TW200416976A - Electromagnetic-wave absorptive heat-conduction sheet - Google Patents
Electromagnetic-wave absorptive heat-conduction sheet Download PDFInfo
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- TW200416976A TW200416976A TW092136240A TW92136240A TW200416976A TW 200416976 A TW200416976 A TW 200416976A TW 092136240 A TW092136240 A TW 092136240A TW 92136240 A TW92136240 A TW 92136240A TW 200416976 A TW200416976 A TW 200416976A
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- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
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Abstract
Description
200416976 (1) 玖、發明說明 【發明所屬之技術領域】 本發明爲關於¥彳電fe;波吸收性導熱層之至少一面，疊 層電絕緣性之高分子薄膜之兼具柔軟性和強度之電絕緣性 的電磁波吸收性導熱薄片。 【先前技術】 近年，隨著發展移動體通訊、雷達、行動電話、無線 LAN等之電磁波利用，於生活空間中頻頻發生電磁波散 亂，且阻礙電磁波、電子機器的錯誤動作等之問題。 又，發展個人電腦、行動電話等內部所配置的CPU、 MPU、LSI等之電子機器要素的高密度化、高集成化、及 電子機器要素對於印刷電路基板的高密度裝配化，且隨著 電磁波於機器內部放射，使得此電磁波於機器內部反射、 充滿，並且經由機器本身所發生的電磁波而亦引起內部電 磁干涉的問題。 以往，於進行阻礙電磁干涉對策之情形中，必須具有 雜訊對策的專門知識和經驗，其對策必須以許多時間，加 上於事前確保對策構件之實際裝配空間上具有難點。爲了 解決此類問題點，乃開始使用藉由吸收電磁波而減低反射 波及穿透波的電磁波吸收體。 更且，隨著CPU、MPU、LSI等之電子機器要素的高 密度化、高集成化，使得發熱量變大，若未有效進行冷卻 ，則亦同時具有因熱暴走而錯誤動作的問題。以往’將發 -4 - (2) (2)200416976 熱有效率釋出至外部的手段爲將充塡導熱性粉末的矽油潤 滑脂和矽橡膠，設置於CPU、MPU、LSI等與熱槽之間， 減少接觸熱阻力的方法。但是，此方法並不可能迴避前述 機器內部之電磁干涉的問題。 因此，對於電子機器內部之特別爲CPU、MPU、LSI 等之電子機器要素的高密度化、高集成化的部位，必須具 有電磁波吸收性能、導熱性能的構材。薄片構材視需要， 可分成（1 )磁性粉末於基質聚合物中分散的電磁波吸收 性薄片、（2 )以氧化鋁爲首之導熱性粉末爲於基質聚合 物中分散的導熱性薄片、（3 )將兩粉末共同充塡成爲兼 具電磁波吸收性能和導熱性能的薄片等三種薄片。 近年，以個人電腦爲首的電子機器的信號處理速度爲 非常高速化、各元件的動作周波數亦多爲數百MHz〜數 GHz。因此，於電子機器內部所發生之電磁波雜訊的周波 數亦多爲GHz帶域。爲了抑制此些電磁波雜訊，雖亦考 慮應用將錳鋅系鐵素體、鎳鋅系鐵素體爲代表的尖晶石型 立方晶鐵素體粉末於基質聚合物中均勻分散的薄片，但此 鐵素體薄片所察見之效果主要在MHz帶，對於GHz帶的 效果薄弱。因此，現在令MHz帶至GHz帶爲止效果大的 金屬系軟磁性粉於基質聚合物中均勻分散的薄片乃成爲主 流。 一般，軟磁性金屬爲導電性，故此粉末於基質聚合物 中均勻分散的薄片的絕緣破壞電壓小。因此，於電子機器 內，裝配此薄片時，必須注意不會令電子機器內部的各部 -5- (3) 200416976 分電性短路。特別，兼具電磁波吸收性能 片，多被使用於夾在元件和放熱構材間’ 構材之間的電性連接成爲問題的情況中， 片。於此類情況中，採用將僅具有電性絕 片使用夾於元件與放熱構材間並且令熱由 且於其周圍無電性問題的處所’配置僅具 的薄片，進行抑制電磁波雜訊的煩雜方法 電子機器內部發生電磁波雜訊之處所 CPU、MPU、LSI等元件，但有時以元件 圖案接連之所謂的元件腳部、和印刷電路 且發生電磁波雜訊。於此類情形中，直接 薄片覆蓋此處爲佳，但軟磁性金屬粉於基 分散的薄片則因薄片無絕緣性，故因爲電 無法使用。 基本上，令軟磁性金屬粉於絕緣性之 勻分散的薄片中，導電性之軟磁性金屬粉 聚合物而被彼此絕緣，於提高電磁波吸收 軟磁性金屬粉予以高充塡，使得金屬粉彼 、接觸，故此薄片的絕緣破壞電壓變小。 於特開平1 1 - 4 5 804號公報（專利文 以矽烷系偶合劑於金屬軟磁性粉表面設置 磁波吸收體，於特開平2 0 0 1 - 3 0 8 5 8 4號 2 )中’揭示以長鏈烷基矽烷於金屬軟磁 緣性被膜的電波吸收體，但此些具有有機 和導熱性能的薄 但於元件與放熱 則無法使用此薄 緣導熱性能的薄 元件中散放，並 有電磁波吸收性 〇 多爲局速驅動的 與印刷電路基板 圖案成爲天線並 以電磁波吸收性 質聚合物中均勻 路短路的問題而 基質聚合物中均 彼此間經由基質 性能上，必須將 此間的距離變近 獻1 )中，揭示 絕絕性被膜的電 公報（專利文獻 性粉表面設置絕 基分子的被膜， -6- (4) (4)200416976 難以取得具有充分絕緣破壞電壓的電磁波吸收性薄片。 於特開平9 一 1 1 5 3 3 2號公報（專利文獻3 )中，揭示 將磁性粉末與高分子樹脂混合成形之電磁波吸收體的電波 入射面’與1〜5 GHz之周波數區域中之複介電率實數部 爲8以下的著色樹脂薄膜予以疊層的內裝用電波吸收體， 於特開平1 1 一 1 9 5 8 93號公報（專利文獻4 )中，揭示於 軟磁性粉末與有機黏合劑所構成之複合磁性體層的至少一 面設置絕緣層的電磁波干涉抑制體，於特開 2 0 0 0 -2 3 2 2 9 7號公報（專利文獻5 )中，揭示將可撓性高分子材 料中分散金屬磁性粉末之電磁波吸收層的外表面，以介電 率爲1 〇以下的可撓性高分子材料所覆蓋的電磁波吸收體 ，此些構成雖可製作電絕緣性的薄片，但關於導電性能則 不夠充分。 於特開200 1 — 1 68246號公報（專利文獻6 )中，揭 示包含於基材及該基材之至少單面施以導熱性樹脂層的導 熱性薄片，且再提案該基材爲由塑膠薄膜、金屬箔或單面 黏合薄膜所構成，但此構成缺乏電磁波吸收性能。 〔專利文獻1〕 特開平1 1 — 45 8 04號公報 〔專利文獻2〕 特開2 00 1 - 3 08 5 84號公報 〔專利文獻3〕 特開平9 — 1 1 5 3 3 2號公報 〔專利文獻4〕 (5) (5)200416976 特開平1 1 — 1 9 5 8 93號公報 〔專利文獻5〕 特開2000 — 232297號公報 〔專利文獻6〕 特開2 0 0 1 — 1 6 8 2 4 6號公報 〔發明所欲解決之課題〕 本發明爲鑑於此類先前之問題，以提供兼具高電磁波 吸收性能和高導熱性能、柔軟且具有強度，操作容易且具 有電絕緣性的電磁波吸收性導熱性薄片爲其目的。 【發明內容】 〔用以解決課題的手段及發明的實施形態〕 本發明者等人爲了達成上述目的而重覆致力檢討，結 果發現對軟磁性金屬粉及電絕緣性之導熱性充塡劑於基質 聚合物中分散之電磁波吸收性導熱層的至少一面，疊層電 絕緣性高分子薄膜，且令薄片厚度方向的絕緣破壞電壓爲 1 kV以上，則可取得兼具高電磁波吸收性能和高導熱性 能、柔軟且具有強度並且操作容易，可適用於各種電子機 器之電絕緣性的電磁波吸收性導熱性薄片，並且完成本發 明。 因此，本發明爲提供對軟磁性金屬粉及電絕緣性之導 熱性充塡劑於基質聚合物中分散之電磁波吸收性導熱層的 至少一面，疊層電絕緣性高分子薄膜的電磁波吸收性導熱 -8- (6) (6)200416976 性薄片，於薄片厚度方向之絕緣破壞電壓爲1 kV以上之 電絕緣性的電磁波吸收性導熱性薄片。 以下，更詳細說明本發明。 本發明之電絕緣性電磁波吸收性導熱性薄片爲對軟磁 性金屬粉及電絕緣性之導熱性充塡劑於基質聚合物中分散 之電磁波吸收性導熱層的至少一面，疊層電絕緣性之高分 子薄膜則可取得。 本發明之電絕緣性電磁波吸收性導熱性薄片於薄片厚 度方向的絕緣破壞電壓爲1 kV以上，較佳爲1.5 kV以上 ，更佳爲2 kV以上。本發明之薄片中的電磁波吸收性導 熱層爲令軟磁性金屬粉於基質聚合物中分散的構造，故其 絕緣破壞電壓小。因此，經由疊層電絕緣性的高分子薄膜 ，則可確保薄片厚度方向上的絕緣破壞電壓。絕緣破壞電 壓未滿1 kV，則於電子機器內之電路短路的危險性增加 ，且適用範圍狹窄。 又，本發明之電絕緣性電磁波吸收性導電性薄片中的 電磁波吸收性導熱層的導熱率，爲2 W / mK以上爲佳， 且以3 W/ mK以上爲更佳。於本發明之電絕緣性電磁波 吸收性導熱性薄片中，因爲疊層導電率較小的高分子薄膜 ，故於薄片全體厚度方向上的導熱率，小於電磁波吸收性 導熱層的導熱率。因此，電磁波吸收性導熱層的導熱率必 須設計爲高。電磁波吸收性導熱層之導熱率未滿2 W / mK，則導熱性能不夠充分，且用途亦受到限定。 於本發明之電絕緣性電磁波吸收性導熱性薄片中，於 -9 - (7) (7)200416976 疊層電絕緣性高分子薄膜之電磁波吸收性導熱層面之反面 ，將導熱率爲2 W/ mK以上之比該高分子薄膜更柔軟之 電絕緣性的導熱性充塡劑於基質聚合物中分散的導熱層、 或軟磁性金屬粉及電絕緣性之導熱性充塡劑於基質聚合物 中分散的電磁波吸收性導熱層予以疊層亦可。藉此’可令 本發明之電絕緣性電磁波吸收性導熱性薄片與發熱源和/ 或放熱裝置之接觸熱阻力變小，可取得更良好的放熱特性 〇 本發明之電絕緣性電磁波吸收性導熱性薄片中之電絕 緣性高分子薄膜的厚度爲5 0 // m以下爲佳，且以3 0 // m 以下爲更佳。一般，高分子薄膜的導熱率爲小至0.2 W/ mK左右，故於薄片全體之厚度方向的平均導熱率爲比電 磁波吸收性導熱層的導熱率小。經由高分子薄膜的疊層， 則薄片全體之厚度方向上的導熱率，爲隨著高分子薄膜之 厚度變厚而呈現指數函數性地減少。因此，高分子薄膜的 厚度愈薄愈佳。高分子薄膜之厚度若超過50//m，則於 薄片全體厚度方向上之平均導熱率並不充分，且恐其用途 亦受限定。還有，上述高分子薄膜之厚度若過薄，則因絕 緣破壞電壓並不充分，且操作性變差，故以1 // m以上爲 佳。 於本發明中，與電磁波吸收性導熱疊層之高分子薄膜 的材質，若爲可形成薄膜的高分子材料即可，並無特別限 制’可使用公知的熱硬化性樹脂、熱塑性樹脂。但，必須 根據本發明之電絕緣性電磁波吸收性導熱性薄片的使用溫 -10- (8) (8)200416976 度，考慮高分子薄膜的材質。熱硬化性薄膜可例示例如環 氧樹脂、聚酯樹脂、丙烯酸樹脂、聚矽氧烷樹脂、聚胺基 甲酸乙酯樹脂等。熱塑性樹脂例如可使用聚乙烯、聚對酞 酸乙二酯、聚萘酸乙二酯、聚丙烯、聚苯乙烯、尼龍、聚 醯亞胺樹脂、ABS樹脂、聚甲基丙烯酸甲酯、丁二烯橡膠 、腈橡膠等。此些高分子材料可爲單獨一種、或混合使用 二種以上。 .本發明之電磁波吸收性導熱層中所含之軟磁性金屬粉 末由供給安定性、價格等方面而言，以含有鐵元素爲佳。 可列舉例如羰基鐵、電解鐵、Fe — Cr系合金、Fe — Si系 合金、Fe—Ni系合金、Fe— A1系合金、Fe — Co系合金、 Fe— Al— Si 系合金、Fe— Cr— Si 系合金、Fe— Cr— A1 系 合金、Fe— Si— Ni系合金、Fe — Si— Cr-Ni系合金等， 但並非限定於此。此時，由價格等方面而言，以含有15 重量％以上之鐵元素爲佳。 此些軟磁性金屬粉末可單獨使用一種，且亦可組合使 用二種以上。粉末之形狀可單獨使用扁平狀、粒狀之任一 者，且倂用兩者亦可。 軟磁性金屬粉末之平均粒徑爲0.1 // m以上100 // m 以下爲佳，且特別使用1 // m以上5 0 // m以下爲佳。平均 粒徑未滿0.1 // m之情形中，則粒子的比表面積變成過大 •，且恐難以高充塡化。又，於平均粒徑爲超過1 00 // m情 形中，於薄片表面出微小的凹凸，且恐令接觸熱阻力變大 -11 - (9) (9)200416976 電磁波吸收性導熱層中之軟磁性金屬粉末的含量’以 電磁波吸收性導熱層全量之1 0〜8 0 V ο 1 % (容量％、以下 相同），特別以15〜70 vol%爲佳。未滿10 vol%，則有 時無法取得充分的電磁波吸收性能，於超過80 vol%之情 形中，則恐令電磁波吸收性能層變脆。 本發明之電磁波吸收性導熱層及導熱層中所含之電絕 緣性的導熱性充塡劑，以電絕緣性物質之氧化鋁、氧化砍 、鐵素體、氮化矽、氮化硼、氮化鋁之粉末等爲佳。 以鐵素體做爲導熱性充塡劑時，以使用電絕緣性高之 Ni-Zn系和Μη— Zn系等之尖晶石型立方晶鐵素體粉末 爲佳。此些軟磁性鐵素體因爲亦兼具電磁波吸收性能’故 可彌補本發明之軟磁性金屬粉的電磁波吸收性能，且爲佳 〇 導熱性粉末可單獨使用一種，且亦可組合使用二種以 上。 導熱性粉末之平均粒徑爲0.1 # m以上1 0 0 // m以下 爲佳，且特別以使用1 # m以上5 0 // m以下爲佳。平均粒 徑爲未滿0.1 μ m之情形中，粒子的比表面積變得過大且 恐難高充塡化，且於充塡率爲相同時’薄片的導熱率變小 。又，於平均粒徑爲超過1 00 // m之情形中，於薄片表面 出現微小的凹凸’且恐令接觸熱阻力變大。 電磁波吸收性導熱層中之導熱性粉末的含量，於取得 指定之電磁波吸收性能上’考慮與軟磁性金屬粉之充塡率 的均衡而言，則以電磁波吸收性導熱層全體之1 0〜7 0 v 01 -12- (10) (10)200416976 %，特別以2 0〜5 0 ν ο 1 %爲佳。未滿1 〇 v 〇 1 %則有時無法 取得充分的導熱性能，於超過νο1%之情形中，則相對 地令軟磁性金屬粉的含有率降低，且具有無法取得充分電 磁波吸收性能的可能性。 又，導熱層中之導熱性粉末的含有量以導熱層全量之 30〜80 vol%，特別以40〜80 vol%爲佳。未滿30 vol% ，則有時無法取得充分的導熱性能，於超過8 5 vol %之情 形中，則恐令導熱層變脆。 本發明之電磁波吸收性導熱層及導熱層之基質聚合物 可列舉有機基聚矽氧烷、丙烯酸橡膠、伸乙基丙烯橡膠、 氟橡膠等，可視目的用途而選擇。此些基質聚合物可單獨 使用一種，或混合使用二種以上。 又，於本發明中，將電磁波吸收性導熱層、導熱層及 視需要之矽烷偶合劑等之粉末表面處理劑、難燃劑、交聯 劑、控制劑、交聯促進劑等予以適當，適量配合亦可。 於本發明中，構成電磁波吸收性導熱層及導熱層之組 成物可經由將各個軟磁性金屬粉末和/或導熱性粉末、與 基質聚合物、與視需要之其他成分混合則可製造。此處， 軟磁性金屬粉末和/或導熱性粉末與基質聚合物的混合可 經由均質器、揑和機、二根輥、星型混合器等之混合機進 行至混合均勻爲止，但並無特別限定。 電磁波吸收性導熱層或導熱層與高分子薄膜的層合方 法爲將上述組成物於高分子薄膜上直接加壓成型、塗層成 型、砑光成型等以疊層的方法、和使用上述組成物並將電 -13- (11) (11)200416976 磁波吸收性導熱層或導熱層以塗層成型和加壓成型等予以 成型後，透過黏合層並將高分子薄膜予以加壓接黏的方法 等，但並非限定於此。又，爲了強化高分子薄膜與各層間 的接黏，亦可將層合前之高分子薄膜的接合面予以塗底處 理。 本發明之電絕緣性電磁波吸收性導熱性薄片的層合構 造可列舉例如，圖1 ( a )所示般之將一層電磁波吸收性 導熱層1與一層局分子薄膜層2予以疊層而成的二層層合 構造，如圖1 (b)所不般之於一層高分子薄膜層2之單 面疊層電磁波吸收性導熱層1，於另一面疊層導熱層3所 構成的三層構造，如圖1 ( c )所示般之於一層高分子薄 膜層2之兩面將電磁波吸收性導熱層1、1予以疊層而成 的三層構造，如圖1 ( d )所示般之於一層電磁波吸收性 導熱層1的兩面將各一層之高分子薄膜層2、2予以疊層 而成的三層構造，如圖1 ( e )所示般之於一層電磁波吸 收性導熱層1的兩面將各一層之高分子薄膜層2予以疊層 ，且再於高分子薄膜層上分別疊層導熱層3所構成的五層 構造等，但並非特別限定於此。 本發明之電絕緣性電磁波吸收性導熱性薄片全體的厚 度爲0.1 mm以上10 mm以下，特別以0.3 mm以上3 mm 以下爲佳。 本發明之電絕緣性電磁波吸收性導熱性薄片於薄片全 體之厚度方向的平均導熱率爲1.5 W/ mK以上，特別以2 W/ mK以上爲佳。導熱率未滿1.5 W/ mK，則恐令用途 - 14- (12) 200416976 受到限定。200416976 (1) Description of the invention [Technical field to which the invention belongs] The present invention relates to at least one side of a wave-absorbing heat-conducting layer, and a layer of an electrically insulating polymer film having both flexibility and strength. Electrically insulating electromagnetic wave absorbing thermally conductive sheet. [Previous technology] In recent years, with the development of electromagnetic wave use in mobile communications, radar, mobile phones, wireless LAN, etc., electromagnetic wave scattering frequently occurs in living spaces, and problems such as electromagnetic waves and malfunction of electronic equipment are hindered. In addition, electronic devices such as CPUs, MPUs, and LSIs, which are arranged inside personal computers and mobile phones, have been developed to have higher density and higher integration, and higher density assembly of electronic device elements to printed circuit boards has been developed. Radiation inside the machine causes this electromagnetic wave to be reflected and filled inside the machine, and also causes the problem of internal electromagnetic interference via the electromagnetic wave generated by the machine itself. In the past, in the case of countermeasures against electromagnetic interference, it was necessary to have expertise and experience in countermeasures against noise, and the countermeasures had to take a lot of time to ensure the actual assembly space of countermeasure components in advance. In order to solve such problems, electromagnetic wave absorbers that reduce reflected waves and transmitted waves by absorbing electromagnetic waves have begun to be used. Furthermore, with the increase in the density and integration of electronic device elements such as CPUs, MPUs, and LSIs, the amount of heat generated will increase. If cooling is not effectively performed, there will also be a problem of malfunction due to thermal storms. In the past, the means for efficiently releasing the heat to the outside-(2) (2) 200416976 was to dissipate thermally conductive powder-filled silicone oil grease and silicone rubber into the CPU, MPU, LSI, and the heat sink. Method to reduce thermal resistance of contact. However, this method is not possible to avoid the problem of electromagnetic interference inside the aforementioned machine. Therefore, for high-density and highly-integrated parts of electronic devices such as CPUs, MPUs, and LSIs, it is necessary to have a structure that has electromagnetic wave absorption performance and thermal conductivity. The sheet structure can be divided into (1) electromagnetic wave-absorbing sheets in which magnetic powder is dispersed in a matrix polymer, (2) thermally conductive powders such as alumina as heat-conductive sheets dispersed in a matrix polymer, and ( 3) Filling the two powders together into three flakes, such as flakes with electromagnetic wave absorption performance and thermal conductivity performance. In recent years, the speed of signal processing of electronic devices, including personal computers, has been extremely high, and the number of operating cycles of each component has been often in the range of several hundred MHz to several GHz. Therefore, the frequency of the electromagnetic wave noise generated in the electronic equipment is mostly in the GHz band. In order to suppress such electromagnetic noise, it is also considered to use a thin plate in which the spinel-type cubic ferrite powder typified by manganese-zinc-based ferrite and nickel-zinc-based ferrite is dispersed in the matrix polymer. The effect observed in this ferrite sheet is mainly in the MHz band, and the effect on the GHz band is weak. Therefore, a thin sheet of a metal-based soft magnetic powder having a large effect in the MHz band to the GHz band is uniformly dispersed in the matrix polymer. Generally, a soft magnetic metal is conductive, so that a thin film having a uniformly dispersed powder in a matrix polymer has a low dielectric breakdown voltage. Therefore, when assembling this sheet in an electronic device, care must be taken not to short-circuit electrical parts of the electronic device. In particular, sheets that have both electromagnetic wave absorption properties are often used in cases where the electrical connection between the element and the exothermic member becomes a problem. In such cases, only thin sheets are used in places that have only electrical insulators sandwiched between the element and the exothermic structure and that allow heat to escape without electrical problems around them. Methods Electronic components such as CPUs, MPUs, and LSIs are generated inside electronic devices. However, the so-called component feet and printed circuits are sometimes connected in a component pattern and electromagnetic noise occurs. In such cases, it is better to cover the sheet directly, but the sheet with soft magnetic metal powder dispersed on the base is not electrically insulating because the sheet is not insulating. Basically, the soft magnetic metal powder is insulated from each other in the uniformly dispersed sheet of the insulation, and the conductive soft magnetic metal powder polymer is insulated from each other, and the soft magnetic metal powder is highly charged to improve the electromagnetic wave absorption, so that the metal powder is Contact, the insulation breakdown voltage of the sheet becomes smaller. Unexamined in Japanese Unexamined Patent Publication No. 1 1-4 5 804 (Patent document uses a silane-based coupling agent to provide a magnetic wave absorber on the surface of a metal soft magnetic powder, and disclosed in Japanese Unexamined Patent Publication No. 2 0 1-3 0 8 5 8 4 2) Radio wave absorbers with long-chain alkyl silanes on metal soft magnetic edge coatings, but these thin organic and thermal conductive materials, but cannot be used in thin components with heat conduction properties and heat dissipation, and electromagnetic waves Absorptivity is mostly a problem of driving at a local speed with a printed circuit board pattern that becomes an antenna and short-circuiting the uniform path in the polymer with electromagnetic wave absorption properties. The matrix polymers all pass through each other in terms of matrix performance, and the distance between them must be made closer. 1), an electrical bulletin revealing an absolute film (a film with patent-based molecules on the surface of the patent document powder, -6- (4) (4) 200416976, it is difficult to obtain an electromagnetic wave absorbing sheet having a sufficient dielectric breakdown voltage. Kaiping 9 1 1 5 3 3 2 (Patent Document 3) discloses a radio wave incident surface of an electromagnetic wave absorber formed by mixing a magnetic powder and a polymer resin, and a cycle of 1 to 5 GHz. A radio wave absorber for interior use in which a colored resin film with a real dielectric constant of 8 or less in the area is laminated is disclosed in Japanese Patent Application Laid-Open No. 1 1 to 1 9 5 8 93 (Patent Document 4). An electromagnetic wave interference suppressor provided with an insulating layer on at least one side of a composite magnetic layer composed of a magnetic powder and an organic binder is disclosed in Japanese Patent Application Laid-Open No. 2 0 0-2 3 2 2 9 7 (Patent Document 5). The outer surface of the electromagnetic wave absorbing layer in which the metallic magnetic powder is dispersed in the flexible polymer material is an electromagnetic wave absorber covered with a flexible polymer material having a dielectric constant of 10 or less. Although these structures can be used to produce electrically insulating Sheets, however, are insufficient in terms of electrical conductivity. Japanese Patent Application Laid-Open No. 200 1-68246 (Patent Document 6) discloses a thermally conductive sheet that includes a substrate and a thermally conductive resin layer on at least one side of the substrate. Furthermore, it is proposed that the base material is composed of a plastic film, a metal foil, or a single-sided adhesive film, but this structure lacks electromagnetic wave absorption performance. [Patent Document 1] Japanese Patent Application Laid-Open No. 1 1-45 8 04 [Patent Document 2]JP 2 00 1-3 08 5 84 [Patent Document 3] JP 9-1 1 5 3 3 2 [Patent Document 4] (5) (5) 200416976 JP 1 1-1 9 5 8 [Patent Document 5] JP 2000-232297 [Patent Document 6] JP 2 0 1-1 6 8 2 4 6 [Problems to be Solved by the Invention] The present invention is made in view of such prior art. The problem is to provide an electromagnetic wave absorptive and thermally conductive sheet that has both high electromagnetic wave absorption performance and high thermal conductivity, is soft and has strength, is easy to handle, and has electrical insulation. [Summary of the Invention] [Means for Solving the Problems and Embodiments of the Invention] The present inventors and others have repeatedly reviewed in order to achieve the above-mentioned objective, and as a result, have found that the soft magnetic metal powder and the thermally conductive filler of electrical insulation are used in At least one side of the electromagnetic wave-absorbing heat-conducting layer dispersed in the matrix polymer is laminated with an electrically insulating polymer film, and the insulation failure voltage in the thickness direction of the sheet is 1 kV or more, and it can achieve both high electromagnetic wave absorption performance and high thermal conductivity. The present invention has properties, flexibility, strength, and ease of operation, and is applicable to electrically insulating electromagnetic wave-absorbing heat-conductive sheets of various electronic devices. Therefore, the present invention is to provide at least one side of an electromagnetic wave absorbing thermally conductive layer in which a soft magnetic metal powder and an electrically insulating thermally conductive filler are dispersed in a matrix polymer, and the electromagnetic wave absorbing thermal conduction of an electrically insulating polymer film is laminated. -8- (6) (6) 200416976 thin sheet, an electrically insulating electromagnetic wave absorptive and thermally conductive sheet with an insulation breakdown voltage in the thickness direction of the sheet of 1 kV or more. Hereinafter, the present invention will be described in more detail. The electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention is laminated on at least one side of the electromagnetic wave absorptive and thermally conductive layer in which the soft magnetic metal powder and the electrically insulating thermally conductive filler are dispersed in the matrix polymer. Polymer films are available. The dielectric breakdown voltage of the electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention in the thickness direction of the sheet is 1 kV or more, preferably 1.5 kV or more, and more preferably 2 kV or more. The electromagnetic wave absorptive heat-conducting layer in the sheet of the present invention has a structure in which soft magnetic metal powder is dispersed in a matrix polymer, so that its insulation breakdown voltage is small. Therefore, by laminating an electrically insulating polymer film, the dielectric breakdown voltage in the thickness direction of the sheet can be secured. The insulation damage voltage is less than 1 kV, the danger of short circuits in electronic equipment increases, and the scope of application is narrow. The thermal conductivity of the electromagnetic wave-absorbing heat conductive layer in the electrically insulating electromagnetic wave-absorbing conductive sheet of the present invention is preferably 2 W / mK or more, and more preferably 3 W / mK or more. In the electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention, since the polymer film having a relatively low conductivity is laminated, the thermal conductivity in the thickness direction of the entire sheet is smaller than the thermal conductivity of the electromagnetic wave absorptive and thermally conductive layer. Therefore, the thermal conductivity of the electromagnetic wave-absorbing heat conductive layer must be designed to be high. If the thermal conductivity of the electromagnetic wave absorptive heat-conducting layer is less than 2 W / mK, the thermal conductivity is insufficient and the use is limited. In the electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention, on the opposite side of the electromagnetic wave absorptive and thermally conductive layer of the -9-(7) (7) 200416976 laminated electrical insulating polymer film, the thermal conductivity is 2 W / mK or more than the polymer film, a softer electrically insulating thermally conductive filler dispersed in a matrix polymer, or a soft magnetic metal powder and an electrically insulating thermally conductive filler in a matrix polymer The dispersed electromagnetic wave absorptive heat conductive layer may be laminated. Thereby, the contact thermal resistance between the electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention and a heat source and / or a heat radiation device can be reduced, and a better heat release characteristic can be obtained. The electrically insulating electromagnetic wave absorptive heat conduction of the present invention The thickness of the electrically insulating polymer film in the flexible sheet is preferably 50 0 // m or less, and more preferably 30 0 // m or less. Generally, the thermal conductivity of a polymer film is as small as about 0.2 W / mK. Therefore, the average thermal conductivity in the thickness direction of the entire sheet is smaller than the thermal conductivity of the electromagnetic wave-absorbing thermally conductive layer. Through the lamination of polymer films, the thermal conductivity in the thickness direction of the entire sheet decreases exponentially as the polymer film becomes thicker. Therefore, the thinner the polymer film, the better. If the thickness of the polymer film exceeds 50 // m, the average thermal conductivity in the thickness direction of the entire sheet is insufficient, and its use may be limited. In addition, if the thickness of the polymer film is too thin, the insulation failure voltage is insufficient and the operability is deteriorated, so it is preferably 1 // m or more. In the present invention, the material of the polymer film laminated with the electromagnetic wave absorptive and thermally conductive material is not particularly limited as long as it is a polymer material capable of forming a thin film. A known thermosetting resin or thermoplastic resin can be used. However, it is necessary to consider the material of the polymer film according to the use temperature of the electrically insulating electromagnetic wave absorbing and thermally conductive sheet of the present invention -10- (8) (8) 200416976 degrees. Examples of the thermosetting film include epoxy resin, polyester resin, acrylic resin, polysiloxane resin, polyurethane resin, and the like. As the thermoplastic resin, for example, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polystyrene, nylon, polyimide resin, ABS resin, polymethyl methacrylate, butadiene can be used. Ethylene rubber, nitrile rubber, etc. These polymer materials may be used alone or in combination of two or more. The soft magnetic metal powder contained in the electromagnetic wave absorptive heat-conducting layer of the present invention preferably contains an iron element in terms of supply stability, price, and the like. Examples include carbonyl iron, electrolytic iron, Fe—Cr based alloy, Fe—Si based alloy, Fe—Ni based alloy, Fe—A1 based alloy, Fe—Co based alloy, Fe—Al—Si based alloy, and Fe—Cr —Si-based alloy, Fe—Cr—A1 based alloy, Fe—Si—Ni based alloy, Fe—Si—Cr—Ni based alloy, etc., but it is not limited thereto. In this case, in terms of price, it is preferable to contain 15% by weight or more of the iron element. These soft magnetic metal powders may be used singly or in combination of two or more kinds. The shape of the powder may be any one of a flat shape and a granular shape, or both of them may be used. The average particle diameter of the soft magnetic metal powder is preferably from 0.1 // m to 100 // m, and particularly preferably from 1 // m to 5 0 // m. When the average particle size is less than 0.1 // m, the specific surface area of the particles becomes too large, and it is difficult to achieve high charge. In addition, when the average particle diameter is more than 1 00 // m, minute irregularities appear on the surface of the sheet, and the contact thermal resistance may increase. -11-(9) (9) 200416976 Softness in the electromagnetic wave-absorbing heat-conducting layer The content of the magnetic metal powder is 10% to 80% of the total amount of the electromagnetic wave absorbing thermal conductive layer (volume%, the same below), and particularly preferably 15 to 70 vol%. If it is less than 10 vol%, sufficient electromagnetic wave absorption performance may not be obtained. In the case of more than 80 vol%, the electromagnetic wave absorption performance layer may become brittle. The electromagnetic wave absorptive thermally conductive layer and the electrically insulating thermally conductive filler contained in the thermally conductive layer of the present invention are made of electrically insulating materials such as alumina, oxide, ferrite, silicon nitride, boron nitride, and nitrogen. Aluminium powder is preferred. When ferrite is used as the thermally conductive filler, it is preferable to use spinel-type cubic ferrite powders, such as Ni-Zn series and Mn-Zn series, which have high electrical insulation properties. Since these soft magnetic ferrites also have electromagnetic wave absorption performance, they can compensate for the electromagnetic wave absorption performance of the soft magnetic metal powder of the present invention, and are good. The thermally conductive powder can be used alone or in combination of two or more. . The average particle diameter of the thermally conductive powder is preferably 0.1 # m or more and 1 0 0 // m or less, and particularly preferably 1 # m or more and 5 0 // m or less. When the average particle diameter is less than 0.1 µm, the specific surface area of the particles becomes too large and it is difficult to achieve high charge, and the thermal conductivity of the sheet becomes small when the charge rate is the same. When the average particle diameter is more than 1 00 // m, minute irregularities appear on the surface of the sheet, and the thermal resistance to contact may increase. The content of the thermally conductive powder in the electromagnetic wave absorbing thermally conductive layer is to obtain the specified electromagnetic wave absorbing performance. In consideration of the balance with the filling rate of the soft magnetic metal powder, the entire electromagnetic wave absorbing thermally conductive layer is 1 to 7 0 v 01 -12- (10) (10) 200416976%, particularly preferably 20 to 5 0 ν ο 1%. If it is less than 1 〇v 〇1%, sufficient thermal conductivity may not be obtained. If it exceeds νο1%, the content of the soft magnetic metal powder may be relatively reduced, and sufficient electromagnetic wave absorption performance may not be obtained. . The content of the thermally conductive powder in the thermally conductive layer is preferably 30 to 80 vol%, and more preferably 40 to 80 vol%. If it is less than 30 vol%, sufficient thermal conductivity may not be obtained. If it exceeds 85 vol%, the thermally conductive layer may become brittle. The electromagnetic wave absorptive heat-conducting layer and the matrix polymer of the heat-conducting layer of the present invention include organic polysiloxane, acrylic rubber, ethylene propylene rubber, fluorine rubber, and the like, and can be selected according to the intended use. These matrix polymers may be used singly or in combination of two or more kinds. In the present invention, a powder surface treatment agent, a flame retardant, a cross-linking agent, a control agent, a cross-linking accelerator, and the like, such as an electromagnetic wave absorptive heat-conducting layer, a heat-conducting layer, and an optional silane coupling agent, are appropriately and appropriately used Cooperation is also possible. In the present invention, the composition constituting the electromagnetic wave-absorbing heat-conducting layer and the heat-conducting layer can be produced by mixing each soft magnetic metal powder and / or heat-conducting powder with a matrix polymer and other components as necessary. Here, the mixing of the soft magnetic metal powder and / or the thermally conductive powder and the matrix polymer may be performed through a mixer such as a homogenizer, a kneader, two rollers, a star mixer, and the like, but it is not particularly limited. limited. A method for laminating an electromagnetic wave absorbing heat-conducting layer or a heat-conducting layer and a polymer film is a method of laminating the above composition on a polymer film by direct pressure molding, coating molding, calender molding, etc., and using the above composition. The method of forming an electric -13- (11) (11) 200416976 magnetic wave absorptive heat-conducting layer or a heat-conducting layer by coating molding and pressure molding, etc., and then pressing the polymer film through the adhesive layer, etc. , But not limited to this. In addition, in order to strengthen the adhesion between the polymer film and each layer, the bonding surface of the polymer film before lamination may be undercoated. The laminated structure of the electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention includes, for example, a laminate of one electromagnetic wave absorptive and thermally conductive layer 1 and one local molecular film layer 2 as shown in FIG. 1 (a). As shown in Fig. 1 (b), the two-layer laminated structure is a three-layer structure composed of a single-layer laminated electromagnetic wave absorbing heat-conducting layer 1 on a polymer film layer 2 and a heat-conducting layer 3 on the other side. As shown in FIG. 1 (c), a three-layer structure in which electromagnetic wave-absorbing heat-conducting layers 1 and 1 are laminated on both sides of a polymer film layer 2 is shown in FIG. 1 (d). As shown in Fig. 1 (e), the two surfaces of the electromagnetic wave absorptive heat-conducting layer 1 are stacked on both sides of the electromagnetic wave absorptive heat-conducting layer 1, and the two surfaces of the electromagnetic wave-absorptive heat-conducting layer 1 Each layer of the polymer thin film layer 2 is laminated, and a five-layer structure including a heat conductive layer 3 is laminated on the polymer thin film layer, but it is not particularly limited thereto. The thickness of the entire electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention is preferably 0.1 mm or more and 10 mm or less, and particularly preferably 0.3 mm or more and 3 mm or less. The average thermal conductivity of the electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention in the thickness direction of the entire sheet is 1.5 W / mK or more, particularly preferably 2 W / mK or more. If the thermal conductivity is less than 1.5 W / mK, the application may be restricted-14- (12) 200416976 Limited.
本發明之電絕緣性電磁波吸收性導熱性薄片之表面層 中’於至少一面之裝配面，即於發熱物和/或放熱構材之 表面所配置層的硬度，以A s c ar C硬度計測定時爲7 〇以 上’特別以60以下爲佳。於薄片表面變軟下，則薄片表 面追隨發熱物和/或放熱構材表面的微細凹凸而變形，若 以微觀而言，則兩者的接觸面積變大。結果，可令薄片與 發熱物和/或放熱構材的接觸熱阻力樊小。Ascar C硬度 若大於7〇，則薄片與發熱物和/或放熱構材的接觸熱阻 力變大，具有放熱特性不夠充分的可能性。In the surface layer of the electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention, the hardness of the layer disposed on at least one side of the surface layer, that is, the surface disposed on the surface of the heating object and / or the exothermic structure, is measured by an Asc ar C hardness meter. It is preferably 70 or more, and particularly preferably 60 or less. When the surface of the sheet becomes soft, the surface of the sheet deforms following the fine unevenness on the surface of the heat-generating object and / or the exothermic material, and in microscopic terms, the contact area between the two becomes larger. As a result, it is possible to reduce the contact thermal resistance of the sheet and the heat-generating object and / or the exothermic structure. If the Ascar C hardness is greater than 70, the contact thermal resistance between the sheet and the heat-generating object and / or the exothermic structure becomes large, and there is a possibility that the exothermic characteristics are insufficient.
本發明之電絕緣性電磁波吸收性導熱性薄片，因爲兼 具高電磁波吸收性能和高導熱性能，且爲電絕緣性，故裝 配於電子機器內部時，並不必要特別照料對於印刷配線電 路爲首之各部分的電性短路，且可裝配於最適的，處所。因 此，可抑制以往所增加之電子機器內部的電磁波雜訊，並 且亦可抑制電磁波對於外部的漏洩量，並且亦可將電子機 器要素所發生之熱放熱至機器外部。 【實施方式】 〔實施例〕 以下，示出實施例及比較例，具體說明本發明，但本 發明並非被下述實施例所限制。 〔實施例1〕 -15- (13) (13)200416976 將室溫下之黏度爲30 Pa · s ’以二甲基乙烯基甲矽烷 氧基將兩端封閉之含乙燃基一甲基聚砂氧院做爲基質油’ 且以下述式 /?H3\ CH3^SiO-4-Si-(OCH3)3 \ GH3/3〇 所示之含有矽原子結合烷氧基之有機基聚矽氧烷做爲各種 充塡粉末之表面處理劑，並且相對於該充塡粉末之合計量 1 〇 〇重量份添加1重量份，再加入平均粒徑1 0 // m之球狀 Fe- 12% Cr- 3% S i軟磁性金屬粉末和導熱性粉末之平 均粒徑1 // m的粒狀氧化鋁粉末（昭和電工股份有限公司 製商品名：A L — 4 7 — 1 )，且以星型混合器於室溫中攪拌 混合後，再一邊攪拌一邊進行1 2 0 °C、1小時的熱處理， 製作本發明之電絕緣性電磁波吸收性導熱性薄片中之電磁 波吸收性導熱層的基質組成物。 其次，將1分子中具有二個以上結合至矽原子之氫原 子的有機基氣聚砂氧院、舶族金屬系觸媒、乙快醇系反應 控制劑添加混合。有機基氫聚矽氧烷的添加量爲令其氫原 子之莫耳數與上述基質組成物中之二甲基乙烯基甲矽烷氧 基的旲耳數比爲〇 · 7。最終的配合組成爲相對於聚砂氧院 成分1 0 0重量份，調整成軟磁性金屬粉末丨〇 〇重量份、導 熱性粉末之氧化鋁粉末4 0 0重量份。 將做爲此電磁波吸收性導熱層的組成物，於預先以塗 底劑C (信越化學工業股份有限公司製商品名）予以塗底 處理之12.5// m厚度的聚醯亞胺薄膜上，以加壓成型並於 -16- (14) (14)200416976 1 2 0 °c、加熱硬化1 〇分鐘，取得圖1 ( a )所示之二層構 造之合計薄膜厚度1 mm之本發明的電絕緣性電磁波吸收 性導熱性薄片。 〔實施例2〕 除了令電磁波吸收性導熱層之軟磁性金屬粉爲平均粒 徑30// m之扁平形狀Fe— 5.5% Si，且電磁波吸收性導 熱層之最終的配合組成爲相對於聚矽氧烷成分1 〇〇重量份 ，調整爲軟磁性金屬粉末900重量份、導熱性粉末之氧化 鋁粉末5 00重量份以外，同實施例1處理，取得圖1 ( a )所示二層構造之合計薄片厚度0.3 mm之本發明的電絕 緣性電磁波吸收性導熱性薄片。 〔實施例3〕 電磁波吸收性導熱層之基質聚合物爲使用日信化學工 業股份有限公司製的丙烯酸橡膠RV- 25 20，且相對於此 丙烯酸橡膠1 0 0重量份，將平均粒徑3 0 // m之扁平形狀 F e — 5 _ 5 % S i軟磁性金屬粉末1 2 0 0重量份、平均粒徑1 // m之氧化鋁粉末（昭和電工股份公司製商品名：AL 一 4 7 — 1 ) 3 0 0重量份以揑和機予以均勻混合，作成電磁波 吸收性導熱層的基質組成物。相對於此基質組成物1 〇〇重 量份，將有機過氧化物之二（鄰）-甲基苯甲醯）過氧化 物〇 · 8重量份以二根輥予以混合後，以1 5 〇 t、1 0分鐘之 條件，於預先以塗底劑C (信越化學工業股份有限公司製 -17 - (15) 200416976 商品名）予以塗底處理之1 2 · 5从m厚度的聚醯亞胺薄膜上 ，以1 5 0 °C、1 〇分鐘之條件加壓成型’取得圖1 ( a )所 示之二層構造之合計薄片厚度1 m m之本發明的電絕緣性 電磁波吸收性導熱性薄片。 〔實施例4〕The electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention has both high electromagnetic wave absorption performance and high thermal conductivity, and is electrically insulating. Therefore, it is not necessary to take special care for printed wiring circuits when it is assembled inside an electronic device. Each part is electrically shorted and can be assembled in the most suitable place. Therefore, it is possible to suppress the electromagnetic wave noise inside the electronic device which has been increased in the past, and also to suppress the leakage amount of the electromagnetic wave to the outside, and it is also possible to dissipate the heat generated by the electronic device elements to the outside of the device. [Embodiments] [Examples] Hereinafter, examples and comparative examples will be shown to specifically describe the present invention, but the present invention is not limited to the following examples. [Example 1] -15- (13) (13) 200416976 The viscosity at room temperature was 30 Pa · s', and the two ends of the ethane-containing monomethyl polymer were closed with dimethylvinylsilyloxy As a base oil, the sand oxygen institute is an organic polysiloxane containing a silicon atom and an alkoxy group, which is represented by the following formula /? H3 \ CH3 ^ SiO-4-Si- (OCH3) 3 \ GH3 / 3〇 As a surface treatment agent for various filling powders, 1 part by weight is added to 1,000 parts by weight of the total amount of the filling powder, and spherical Fe- 12% Cr- 3% Si soft magnetic metal powder and thermally conductive powder with an average particle size of 1 // m granular alumina powder (trade name: AL — 4 7 — 1 manufactured by Showa Denko Corporation) and a star mixer After stirring and mixing at room temperature, heat treatment was performed at 120 ° C for 1 hour while stirring to prepare a matrix composition of an electromagnetic wave absorbing and thermally conductive layer in the electrically insulating electromagnetic wave absorbing and thermally conductive sheet of the present invention. Next, one molecule of an organic-based gas polysand oxygen plant having two or more hydrogen atoms bonded to silicon atoms, a family metal catalyst, and an ethylene glycol reaction control agent are added and mixed. The organic hydrogen polysiloxane is added in an amount such that the molar number ratio of the hydrogen atom to the molar number of the dimethylvinylsilyloxy group in the matrix composition is 0.7. The final compounded composition was adjusted to 100 parts by weight of the polysand oxygen compound, and was adjusted to soft magnetic metal powder, 400 parts by weight, and thermally conductive powder, 400 parts by weight of alumina powder. A composition of this electromagnetic wave-absorbing heat-conducting layer was coated on a polyimide film having a thickness of 12.5 / m in advance with a primer C (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.). It was press-molded and hardened at -16- (14) (14) 200416976 1 2 0 ° C and heat-hardened for 10 minutes to obtain the electricity of the present invention with a total film thickness of 1 mm as shown in Fig. 1 (a). Insulating electromagnetic wave absorbing thermally conductive sheet. [Example 2] Except that the soft magnetic metal powder of the electromagnetic wave absorptive heat conductive layer was a flat shape Fe—5.5% Si with an average particle diameter of 30 // m, and the final compound composition of the electromagnetic wave absorptive heat conductive layer was relative to polysilicon The oxane component was 100 parts by weight, and adjusted to 900 parts by weight of soft magnetic metal powder and 5,000 parts by weight of alumina powder of thermally conductive powder, and treated in the same manner as in Example 1 to obtain a two-layer structure shown in FIG. 1 (a). The electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention having a total sheet thickness of 0.3 mm. [Example 3] The matrix polymer of the electromagnetic wave-absorbing heat-conducting layer was an acrylic rubber RV-25 25 manufactured by Nissin Chemical Industry Co., Ltd., and the average particle size was 30 based on 100 parts by weight of the acrylic rubber. // flat shape of m F e — 5 _ 5% S i soft magnetic metal powder 1 2 0 0 parts by weight, average particle diameter 1 // m of alumina powder (trade name: Showa Denko Corporation: AL 1 4 7 — 1) 300 parts by weight are uniformly mixed with a kneader to form a matrix composition of an electromagnetic wave-absorbing heat conductive layer. With respect to 1,000 parts by weight of this matrix composition, 0.8 parts by weight of organic peroxide bis (o-)-methylbenzidine) peroxide was mixed by two rollers, and then 1500 t For 10 minutes, a polyimide film with a thickness of 1 to 5 m in thickness is prepared in advance with primer C (made by Shin-Etsu Chemical Industry Co., Ltd.-17-(15) 200416976). Then, press molding under the conditions of 150 ° C and 10 minutes was performed to obtain the electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention having a total sheet thickness of 1 mm in the two-layer structure shown in FIG. 1 (a). [Example 4]
除了令電磁波吸收性導熱層之最終的配合組成，相對 於聚矽氧烷成分100重量份，調整成軟磁性金屬粉末900 重量份、導熱性粉末氧化鋁粉末200重量份，且使用12.5 A m之PEN (聚萘酸乙二酯）薄膜做爲高分子薄膜以外， 同實施例2處理，取得圖1 ( a )所示之二層構造之合計 薄片厚度1 mm之本發明的電絕緣性電磁波吸收性導熱性 薄片。 〔實施例5〕In addition to the final blended composition of the electromagnetic wave-absorbing heat-conducting layer, it is adjusted to 900 parts by weight of soft magnetic metal powder and 200 parts by weight of thermally conductive alumina powder with respect to 100 parts by weight of the polysiloxane component. Except for PEN (polyethylene naphthalate) film as a polymer film, it was treated in the same manner as in Example 2 to obtain the two-layer structure shown in Fig. 1 (a) with a total sheet thickness of 1 mm and the electrically insulating electromagnetic wave absorption of the present invention. Thermally conductive sheet. [Example 5]
除了令導熱性粉末爲平均粒徑〇·9 #nl之氧化鋁粉末 (二井化學股份有限公司製商品名：HAN — 2)以外，同 實施例4處理，取得圖1 ( a )所示之二層構造之合計薄 片厚度1 m m之本發明的電絕緣性電磁波吸收性導熱性薄 片。 〔實施例6〕 除了電磁波吸收性導熱層之氧化鋁代替平均粒徑$ // m之粒狀Ni - Zn鐵素體粉末（戶田工業股份有限公司 -18- (16) (16)200416976 製商品名：BSN— 714 )，且其添加份數爲3 00重量份以 外，同實施例4處理，取得圖1 ( a )所示之二層構造之 合計薄片厚度1 mm之本發明的電絕緣性吸收性導熱性薄 片。 〔實施例7〕 基質聚合物爲使用有機過氧化物硬化型之聚矽氧烷橡 膠組成物，且將導熱層於厚度12.5//m之聚醯亞胺薄膜上 予以塗層成型。 將平均聚合度7,000之二甲基乙烯基生橡膠88重量 份、含有矽原子結合烷氧基之有機聚矽氧烷做爲導熱性充 塡粉末的表面處理劑1 2重量份、及做爲導熱性充塡劑之 平均粒徑1 8 // m的氧化鋁粉末（昭和電工股份有限公司 製商品名：AS — 3 0 ) 8 00重量份和平均粒徑4 // m之氧化 鋁粉末（昭和電工股份有限公司製商品名：AL — 24 ) 400 重量份以揑合混合至均勻爲止，製作導熱層的基質組成物 〇 相對於此基質組成物1 00重量份，將有機過氧化物之 二（鄰）甲基苯甲醯）過氧化物0.8重量份和甲苯40重 量份以均質器予以攪拌混合後，於預先以塗底劑C (信越 化學工業股份有限公司製商品名）予以塗底處理之厚度 12.5/zm的聚醯亞胺薄膜上塗層。再者，爲了除去甲苯， 設置4 0 °C — 5分鐘、8 0 °C — 5分鐘之階段性加熱步驟後， 於1 5 (TC - 5分鐘之條件下，令塗層薄片進行交聯、硬化 -19- (17) (17)200416976 ，於12·5 // m厚之聚醯亞胺薄膜的單面層合厚度〇·1 mm 的導熱層。 其次，將此層合品之導熱層層合面反側之聚醯亞胺薄 膜面，以塗底劑C (信越化學工業股份有限公司製商品名 )予以塗底處理後，將做爲實施例1所示之電磁波吸收性 導熱層的組成物，以加壓成型，於1 2 0 °C，加熱硬化1 0 分鐘，取得圖1(b)所示之三層構造之合計薄片厚度2 mm之本發明的電絕緣性電磁波吸收性導熱性薄片。 〔實施例8〕 除了使用厚度25//m之聚醯亞胺薄膜以外，同實施 例7處理，取得圖1 ( b )所示之三層構造之合計薄膜厚 度1 mm之本發明的電絕緣性電磁波吸收性導熱性薄片。 〔實施例9〕 除了令電磁波吸收性導熱層之厚度爲0.7 mm以外， 同實施例1處理，取得對1 2.5 // m厚之聚醯亞胺薄膜疊 層0 · 7 mm厚之電磁波吸收性導熱層者。 其次，相對於做爲基質聚合物之實施例1中電磁波吸 收性導熱層所用之聚矽氧烷組成物1 00重量份，將做爲導 熱性充塡劑之平均粒徑1 8 // m的氧化鋁粉末（昭和電工 股份有限公司製商品名：AS - 3 0 ) 600重量份和平均粒徑 4 // m的氧化鋁粉末（昭和電工股份有限公司製商品名： AL- 24 ) 3 0 0重量份充塡，作成導熱層組成物。 -20- (18) (18)200416976 將上述層合品之電磁波吸收性導熱層面反側之聚醯亞 胺薄膜面，以塗底劑C (信越化學工業股份有限公司製商 品名）予以塗底處理後，將此導熱層組成物於聚醯亞胺薄 膜面上，以0.3 mm之厚度予以無溶劑塗層後，以120°c 、10分鐘之條件令其交聯、硬化，取得圖1 ( b )所示之 三層構造之合計薄片厚度1 mm之本發明的電絕緣性電磁 波吸收性導熱性薄片。 〔實施例1 〇〕 使用有機過氧化物硬化型之聚矽氧烷橡膠組成物做爲 基質聚合物，並於厚度12.5 // m之聚醯亞胺薄膜上將電磁 波吸收性導熱層予以塗層成型。 將平均聚合度7, 〇〇〇之二甲基乙烯基生橡膠88重量 份，含有矽原子結合烷氧基有機聚矽氧烷做爲導熱性充塡 粉末之表面處理劑（2重量份，及'做爲軟磁性金屬粉之平 均粒徑3 0 // m之扁平形狀的F e — 5 . 5 % S i 9 0 0重量份和 導熱性粉末之平均粒徑1 // m的粒狀氧化鋁粉末（昭和電 工股份有限公司製商品名：AL — 47 - 1 ) 5 00重量份以揑 和機予以混合至均勻爲止，製作導熱層基質組成物。 相對於此基質組成物1 〇〇重量份，將有機過氧化物之 I (鄰一甲基苯甲醯）過氧化物0.8重量份和甲苯40重 量份以均質器予以攪拌混合後，於預先以塗底劑C (信越 t學工業股份有限公司製商品名）予以塗底處理之厚度 12_5//m的聚醯亞胺薄膜上塗層。再者，爲了除了甲苯， -21 - (19) 200416976 設置4(TC — 5分鐘、8(TC — 5分鐘之階段性加熱步驟後， 於1 5 (TC - 5分鐘之條件下，令塗層薄片進行交聯、硬化 ，於12.5//m厚之聚醯亞胺薄膜的單面層合厚度0.1 mm 的電磁波吸收性導熱層。Except that the thermally conductive powder was an alumina powder with an average particle diameter of 0.9 # nl (trade name: HAN-2 manufactured by Nikai Chemical Co., Ltd.), the same treatment as in Example 4 was performed to obtain the second one shown in FIG. 1 (a). The electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention having a total sheet thickness of 1 mm in the layer structure. [Example 6] Except for the electromagnetic wave absorbing heat-conducting layer, alumina replaces granular Ni-Zn ferrite powder with an average particle size of $ // m (Toda Industry Co., Ltd.-18- (16) (16) 200416976 Trade name: BSN- 714), and its added parts are other than 300 parts by weight, and treated in the same manner as in Example 4 to obtain the electrical insulation of the present invention with a total sheet thickness of 1 mm in the two-layer structure shown in FIG. 1 (a) Absorptive thermally conductive sheet. [Example 7] The matrix polymer was a silicone rubber composition using an organic peroxide curing type, and a thermally conductive layer was coated on a polyimide film having a thickness of 12.5 // m. 88 parts by weight of dimethyl vinyl raw rubber with an average degree of polymerization of 7,000, and organopolysiloxane containing a silicon atom-bound alkoxy group as the surface-treating agent for the thermally conductive powder 12 parts by weight, and as the thermal conductivity Alumina powder with an average particle size of 1 8 // m (as Showa Denko Corporation, trade name: AS — 3 0), 8 00 parts by weight and an alumina powder with an average particle size of 4 // m (Showa Product name: DAL 24) 400 parts by weight, kneaded and mixed until homogeneous, to produce a matrix composition of a thermally conductive layer. 0. 100 parts by weight of this matrix composition. ) Methyl benzamidine) 0.8 parts by weight of peroxide and 40 parts by weight of toluene are stirred and mixed in a homogenizer, and then the thickness is pre-coated with primer C (trade name of Shin-Etsu Chemical Industry Co., Ltd.) beforehand. 12.5 / zm polyimide film coating. Furthermore, in order to remove toluene, a step of heating at 40 ° C — 5 minutes and 80 ° C — 5 minutes was set, and then the coated sheet was crosslinked at 15 (TC-5 minutes). Hardened-19- (17) (17) 200416976, laminated with a thermally conductive layer with a thickness of 0.1 mm on one side of a polyimide film with a thickness of 12.5 // m. Second, the thermally conductive layer with this laminate The polyimide film on the opposite side of the lamination surface was primed with primer C (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and used as the electromagnetic wave-absorbing heat-conducting layer shown in Example 1. The composition is pressure-molded and heated and hardened at 120 ° C for 10 minutes to obtain the three-layer structure shown in Fig. 1 (b) with a total sheet thickness of 2 mm and the electrically insulating electromagnetic wave absorptive heat conduction of the present invention. [Example 8] Except that a polyimide film having a thickness of 25 // m was used, the same treatment as in Example 7 was performed to obtain a total film thickness of 1 mm according to the three-layer structure shown in FIG. 1 (b). [Electric Insulation Electromagnetic Wave Absorptive Thermally Conductive Sheet] [Example 9] Except that the thickness of the electromagnetic wave absorptive and thermally conductive layer is 0.7 Other than mm, the same treatment as in Example 1 was carried out to obtain a 1 · 5 // m thick polyimide film laminated with a thickness of 0 · 7 mm of electromagnetic wave absorptive heat-conducting layer. Second, compared to the example of the matrix polymer 1 100 parts by weight of the polysiloxane composition used in the electromagnetic wave-absorbing heat-conducting layer in 1 will be an alumina powder having an average particle diameter of 1 8 // m (a trade name manufactured by Showa Denko Corporation) : AS-3 0) 600 parts by weight and an alumina powder with an average particle diameter of 4 // m (trade name: AL-24, manufactured by Showa Denko Co., Ltd.) 3 0 0 parts by weight is filled to form a heat conductive layer composition.- 20- (18) (18) 200416976 The polyimide film on the opposite side of the electromagnetic wave absorptive and thermally conductive layer of the above-mentioned laminated product is coated with primer C (trade name of Shin-Etsu Chemical Industry Co., Ltd.) Then, the thermal conductive layer composition was coated on the surface of the polyimide film with a solvent-free coating thickness of 0.3 mm, and then cross-linked and hardened at 120 ° C for 10 minutes to obtain Figure 1 (b The three-layer structure shown in the figure shows a total sheet thickness of 1 mm. Magnetic wave-absorbing thermally conductive sheet. [Example 1 〇] An organic peroxide-cured polysiloxane rubber composition was used as a matrix polymer, and an electromagnetic wave was applied to a polyimide film having a thickness of 12.5 // m. The absorptive heat-conducting layer is formed by coating. 88 parts by weight of dimethyl vinyl raw rubber having an average polymerization degree of 7,000, and a silicon atom-bound alkoxy-organopolysiloxane is used as a heat-conducting filling powder. Surface treatment agent (2 parts by weight, and 'Fe — 5.5% of flat shape as soft magnetic metal powder with an average particle diameter of 3 0 // m] and average particle size of thermally conductive powder Granular alumina powder with a diameter of 1 // m (trade name: AL — 47-1 manufactured by Showa Denko Co., Ltd.) 5 00 parts by weight are mixed with a kneader until homogeneous to produce a matrix composition of a thermally conductive layer. With respect to 100 parts by weight of this matrix composition, 0.8 parts by weight of organic peroxide I (o-methylbenzophenazine) peroxide and 40 parts by weight of toluene were stirred and mixed in a homogenizer, and then preliminarily Primer C (trade name, manufactured by Shin-Etsu Takaku Co., Ltd.) is a polyimide film having a thickness of 12-5 // m for primer coating. In addition, in order to remove toluene, -21-(19) 200416976 was provided with 4 (TC — 5 minutes, 8 (TC — 5 minutes) stepwise heating steps, and the coating was applied at 15 (TC-5 minutes). The sheet was crosslinked and hardened, and an electromagnetic wave absorptive heat conductive layer having a thickness of 0.1 mm was laminated on one side of a 12.5 // m thick polyimide film.
其次，將此層合品之導熱層層合面反側之聚醯亞胺薄 膜面，以塗底劑C (信越化學工業股份有限公司製商品名 )予以塗底處理後，將做爲實施例1所示之電磁波吸收性 導熱層的組成物，以加壓成型，並於120 °C、加熱硬化10 分鐘，取得圖1(c)所示之三層構造之合計薄片厚度1 mm之本發明的電絕緣性電磁波吸收性導熱性薄片。 〔實施例11〕Next, the polyimide film surface on the opposite side of the heat-conducting layer lamination surface of this laminate was primed with primer C (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and it will be taken as an example. The composition of the electromagnetic wave absorptive heat-conducting layer shown in 1 is press-molded, and heated and hardened at 120 ° C for 10 minutes to obtain the present invention having a total sheet thickness of 1 mm in the three-layer structure shown in FIG. 1 (c). Electrically insulating electromagnetic wave absorbing thermally conductive sheet. [Example 11]
將做爲實施例1所示之電磁波吸收性導熱層的組成物 ，以預先經塗底劑C (信越化學工業股份有限公司製商品 名）予以塗底處理之12.5// m厚的聚醯亞胺薄膜由上下夾 住，並以加壓成型於120°C、加熱硬化1〇分鐘’取得圖1 (d)所示之三層構造之合計薄片厚度1 mm之本發明的 電絕緣性電磁波吸收性導熱性薄片。 〔實施例1 2〕 準備於實施例7所示之1 2 · 5 // m厚之聚醯亞胺薄膜的 單面，疊層厚度〇·1 mm之導熱層者，並於此層合品之導 熱層層合面之反側的聚醯亞胺薄膜面，以塗底劑c (信越 化學工業股份有限公司製商品名）予以塗底處理。 -22- (20) (20)200416976 其次，將做爲實施例2所示之電磁波吸收性導熱層的 組成物，以上述層合品之預先經塗底劑C (信越化學工業 股份有限公司製商品名）予以塗底處理之聚醯亞胺薄膜面 側由上下夾住，並以加壓成型於1 2 (TC、加熱硬化1 0分 鐘，取得圖1 ( e )所示之五層構造之合計薄片厚度1 mm 之本發明的電絕緣性電磁波吸收性導熱性薄片。 〔比較例1〕 除了令實施例1之電磁波吸收性導熱層以實施例9之 導熱層之組成代替以外，同實施例1處理，取得由導熱 層和聚醯亞胺薄膜所構成之二層構造之合計薄片厚度1 m in的導熱性薄片。 〔比較例2〕 除了令做爲實施例1之電磁波吸收性導熱層之組成物 的配合組成，相對於聚矽氧烷成分1 00重量份’以軟磁性 金屬粉末900重量份，且未充塡導熱性粉末以外’同實施 例1處理，取得由電磁波吸收性層和聚醯亞胺薄膜所構 成之二層構造之合計薄片厚度1 mm的電磁波吸收性薄片 〔比較例3〕 使用日信化學工業股份有限公司製之丙烯酸橡膠 RV - 2 5 20，做爲電磁波吸收層的基質聚合物，且相對於 -23- (21) 200416976The composition as the electromagnetic wave-absorbing heat-conducting layer shown in Example 1 was a 12.5 // m thick polyfluorene coated with primer C (trade name of Shin-Etsu Chemical Industry Co., Ltd.) beforehand. The amine film was sandwiched between the top and bottom, and was press-molded at 120 ° C and heated and hardened for 10 minutes to obtain the three-layer structure shown in Fig. 1 (d). The total sheet thickness was 1 mm, and the electrically insulating electromagnetic wave absorption of the present invention was absorbed. Thermally conductive sheet. [Example 1 2] A 1 ·· 5 // m thick polyimide film as shown in Example 7 was prepared on one side, and a thermally conductive layer with a thickness of 0.1 mm was laminated, and then laminated thereon. The polyimide film surface on the opposite side of the heat-conducting layer lamination surface was coated with a primer c (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.). -22- (20) (20) 200416976 Next, as the composition of the electromagnetic wave-absorbing heat-conducting layer shown in Example 2, the above-mentioned laminated product was previously coated with primer C (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (Brand name) The bottom surface of the polyimide film is sandwiched between the top and bottom, and is pressure-molded at 12 (TC, heat-hardened for 10 minutes) to obtain the five-layer structure shown in Figure 1 (e). The electrically insulating electromagnetic wave absorptive and thermally conductive sheet of the present invention with a total sheet thickness of 1 mm. [Comparative Example 1] The same as the example except that the electromagnetic wave absorptive and thermally conductive layer of Example 1 was replaced with the composition of the thermally conductive layer of Example 9. 1 treatment to obtain a thermally conductive sheet with a total sheet thickness of 1 mm in a two-layer structure composed of a thermally conductive layer and a polyimide film. [Comparative Example 2] Except for the electromagnetic wave-absorbing thermally conductive layer of Example 1, The compound composition of the composition was treated in the same manner as in Example 1 with respect to 100 parts by weight of the polysiloxane component, 900 parts by weight of a soft magnetic metal powder and not containing a thermally conductive powder, to obtain an electromagnetic wave absorbing layer and a polymer. Arsenide Electromagnetic wave absorptive sheet with a total sheet thickness of 1 mm for the two-layer structure [Comparative Example 3] Acrylic rubber RV-2 5 20 manufactured by Nissin Chemical Industry Co., Ltd. was used as the matrix polymer of the electromagnetic wave absorbing layer, and relatively At -23- (21) 200416976
此丙烯酸橡膠100重量份，將平均粒徑30 // m之扁平形 狀的鐵矽鋁磁性合金組成Fe - A1 - Si合金軟磁性金屬粉 末9 00重量份以揑和機予以均勻混合，作成電磁波吸收層 的基質組成物。相對於此基質組成物100重量份，將有機 過氧化物之二（鄰一甲基苯甲醯）過氧化物0.8重量份以 二根輥混合後，於預先以塗底劑C (信越化學工業股份有 限公司製商品名）予以塗底處理之12.5//m厚之聚醯亞胺 薄膜上，於1 5 0 °C、1 〇分鐘之條件下加壓成型，取得由電 磁波吸收層與聚醯亞胺薄膜所構成之二層構造之合計薄片 厚度1 mm的電磁波吸收性薄片。 以下述所示之方法評價實施例1〜1 2、比較例1〜3 所得薄片之薄片厚度方向的絕緣破壞電壓、薄片厚度方向 的平均導熱率、各層的導熱率、薄片表面層的Ascar C硬 度，及做爲電磁波吸收特性的放射電磁波衰減量，且結果 示於表 1〜3 〇 《絕緣破壞電壓》 絕緣破壞電壓的測定爲根據JIS C 2 1 1 0進行測定。 《導熱率》 導熱率爲根據ASTM E 1 5 3 0進行測定。 《AscarC硬度》 製造單獨之薄片表面層的6 mm厚薄片’並將此薄片 -24- (22) 200416976 以薄片間不會混入氣泡般地重疊二枚，作成合計12mm 厚的被測定樣品。使用高分子計器股份有限公司製Ascar C硬度計，將負重1公斤下之1 0秒後的讀數視爲測定値 《放射電磁波衰減量》100 parts by weight of this acrylic rubber, a flat iron-silicon-aluminum magnetic alloy with an average particle diameter of 30 // m is composed of Fe-A1-Si alloy soft magnetic metal powder. 900 parts by weight are uniformly mixed with a kneader to make electromagnetic wave absorption. The matrix composition of the layer. With respect to 100 parts by weight of the base composition, 0.8 parts by weight of the second organic peroxide (o-methyl benzamidine) peroxide was mixed with two rollers, and then a primer C (Shin-Etsu Chemical Industries Co., Ltd.) was applied beforehand. Co., Ltd.'s trade name) a polyimide film with a thickness of 12.5 // m which has been treated with a primer, and it is pressure-molded at 150 ° C for 10 minutes to obtain an electromagnetic wave absorbing layer and polymer An electromagnetic wave absorbing sheet with a total thickness of 1 mm in a two-layer structure composed of an imine film. The methods shown below were used to evaluate Examples 1 to 1, 2 and Comparative Examples 1 to 3, and the dielectric breakdown voltage in the sheet thickness direction, the average thermal conductivity in the sheet thickness direction, the thermal conductivity of each layer, and the Ascar C hardness of the sheet surface layer. And the amount of attenuation of radiated electromagnetic waves as electromagnetic wave absorption characteristics, and the results are shown in Tables 1 to 30. "Insulation breakdown voltage" The insulation breakdown voltage was measured in accordance with JIS C 2 110. << thermal conductivity >> The thermal conductivity is measured in accordance with ASTM E 1530. "AscarC Hardness" A 6-mm-thick sheet with a single sheet surface layer was produced. -24- (22) 200416976 Two sheets were laminated so that no bubbles were mixed between the sheets, and a total of 12 mm thick samples were measured. Using Ascar C hardness tester manufactured by Polymer Meter Co., Ltd., the reading after 10 seconds under a load of 1 kg was regarded as the measurement 値 "radiated electromagnetic wave attenuation"
評價放射電磁波衰減量的方法示於圖2。首先，於電 波暗室4內，將被測定薄片，捲放於發生周波數2 GHz電 磁波之偶極天線6，並由此偶極天線6距離3 m之位置設 置受信天線8。即，其爲符合根據FCC的3 m法。其次， 以連接受信天線8之密封室5內之EMI接收機（光譜分 析器）9測定所發生的電磁波。還有，圖2中7爲訊號發 電機。將此測定結果與未設置薄片時之電磁波發生量之差 ，視放射電磁波衰減量。 -25- (23)200416976 表1 實施例 1 2 3 4 5 6 層構造(注1) EMITC EMITC EMITC EMITC EMITC EMITC /F /F IF /F /F /F 基質聚合 種類 聚矽氧烷 聚矽氧烷 丙烯酸 聚矽氧烷 聚矽氧烷 聚矽氧烷 物 配合(重量份） 100 100 100 100 100 100 軟磁性金 組成 Fe-12% Fe-5.5% Fe-5.5%Si Fe-5.5%Si Fe-5.5%Si Fe-5.5%Si 屬粉 Cr-3%Si Si 扁平 電磁波吸收 形狀 球狀 扁平 1200 扁平 扁平 扁平 性導熱層 配合(重量份） 1000 900 900 900 900 1 導熱性充 種類 氧化銘 氧化鋁 氧化鋁 氧化鋁 氮化鋁 NiZn 塡劑 配合(重量份） 400 500 300 200 鐵素體 300 厚度(// ΙΏ) 1 0.3 1 1 1 1 導熱率(W/mK) 3.6 3.2 3.3 2.1 3.0 2.0 材質 PI PI PI PEN PEN PEN 薄膜 厚度〇m) 12.5 12.5 12.5 12.5 12.5 12.5 基質聚合 種類 物 配合(重量份） 軟磁性金 組成 導熱層或 屬粉 形狀 電磁波吸收 配合(重量份） 無 無 無 無 無 無 性導熱層2 導熱性充 種類 塡劑 配合(重量份） 厚度(//ΙΏ) 導熱率(W/mK) 絕緣破壞電壓(kV) 2.8 3.2 3.1 2.5 2.7 2.8 薄片全體厚度方向上之平均導熱率(W/mK) 3.1 2.7 2.9 1.9 2.6 1.7 表面層之 硬度 30 60 55 65 60 Ascar C硬度 70以下之層名(注1) EMITC EMITC 無 EMITC EMITC EMITC 電磁波吸收性能(dB) 3.6 3.1 9.5 7.9 7.3 8.5A method for evaluating the amount of attenuation of radiated electromagnetic waves is shown in FIG. 2. First, in the anechoic chamber 4, a sheet to be measured is rolled up on a dipole antenna 6 having an electromagnetic wave frequency of 2 GHz, and a receiving antenna 8 is set at a distance of 3 m from the dipole antenna 6. That is, it is in compliance with the 3 m method according to the FCC. Next, an EMI receiver (spectrum analyzer) 9 in a sealed room 5 connected to the receiving antenna 8 is used to measure the generated electromagnetic waves. In addition, 7 in FIG. 2 is a signal generator. The difference between the result of this measurement and the amount of electromagnetic wave generated when no sheet is set is determined by the amount of electromagnetic wave attenuation. -25- (23) 200416976 Table 1 Example 1 2 3 4 5 6 Layer structure (Note 1) EMITC EMITC EMITC EMITC EMITC EMITC / F / F IF / F / F / F Matrix polymerization type polysiloxane polysiloxane Alkyl acrylic polysiloxane polysiloxane polysiloxane compound (parts by weight) 100 100 100 100 100 100 Soft magnetic gold composition Fe-12% Fe-5.5% Fe-5.5% Si Fe-5.5% Si Fe- 5.5% Si Fe-5.5% Si Metal powder Cr-3% Si Si Flat electromagnetic wave absorption shape Spherical flat 1200 Flat flat flat heat-conducting layer (weight part) 1000 900 900 900 900 1 Thermal conductivity Type Oxidation aluminum oxide oxidation Aluminum alumina aluminum nitride NiZn tincture compound (parts by weight) 400 500 300 200 Ferrite 300 Thickness (/ // ΙΏ) 1 0.3 1 1 1 1 Thermal conductivity (W / mK) 3.6 3.2 3.3 2.1 3.0 2.0 Material PI PI PI PEN PEN PEN film thickness 0m) 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 Layer 2 Thermal conductivity Filler type (weight part) Thickness (// ΙΏ) Thermal conductivity (W / mK) Insulation breakdown voltage (kV) 2.8 3.2 3.1 2.5 2.7 2.8 Average thermal conductivity in the thickness direction of the entire sheet (W / mK) 3.1 2.7 2.9 1.9 2.6 1.7 Surface layer hardness 30 60 55 65 60 Ascar C Layer name below 70 (Note 1) EMITC EMITC No EMITC EMITC EMITC Electromagnetic wave absorption performance (dB) 3.6 3.1 9.5 7.9 7.3 8.5
(注1)層構造及表面層之A scar C硬度之70以下之層名 之欄的記號說明 EMITC :電磁波吸收導熱層 F :薄膜 TC :導熱層 26- (24) (24)200416976 表2 1 ί施例 7 8 9 10 11 12 層構造(注1) EMITC/F/ TC EMITC/F/ TC EMITC/F/ TC EMITC 1/ F/EMITC2 FEMITC /F TC/F/ EMITC/F/丁 C 電磁波吸收 性導熱層 1 基質聚合 物 種類 配合(重量份） 聚矽氧烷 100 聚矽氧烷 100 聚矽氧烷 100 聚矽氧烷 100 聚矽氧烷 100 聚矽氧烷 】00 軟磁性金 屬粉 組成 形狀 配合(重量份） Fe-12% Cr-3%Si 球狀 1000 Fe-12% Cr-3%Si 球狀 1000 Fe-12% Cr-3%Si 球狀 1000 Fe-12% Cr-3%Si 球狀 】000 Fe-12% Cr-3%Si 球狀 1000 Fe-5.5%Si 扁平 900 導熱性充 塡劑 種類 配合(重量份） 氧化鋁 400 氧化鋁 400 氧化鋁 400 氧化鋁 400 氧化鋁 400 氧化鋁 500 厚度(//in) 1.9 0.9 0.7 0.9 1 0.8 導熱率(W/mK) 3.6 3.6 3.6 3.6 3.6 3.2 薄膜 材質 厚度(#m) PI 12.5 ΡΪ 12.5 PI 12.5 PI 12.5 PI 12.5 PI 12.5 導熱層或 電磁波吸收 性導熱層2 基質聚合物 種類 配合(重量份） 聚矽氧烷 100 聚矽氧烷 100 聚矽氧烷 100 聚矽氧烷 100 無 聚石夕氧院 100 軟磁性金屬 粉 組成 形狀 配合(重量份） 無 無 無 Fe-5.5%Si 扁平 900 無 導熱性充塡 劑 種類 配合(重量份） 氧化鋁 1200 氧化鋁 1200 氧化鋁 900 氧化鋁 500 氧化鋁 1200 厚度(#m) 0.1 0.1 0.3 0.1 0.1 導熱率(W/mK) 5.1 5.1 3.7 3.2 5.1 絕緣破壞電壓(kV) 4.7 7.9 8.8 3.2 5.8 9.1 薄片全體厚度方向上之平均導熱率 (W/mK) 3.4 2.6 3.0 3.0 2.6 3.0 表面層之 Ascar C硬度 硬度 70以下之層名(注1) 30 EMITC 30 EMITC 30 EMITC 30 EMITC 無 無 10 TC 電磁波吸收性能(dB) 6.3 3.1 2.8 3.6 3.3 6.8 (注1)層構造及表面層之A scar C硬度之70以下之層名 之欄的記號說明 EMITC :電磁波吸收導熱層 F :薄膜 TC :導熱層 -27- (25)200416976 表3 比較例 1 2 3 層構造(注1) TC/F EMITC/F EMITC/F 電磁波吸收 基質聚合物 種類 聚矽氧烷 丙烯酸 性導熱層1 配合(重量份） 100 100 軟磁性金屬 組成 Fe-12%Cr- Fe-Al-Si 粉 3%Si 形狀 Μ j \ \\ 球狀 扁平 配合(重量份） 900 900 導熱性充塡 種類 Μ ίκ j \ 劑 配合(重量份） 厚度(mm) i i 導熱率(W/mK) 1.6 .4 薄膜 材質 ΡΙ PI PI 厚度(//m) 12.5 12.5 12.5 基質聚合物 種類 聚石夕氧院 配合(重量份） 100 軟磁性金屬 組成 Μ j\\\ 導熱層或 粉 形狀 電磁波吸收 配合(重量份） 姐 J\ w 性導熱層2 導熱性充塡 種類 氧化鋁 劑 配合(重量份） 900 厚度(mm) 1 導熱率(W/mK) 3.7 絕緣破壞電壓(kv) 22.3 3.1 3.2 薄片全體厚度方向之平均導熱率(W/mK) 3.2 1.4 1.3 表面層之 硬度 5 5 Ascar C硬度 70以下之層名(注1) TC EMITC M 電磁波吸收性能(dB) 0.0 4.3 8.9(Note 1) The layer structure and the surface layer have a scar C hardness of 70 or less. The name of the column name indicates EMITC: electromagnetic wave absorption and thermal conductivity layer F: thin film TC: thermal conductivity layer 26- (24) (24) 200416976 Table 2 1 Example 7 8 9 10 11 12-layer structure (Note 1) EMITC / F / TC EMITC / F / TC EMITC / F / TC EMITC 1 / F / EMITC2 FEMITC / F TC / F / EMITC / F / Ding Absorptive thermal conductive layer 1 Type of matrix polymer (parts by weight) Polysiloxane 100 Polysiloxane 100 Polysiloxane 100 Polysiloxane 100 Polysiloxane 100 Polysiloxane] 00 Soft magnetic metal powder composition Shape fit (parts by weight) Fe-12% Cr-3% Si spherical 1000 Fe-12% Cr-3% Si spherical 1000 Fe-12% Cr-3% Si spherical 1000 Fe-12% Cr-3% Si Spherical] 000 Fe-12% Cr-3% Si Spherical 1000 Fe-5.5% Si Flat 900 Thermal Conductive Filler Type Compounding (weight parts) Alumina 400 Alumina 400 Alumina 400 Alumina 400 Alumina 400 Alumina 500 thickness (// in) 1.9 0.9 0.7 0.9 1 0.8 Thermal conductivity (W / mK) 3.6 3.6 3.6 3.6 3.6 3.2 Film material thickness (#m) PI 12.5 ΡΪ 12.5 PI 12.5 PI 12.5 PI 12.5 PI 12.5 Thermally conductive layer or Electromagnetic wave Absorptive thermal conductive layer 2 Type of matrix polymer (parts by weight) Polysiloxane 100 Polysiloxane 100 Polysiloxane 100 Polysiloxane 100 Polysilicone-free Oxygen Institute 100 Soft magnetic metal powder composition shape (weight Parts) No No Fe-5.5% Si Flat 900 Non-thermal conductive fillers (weight parts) Alumina 1200 Alumina 1200 Alumina 900 Alumina 500 Alumina 1200 Thickness (#m) 0.1 0.1 0.3 0.1 0.1 Thermal conductivity Rate (W / mK) 5.1 5.1 3.7 3.2 5.1 Insulation breakdown voltage (kV) 4.7 7.9 8.8 3.2 5.8 9.1 Average thermal conductivity (W / mK) in the thickness direction of the entire sheet 3.4 2.6 3.0 3.0 2.6 3.0 Ascar C hardness of the surface layer Layer names below 70 (Note 1) 30 EMITC 30 EMITC 30 EMITC 30 EMITC None 10 TC Electromagnetic wave absorption performance (dB) 6.3 3.1 2.8 3.6 3.3 6.8 (Note 1) Layer structure and surface layer A scar C hardness below 70 Explanation of the symbol in the column of the layer name EMITC: Electromagnetic wave absorption thermal conductive layer F: Thin film TC: Thermal conductive layer-27- (25) 200416976 Table 3 Comparative Example 1 2 3 layer structure (Note 1) TC / F EMITC / F EMITC / F Polysiloxane Alkyl-acrylic heat conductive layer 1 Blend (parts by weight) 100 100 Soft magnetic metal composition Fe-12% Cr- Fe-Al-Si powder 3% Si Shape Μ j \ \\ Spherical flat fit (parts by weight) 900 900 Thermal conductivity Filling type M ίκ j \ Additive (weight part) Thickness (mm) ii Thermal conductivity (W / mK) 1.6.4 Film material PI PI PI Thickness (// m) 12.5 12.5 12.5 Matrix polymer type Hospital compound (parts by weight) 100 Soft magnetic metal composition Μ j \\\ Thermally conductive layer or powder shape electromagnetic wave absorption compound (parts by weight) Sister J \ w Thermally conductive layer 2 Thermal conductivity filling type alumina agent compounding (parts by weight) 900 Thickness (mm) 1 Thermal conductivity (W / mK) 3.7 Insulation breakdown voltage (kv) 22.3 3.1 3.2 Average thermal conductivity (W / mK) of the entire thickness of the sheet 3.2 1.4 1.3 Hardness of the surface layer 5 5 Ascar C hardness 70 or less Layer name (Note 1) TC EMITC M Electromagnetic wave absorption performance (dB) 0.0 4.3 8.9
(注1)層構造及表面層之A scar C硬度之70以下之層名 之欄的記號說明 EMITC :電磁波吸收導熱層 F :薄膜 TC :導熱層 28- (26) (26)200416976 由表1可確認，根據本發明的實施例1〜1 2，絕緣破 壞電壓爲高至1 kV以上，且導熱率亦高至1.5 W/ mK以 上，且電磁波吸收性能亦於本評價方法中取得2 d B以上 的値，具有充分的電磁波吸收性能。 經由將實施例1與比較例1予以比較，則可知僅充塡 無電磁波吸收性能之導熱性充塡劑時，薄片與高分子薄膜 的層合品雖可取得1 kV以上的絕緣破壞電壓，但並無電 磁波吸收性能。 經由將實施例1與比較例2及3予以比較，則可知與 薄膜疊層之電磁波吸收性導熱層中不含有導熱性充塡劑、 且僅充塡軟磁性金屬粉時，電磁波吸收性導熱層之導熱率 爲低至2 W/mK以下，且層合薄片全體厚度方向之平均 導熱率亦低壓1 .5 W / mK以下。 〔發明之效果〕 本發明之電絕緣性電磁波吸收性導熱性薄片爲兼具高 電磁波吸收性能和高導熱性能，且爲電絕緣性，故裝配於 電子機器內部時，並不必要特別照料對於印刷配線電路爲 首之各部分的電性短路，可裝配於最適當的處所。因此， 可抑制先前增加之電子機器內部的電磁波雜訊，並且亦可 抑制電磁波洩漏至外部。更且，亦可令電子機器要素所發 生之熱放熱至機器外部。 因此’對於先前必須以電磁波吸收性薄片和導熱性薄 片二種薄片的處所，可以一種薄片簡單應付。可在小空間 -29- (27) (27)200416976 中同時進行電磁波雜訊對策和發熱對策，亦可令電子機器 小型化。 【圖式簡單說明】 〔圖1〕示出本發明之電磁波吸收性導熱性薄片構造 的槪略截面圖，（a )爲由電磁波吸收性導熱層和高分子 薄膜層疊層而成之二層構造的電磁波吸收性導熱性薄片、 (b )爲由電磁波吸收性導熱層和高分子薄膜層和導熱層 疊層而成之三層構造的電磁波吸收性導熱性薄片、（^ ) 、（d )爲由電磁波吸收性導熱層和高分子薄膜層疊層而 成之三層構造的電磁波吸收性導熱性薄片、（e )爲由電 磁波吸收性導熱層和高分子薄膜層和導熱層疊而成之五層 構造的電磁波吸收性導熱性薄片。 〔圖2〕示出放射電磁波衰減量測定方法之方塊圖。 〔主要元件對照表〕 1 電磁波吸收性導熱層 2 高分子薄膜層 3 導熱層 4 電波暗室 5 密封室 6 偶極天線 7 訊號發電機 8 受信天線 (28) 200416976 (28) 9 EMI接收器 - 31(Note 1) The layer structure and the surface layer have a scar C hardness of 70 or less. The name of the column name is EMITC: Electromagnetic Wave Absorption Thermally Conductive Layer F: Thin Film TC: Thermally Conductive Layer 28- (26) (26) 200416976 Table 1 It can be confirmed that according to Examples 1 to 12 of the present invention, the insulation breakdown voltage is as high as 1 kV or more, and the thermal conductivity is also as high as 1.5 W / mK or more, and the electromagnetic wave absorption performance also achieved 2 d B in this evaluation method. The above radon has sufficient electromagnetic wave absorption performance. By comparing Example 1 and Comparative Example 1, it can be seen that when only a thermally conductive filler having no electromagnetic wave absorption performance is charged, the laminated product of the sheet and the polymer film can obtain an insulation breakdown voltage of 1 kV or more, but There is no electromagnetic wave absorption performance. By comparing Example 1 with Comparative Examples 2 and 3, it can be seen that when the electromagnetic wave absorbing thermally conductive layer laminated with the thin film does not contain a thermally conductive filler and is filled only with soft magnetic metal powder, the electromagnetic wave absorbing thermally conductive layer The thermal conductivity is as low as 2 W / mK or less, and the average thermal conductivity in the thickness direction of the entire laminated sheet is also lower than 1.5 W / mK. [Effects of the Invention] The electrically insulating electromagnetic wave absorbing and thermally conductive sheet of the present invention has both high electromagnetic wave absorption performance and high thermal conductivity, and is electrically insulating. Therefore, it is not necessary to take special care for printing when assembled in electronic equipment. Each part of the wiring circuit is electrically shorted and can be assembled in the most appropriate place. Therefore, it is possible to suppress the electromagnetic wave noise inside the electronic device that was previously increased, and also to suppress the leakage of the electromagnetic wave to the outside. Furthermore, the heat generated by the electronic device elements can be radiated to the outside of the device. Therefore, for a space which previously had to be two sheets of electromagnetic wave absorbing sheet and thermally conductive sheet, one sheet can be handled simply. The small space -29- (27) (27) 200416976 can be used for electromagnetic noise countermeasures and heat countermeasures at the same time, and electronic equipment can be miniaturized. [Brief description of the drawings] [Fig. 1] A schematic cross-sectional view showing the structure of an electromagnetic wave-absorbing heat conductive sheet of the present invention. (A) is a two-layer structure formed by laminating an electromagnetic wave-absorbing heat conductive layer and a polymer film. (B) is a three-layer structure of electromagnetic wave absorptive and thermally conductive sheet composed of an electromagnetic wave absorptive and thermally conductive layer, a polymer film layer and a thermally conductive laminated layer, (^), (d) Electromagnetic wave absorbing thermally conductive layer and polymer film are laminated in a three-layer structure. The electromagnetic wave absorbing thermally conductive sheet (e) is a five-layer structure composed of an electromagnetic wave absorbing thermally conductive layer and a polymer film layer and thermally conductive. Electromagnetic wave absorbing thermally conductive sheet. [Fig. 2] A block diagram showing a method for measuring the amount of attenuation of a radiated electromagnetic wave. [Comparison table of main components] 1 Electromagnetic wave absorptive thermal conductive layer 2 Polymer film layer 3 Thermal conductive layer 4 Anechoic chamber 5 Sealed chamber 6 Dipole antenna 7 Signal generator 8 Receiving antenna (28) 200416976 (28) 9 EMI receiver-31
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| JP2002369225A JP2004200534A (en) | 2002-12-20 | 2002-12-20 | Electromagnetic wave absorbing thermal conductive sheet |
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| CN112352476A (en) * | 2018-07-12 | 2021-02-09 | 迪睿合株式会社 | Pickup apparatus, mounting apparatus, pickup method, and mounting method |
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| JP2007027520A (en) * | 2005-07-20 | 2007-02-01 | Nec Access Technica Ltd | Radiator |
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| JP4731431B2 (en) * | 2006-09-05 | 2011-07-27 | アキレス株式会社 | Acrylic resin laminated sheet-like molded product |
| KR100830945B1 (en) | 2006-10-24 | 2008-05-20 | (주) 아모센스 | Preparation method of thermal conductive sheet comprised electromagnetic interference shielding used the nanocomposite carbon fiber |
| JP4798629B2 (en) * | 2006-11-13 | 2011-10-19 | 北川工業株式会社 | Thermally conductive electromagnetic shielding sheet and electromagnetic shielding structure |
| JP5533787B2 (en) * | 2011-06-09 | 2014-06-25 | 株式会社豊田自動織機 | Heat dissipation device |
| KR101266390B1 (en) | 2012-10-05 | 2013-05-22 | 주식회사 엘엠에스 | Heat conduction composition and sheet |
| EP2897164B1 (en) * | 2014-01-17 | 2020-01-01 | Henkel IP & Holding GmbH | Thermally-conductive interface pad for EMI-suppression |
| JP2014239236A (en) * | 2014-07-11 | 2014-12-18 | デクセリアルズ株式会社 | Thermally conductive sheet |
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| JP6366627B2 (en) * | 2016-03-25 | 2018-08-01 | デクセリアルズ株式会社 | Electromagnetic wave absorbing heat conducting sheet, method for producing electromagnetic wave absorbing heat conducting sheet, and semiconductor device |
| CN109256255B (en) * | 2018-11-19 | 2023-12-12 | 宴晶科技(北京)有限公司 | Composite metal soft magnetic sheet and wireless charging device |
| JP2020158633A (en) * | 2019-03-26 | 2020-10-01 | 積水化学工業株式会社 | Cross-linked foam sheet |
| KR102065952B1 (en) * | 2019-07-04 | 2020-01-14 | 정상희 | The composite sheet for absorption of radiant heat and electromagnetic waves |
| KR102261248B1 (en) * | 2020-12-29 | 2021-06-07 | 대진첨단소재 주식회사 | Electromagnetic wave absorption heat conductive heat dissipation sheet manufacturing device |
| JP7293522B1 (en) * | 2021-11-10 | 2023-06-19 | デンカ株式会社 | Heat dissipation sheet |
| KR102644508B1 (en) * | 2022-04-13 | 2024-03-08 | (주)트러스 | Composite sheet with thermal conductivity and electromagnetic wave absorbing property and method of manufacturing same |
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| CN112352476A (en) * | 2018-07-12 | 2021-02-09 | 迪睿合株式会社 | Pickup apparatus, mounting apparatus, pickup method, and mounting method |
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| JP2004200534A (en) | 2004-07-15 |
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