Teijin Chemicals Ltd., Fireguard FG2000), a curing accelerator 1-cyanoethyl-2-phenylimidazole (Curesol 2PZ-CN, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator 1.2 parts by weight, epoxy group-containing acrylic as an epoxy group-containing acrylic copolymer 210 parts by weight of ril rubber (molecular weight 1 million, manufactured by Nagase ChemteX Corporation, HTR-860P-3), 24 parts by weight of antimony trioxide (Nippon Seiko Co., Ltd., PATOX-U) as an antimony oxide, as a dispersant Methyl ethyl ketone was added to a composition comprising 8 parts by weight of a copolymer containing a carboxyl group (manufactured by Big Chemie Japan Co., Ltd., Disperbyk111), stirred and mixed, kneaded using a bead mill, and vacuum degassed.
This varnish was applied onto a 50 μm-thick polyethylene terephthalate film subjected to a release treatment using a doctor blade and dried by heating at a temperature of 150 ° C. for 5 minutes to form a semi-cured noise suppression sheet. On the surface of this sheet, a polyethylene terephthalate film having a release treatment of 50 μm in thickness was superposed so that the release surface was in contact with the surface of the noise suppression sheet, and cured by heating and pressing at a temperature of 170 ° C. and a pressure of 4 MPa for 30 minutes. It was 40 micrometers when the thickness of the hardening noise suppression sheet single-piece | unit was measured.
（比較例２）
扁平軟磁性材料粉末とし、Ｆｅ−Ａｌ−Ｓｉ合金であるＦｅ８５Ａｌ５．５Ｓｉ９．５の溶湯を水噴霧し、得られた粉末をアトライタで処理して、扁平粉末（平均粒子径６０μｍ、平均厚み３μｍ）としたもの１０００重量部、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５）２０重量部、クレゾールノボラック型エポキシ樹脂（東都化成株式会社製、ＹＤＣＮ−７０３）１５重量部、臭素化フェノール樹脂（帝人化成株式会社製、ファイヤーガードＦG２０００）５０重量部、硬化促進剤として硬化促進剤１−シアノエチル−２−フェニルイミダゾール（キュアゾール２ＰＺ−ＣＮ、四国化成株式会社製を使用）０．４重量部、エポキシ基含有アクリル系共重合体としてエポキシ基含有アクリルゴム（分子量１００万、ナガセケムテックス株式会社製、ＨＴＲ−８６０Ｐ−３）７０重量部、分散剤としてカルボキシル基を含む共重合体（ビックケミー・ジャパン株式会社製、Ｄｉｓｐｅｒｂｙｋ１１１）８重量部からなる組成物（アンチモン酸化物の添加無）に、メチルエチルケトンを加えて撹拌混合し、さらにビーズミルを用いて混練し、真空脱気した。
このワニスを、厚み５０μｍの離型処理したポリエチレンテレフタレートフィルム上にドクターブレードを用いて塗布し、温度１５０℃で５分間加熱乾燥して、半硬化状態のノイズ抑制シートを形成した。このシートの表面に、さらに厚み５０μｍの離型処理したポリエチレンテレフタレートフィルムを離型面がノイズ抑制シート表面に接するように重ね合わせ、温度１７０℃、圧力４ＭＰａ、３０分間、加熱加圧硬化した。硬化したノイズ抑制シート単体の厚みを測定したところ、４０μｍであった。
(Comparative Example 2)
A flat soft magnetic material powder, Fe 85 Al 5.5 Si 9.5 , which is an Fe—Al—Si alloy, is sprayed with water, and the obtained powder is treated with an attritor to obtain a flat powder (average particle size 60 μm). , Average thickness 3 μm) 1000 parts by weight, epoxy resin bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., YD-8125), cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDCN-703) ) 15 parts by weight, 50 parts by weight of brominated phenol resin (manufactured by Teijin Chemicals Ltd., Fireguard FG2000), curing accelerator 1-cyanoethyl-2-phenylimidazole (Curesol 2PZ-CN, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator 0.4 parts by weight, epoxy group-containing acrylic as an epoxy group-containing acrylic copolymer A composition comprising 70 parts by weight of rubber (molecular weight: 1 million, manufactured by Nagase ChemteX Corporation, HTR-860P-3) and 8 parts by weight of a copolymer containing a carboxyl group as a dispersant (Disperbyk 111, manufactured by Big Chemie Japan Co., Ltd.) Methyl ethyl ketone was added to (mixed with no antimony oxide), mixed with stirring, kneaded using a bead mill, and vacuum degassed.
This varnish was applied onto a 50 μm-thick polyethylene terephthalate film subjected to a release treatment using a doctor blade and dried by heating at a temperature of 150 ° C. for 5 minutes to form a semi-cured noise suppression sheet. On the surface of this sheet, a polyethylene terephthalate film having a release treatment of 50 μm in thickness was superposed so that the release surface was in contact with the surface of the noise suppression sheet, and cured by heating and pressing at a temperature of 170 ° C. and a pressure of 4 MPa for 30 minutes. It was 40 micrometers when the thickness of the hardening noise suppression sheet single-piece | unit was measured.
（比較例３）
扁平軟磁性材料粉末とし、Ｆｅ−Ａｌ−Ｓｉ合金であるＦｅ８５Ａｌ５．５Ｓｉ９．５の溶湯を水噴霧し、得られた粉末をアトライタで処理して、扁平粉末（平均粒子径６０μｍ、平均厚み３μｍ）としたもの１０００重量部、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５）２０重量部、クレゾールノボラック型エポキシ樹脂（東都化成株式会社製、ＹＤＣＮ−７０３）１５重量部、臭素化フェノール樹脂（帝人化成株式会社製、ファイヤーガードＦG２０００）５０重量部、硬化促進剤として硬化促進剤１−シアノエチル−２−フェニルイミダゾール（キュアゾール２ＰＺ−ＣＮ、四国化成株式会社製を使用）０．４重量部、アクリル系共重合体としてアクリルゴム（分子量１０万、日本ゼオン株式会社製、Ｎｉｐｏｌ ＡＲ３１）７０重量部、アンチモン酸化物として三酸化二アンチモン（日本精鉱株式会社製、ＰＡＴＯＸ−Ｕ）８重量部、分散剤としてカルボキシル基を含む共重合体（ビックケミー・ジャパン株式会社製、Ｄｉｓｐｅｒｂｙｋ１１１）８重量部からなる組成物に、メチルエチルケトンを加えて撹拌混合し、さらにビーズミルを用いて混練し、真空脱気した。
このワニスを、厚み５０μｍの離型処理したポリエチレンテレフタレートフィルム上にドクターブレードを用いて塗布し、温度１５０℃で５分間加熱乾燥して、半硬化状態のノイズ抑制シートを形成した。このシートの表面に、さらに厚み５０μｍの離型処理したポリエチレンテレフタレートフィルムを離型面がノイズ抑制シート表面に接するように重ね合わせ、温度１７０℃、圧力４ＭＰａ、３０分間、加熱加圧硬化した。硬化したノイズ抑制シート単体の厚みを測定したところ、４０μｍであった。
(Comparative Example 3)
A flat soft magnetic material powder, Fe 85 Al 5.5 Si 9.5 , which is an Fe—Al—Si alloy, is sprayed with water, and the obtained powder is treated with an attritor to obtain a flat powder (average particle size 60 μm). , Average thickness 3 μm) 1000 parts by weight, epoxy resin bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., YD-8125), cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDCN-703) ) 15 parts by weight, 50 parts by weight of brominated phenol resin (manufactured by Teijin Chemicals Ltd., Fireguard FG2000), curing accelerator 1-cyanoethyl-2-phenylimidazole (Curesol 2PZ-CN, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator 0.4 parts by weight, acrylic rubber as an acrylic copolymer (molecular weight 100,000, Nippon ON Co., Ltd., Nipol AR31) 70 parts by weight, antimony trioxide as antimony oxide (Nippon Seiko Co., Ltd., PATOX-U) 8 parts by weight, and a copolymer containing a carboxyl group as a dispersant (BIC Chemie Japan) Methyl ethyl ketone was added to a composition consisting of 8 parts by weight of Disperbyk 111) manufactured by Co., Ltd., mixed with stirring, kneaded using a bead mill, and vacuum degassed.
This varnish was applied onto a 50 μm-thick polyethylene terephthalate film subjected to a release treatment using a doctor blade and dried by heating at a temperature of 150 ° C. for 5 minutes to form a semi-cured noise suppression sheet. On the surface of this sheet, a polyethylene terephthalate film having a release treatment of 50 μm in thickness was superposed so that the release surface was in contact with the surface of the noise suppression sheet, and cured by heating and pressing at a temperature of 170 ° C. and a pressure of 4 MPa for 30 minutes. It was 40 micrometers when the thickness of the hardening noise suppression sheet single-piece | unit was measured.
実施例・比較例で作製したノイズ抑制シートについて、下記に示す方法により評価した。結果を表１に示す。
（電磁波吸収性）
シールド効果評価器（株式会社アドバンテスト製、ＴＲ１７３０１Ａ）を用い、１０ＭＨｚの磁性シールド特性を測定し、電磁波減衰量が２ｄＢ以上のものを良好、２ｄＢ未満のものを不良とした。尚、プローブは磁界プローブを用いた。
About the noise suppression sheet | seat produced by the Example and the comparative example, it evaluated by the method shown below. The results are shown in Table 1.
(Electromagnetic wave absorption)
Using a shield effect evaluator (manufactured by Advantest Corporation, TR17301A), the magnetic shield characteristics at 10 MHz were measured, and those with an electromagnetic wave attenuation of 2 dB or more were good and those with less than 2 dB were judged as bad. Note that a magnetic field probe was used as the probe.
（難燃性）
ＵＬ９４垂直燃焼試験に準じて行い、分類が９４ＶＴＭ−０又は９４ＶＴＭ−１のものを良好、それ以外を不良とした。
(Flame retardance)
It carried out according to UL94 vertical combustion test, and the classification | category of 94VTM-0 or 94VTM-1 was made favorable, and the others were made bad.
（信頼性）
１２１℃−１００％ＲＨ−２気圧の高温高湿槽に２時間処理し、そのシートを１２０℃で６０分脱湿乾燥した。処理前の引張り試験結果と照らし合わせ、機械的強度（破断強度）の低下の割合が３０％未満のものを良好、それ以外を不良とした。
(reliability)
The sheet was treated in a high-temperature and high-humidity bath at 121 ° C.-100% RH-2 atm for 2 hours, and the sheet was dehumidified and dried at 120 ° C. for 60 minutes. In comparison with the tensile test results before the treatment, those having a decrease in mechanical strength (breaking strength) of less than 30% were judged good, and others were judged defective.
表１に示すように、実施例１〜５で作製したノイズ抑制シートは、いずれも電磁波減衰量が２ｄＢ以上であり良好な電磁波吸収性を示した。また、難燃性もＵＬ９４垂直燃焼試験において良好であった。さらに、１２１℃−１００％ＲＨ−２気圧の環境での機械的強度の低下の割合は３０％未満であり良好であった。これらのことから、本発明のノイズ抑制シートが優れていることは明らかである。これに対し、比較例１のノイズ抑制シートは樹脂総量に対する扁平軟磁性材料粉末量が少ない（言い換えると、扁平軟磁性材料粉末量に対して樹脂総量が多い）ため、電磁波減衰量が小さかった。また、比較例２のノイズ抑制シートはアンチモン酸化物を添加しなかったため、難燃性が不良であった。また、比較例３のノイズ抑制シートはエポキシ基含有アクリル系共重合体を用いなかったため、信頼性が不良であった。 As shown in Table 1, all of the noise suppression sheets prepared in Examples 1 to 5 had an electromagnetic wave attenuation amount of 2 dB or more, and showed good electromagnetic wave absorbability. In addition, flame retardancy was also good in the UL94 vertical combustion test. Furthermore, the rate of decrease in mechanical strength in an environment of 121 ° C.-100% RH-2 atm was good, being less than 30%. From these, it is clear that the noise suppression sheet of the present invention is excellent. In contrast, the noise suppression sheet of Comparative Example 1 had a small amount of flat soft magnetic material powder with respect to the total amount of resin (in other words, a large amount of resin with respect to the amount of flat soft magnetic material powder), and thus the electromagnetic wave attenuation amount was small. Moreover, since the noise suppression sheet | seat of the comparative example 2 did not add an antimony oxide, the flame retardance was unsatisfactory. Moreover, since the noise suppression sheet of Comparative Example 3 did not use an epoxy group-containing acrylic copolymer, the reliability was poor.
１． 扁平軟磁性材料粉末
２． アンチモン酸化物
３． マトリクス樹脂
1. 1. Flat soft
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