TWI627717B - 散熱基板 - Google Patents
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Abstract
一散熱基板為包括金屬基底、導熱電絕緣層和金屬層之層疊結構。該導熱電絕緣層設置於該金屬基底上,且該金屬層設置於該導熱電絕緣層上。該導熱電絕緣層包含高分子聚合物以及散佈於該高分子聚合物中之非圓球形導熱填料。該高分子聚合物包含至少二種不同環氧當量的直鏈型環氧樹脂,該非圓球形導熱填料之平均粒徑和比表面積的乘積在7.5~15mm·m
2/g。該導熱電絕緣層之玻璃轉換溫度在40~90℃,導熱率1~6W/m·K。
Description
本發明係關於一種散熱基板,特別是關於一種使用金屬基底之散熱基板。
一直以來,作為電子零件安裝用散熱基板,多使用金屬芯基板,該金屬芯基板是層合電絕緣材料層於金屬板之上,並於電絕緣材料層之上形成銅箔,該銅箔形成佈線圖型。然後於佈線圖型上使用焊錫,來安裝各種晶片,如晶片零件、矽半導體、端子等。
作為前述電絕緣材料層,例如添加無機填料於熱可塑性聚醯亞胺或聚苯醚(PPE)。但是這樣的熱可塑性聚醯亞胺、PPE之類一般的樹脂,因為樹脂本身之熱傳導率為低,所以要作為具高散熱性之電子零件用之散熱基板有其困難。因此,近年來已對電絕緣材料層之高熱傳導化進行研究,例如使用結晶化樹脂或高熱傳導性填料來作為提高樹脂之熱傳導性之手段。
在車用市場或其他嚴酷環境,因可能於高溫下曝曬及於酷寒環境中使用,該嚴苛使用環境對產品耐用度帶來嚴峻考驗。散熱基板在上述嚴苛的高低溫環境中使用,用來固定連接晶片的焊錫有時會因膨脹收縮的關係產生錫裂,嚴重影響晶片使用上的穩定度和可靠度。本發明係改善上述問題點,並考慮操作上的實用性,從而提供一種高可靠度的散熱基板。
為了解決上述問題,本發明揭示一種金屬基底之散熱基板,通過其中導熱電絕緣層材料的改良,可提升於高低溫環境中使用的穩定度,避免錫裂的問題。另外,本發明的散熱基板改良其表面的金屬層,進一步提升其剝離強度。
根據本發明之一實施例,一散熱基板為包括金屬基底、導熱電絕緣層和金屬層之層疊結構。該導熱電絕緣層設置於該金屬基底上,且該金屬層設置於該導熱電絕緣層上。該導熱電絕緣層包含高分子聚合物以及散佈於該高分子聚合物中之非圓球形導熱填料。該高分子聚合物包含至少二種不同環氧當量的直鏈型環氧樹脂,該非圓球形導熱填料之平均粒徑和比表面積(BET surface area)的乘積在7.5~15μm.m2/g。該導熱電絕緣層之玻璃轉換溫度在40~90℃,導熱率1~6W/m.K。
一實施例中,該非圓球形導熱填料佔該導熱電絕緣層的體積百分比35~65%。
一實施例中,該非圓球形導熱填料係選自氧化鋁、氮化鋁、氮化硼、碳化矽或其組合。
一實施例中,該非圓球形導熱填料包含破碎形導熱填料。
一實施例中,該至少二種不同環氧當量的直鏈型環氧樹脂的平均環氧當量(Epoxy Equivalent Weight;EEW)為400~2000g/eq。
一實施例中,該至少二種不同環氧當量的直鏈型環氧樹脂的平均環氧當量為800~1500g/eq。
一實施例中,該至少二種不同環氧當量的直鏈型環氧樹脂中至少一種直鏈型環氧樹脂的EEW為100~500g/eq,且佔該高分子聚合物的重量百分比大於20%。
一實施例中,該金屬層包含一鍍層,該鍍層材料可以為鋅、鉻、鎳或其組合,且鍍層部份接觸該導熱電絕緣層。
一實施例中,該金屬層包含鍍鎳銅箔,且鍍鎳部份接觸該導熱電絕緣層。
一實施例中,該散熱基板經高壓蒸煮2atm、121℃飽和蒸氣96小時處理,該金屬層的剝離強度降低率在30%之內。
一實施例中,該導熱電絕緣層另包含潛變型硬化劑。
一實施例中,該潛變型硬化劑包含胺加成物(amine adduct)、醯肼(hydrazide)、二醯肼(dihydrazide)、二氰胺複合物(Dicy)、己二酸二醯肼(adipic acid dihydrazide)、以及間苯二甲酸二醯肼(isophthalic dihydrazide)中至少一成分。
一實施例中,該胺加成物係使用咪唑化合物(imidazole compound)、含有3級胺基的化合物(tertiary amino group-containing compound)或醯肼化合物(hydrazide compound)與環氧化合物(epoxy compound)或異氰酸酯化合物(isocyanate compound)反應而成。
一實施例中,該散熱基板在30℃環境下經過3個月後其黏度增加不超過1倍。
本發明之散熱基板中的導熱電絕緣層中選用至少二種不同環氧當量的直鏈型環氧樹脂且特別選用非圓球形導熱填料。因直鏈型環氧樹脂相較於側鏈型環氧樹脂較軟,故有助於防止錫裂。非圓球形導熱填料因為整體的表
面積增大,可以減少導熱填料的使用比例而降低材料的硬度,因而也有助於防止錫裂發生。另外,搭配潛變型硬化劑,將導熱電絕緣層或其中高分子聚合物之玻璃轉換溫度控制在較低溫的40~90℃(高於90℃容易產生錫裂問題,低於40℃時,高壓蒸煮金屬層剝離強度不佳),可有效避免散熱基板固定連接晶片的焊錫有時會因在高低溫環境中使用因膨脹收縮進而產生錫裂的問題。
10‧‧‧散熱基板
11‧‧‧金屬基底
12‧‧‧導熱電絕緣層
13‧‧‧金屬層
20‧‧‧測試片
21‧‧‧焊墊
22‧‧‧測試墊
23‧‧‧電阻晶片
24‧‧‧錫膏
圖1顯示本發明一實施例之散熱基板。
圖2和3顯示本發明散熱基板測試錫裂的方式。
為讓本發明之上述和其他技術內容、特徵和優點能更明顯易懂,下文特舉出相關實施例,並配合所附圖式,作詳細說明如下。
圖1顯示本發明一實施例之散熱基板10,包括一金屬基底11、一導熱電絕緣層12及一金屬層13。該導熱電絕緣層12設置於該金屬基底11上,且該金屬層13設置於該導熱電絕緣層12上。該金屬基底11、導熱電絕緣層12及金屬層13為層疊結構,或特別是本實施例所示的三明治結構。該導熱電絕緣層12包含高分子聚合物以及散佈於該高分子聚合物中之導熱填料。特別是,本發明選用之導熱填料為非圓球形,且該非圓球形導熱填料之平均粒徑和比表面積的乘積在7.5~15μm.m2/g,因整體導熱瑱料的表面積增大,可以利用較少體積百分比的導熱填料達到所需的導熱率,進而降低導熱電絕緣層12的材料硬度,有助於防止錫裂。
以下表1中之實施例1~5顯示導熱電絕緣層12中高分子聚合物的成份,其係選用直鏈型環氧樹脂,包含至少二種不同環氧當量(Epoxy Equivalent Weight;EEW)的環氧樹脂的混合物。因直鏈型環氧樹脂相較於側鏈型環氧樹脂較軟,故有助於防止錫裂。側鏈型環氧樹脂有較佳的耐溫性,可以少量添加,其於高分子聚合物中的體積佔比不超過15vol%或10vol%。實施例1~5中,導熱電絕緣層12中高分子聚合物為環氧樹脂1、環氧樹脂2和環氧樹脂3的組合,可以選用其中兩種或三種環氧樹脂的組合。本實施例中,環氧樹脂1選用Dow Chemical Company的D.E.R.TM 331,其EEW為180g/eq。環氧樹脂2選用南亞塑膠公司的NPES-904,其EEW為780g/eq。環氧樹脂3選用南亞塑膠公司的NPES-619C,其EEW為2700g/eq。本實施例選用不同環氧當量的環氧樹脂組合,可調整平均EEW,提供實際特性需求,如Tg、耐溫性和耐溶解性等。較大的平均EEW會有較低的Tg和較小的交鏈密度(crosslink density)。實施例1~5的平均EEW在400~2000g/eq之間,較佳為800~1500g/eq,例如平均EEW可以是500、600、1000、1200、1500或1800g/eq。比較例1和2的平均EEW約2316g/eq,比較例3單純使用環氧樹脂1,其平均EEW為180g/eq。比較例4的平均EEW約1248g/eq,一實施例中,本發明之高分子聚合物包含EEW小於1000g/eq的環氧樹脂和EEW大於2000g/eq的環氧樹脂,以便於平均EEW的調整。一實施例中,該至少二種不同環氧當量的直鏈型環氧樹脂中至少一種直鏈型環氧樹脂的EEW為100~500g/eq,且佔該高分子聚合物的重量百分比大於20%,以獲得較佳的耐溫性。
參照表2,上述實施例1~5中導熱電絕緣層12中的導熱填料可包含非圓球形氧化鋁,或非圓球形氧化鋁和非圓球形氮化鋁的混合物。例如表2實施例1~5中的非圓球形氧化鋁選用昭和電工型號AL-43M的破碎形氧化鋁,其平均粒徑為5.54μm,比表面積為1.68m2/g;非圓球形氮化鋁選用東洋鋁業株式會社(Toyo Aluminium)品名WJB和WM的氮化鋁粉混合過篩所得到的破碎形氮化鋁,其平均粒徑為5.65μm,比表面積為2.14m2/g。其他非圓球形導熱填料還可以使用氮化硼和碳化矽等。一實施例中,本發明的非圓球形導熱填料的平均粒徑為1~30μm,而比表面積為0.2~10m2/g,通常同樣材質的導熱填料,平均粒徑和比表面積的大小呈反向關係。本發明的非圓球形導熱填料的平均粒徑和比表面積的乘積在7.5~15μm.m2/g之間,或是8、10或12μm.m2/g。因為平均粒徑的意義包含尺寸大小和其分佈關係,故該乘積與整體導熱填料的總表面積成正向關係。導熱填料佔導熱電絕緣層12的體積百分比約在35~65vol%,例如40vol%、50vol%或60vol%。比較例1和4的導熱填料選用DENKA Co.,Ltd型號DAM-05的球形氧化鋁,其平均粒徑為5.4μm,比表面積為1.25m2/g(平均粒徑和比表面積的乘積約6.75μm.m2/g),體積百分比約60~70vol%。比較例2和3選用前述破碎形氧化鋁,其體積百分比約50vol%。表2中破碎形導熱填料的比表面積相較於球形導熱填料的比表面積大20%。導熱電絕緣層12的其餘成份包含上述環氧樹脂及相關硬化劑和促進劑等。以上實施例和比較例中的硬化劑使用潛變型硬化劑,例
如由Ajinomoto公司生產的AJICURETM MY-24。使用潛變型硬化劑可以延長散熱基板固化前半成品的保存時間。
表3顯示前述實施例1~5和比較例1~4中導熱電絕緣層材料的導熱率、玻璃轉移溫度Tg、錫裂測試以及高壓蒸煮96小時的金屬層剝離強度降低率(%)的測試結果。所述金屬層即為設置於該導熱電絕緣層12上的金屬層13,例如銅箔。實施例1~5中導熱電絕緣層材料的導熱率約在1~6W/m.K,導熱電絕緣層材料(高分子聚合物)的玻璃轉移溫度在40~90℃,也可以是50℃、60℃、70℃或80℃,且實施例1~5的散熱基板10全部通過錫裂測試,其電阻量測均為正常。另外,實施例1~5的散熱基板10經96小時於2大氣壓和121℃飽和蒸氣的高壓蒸煮測試,其金屬層剝離(拉力)強度的降低率在30%以內。反觀,比較例3和4的錫裂測試中,測得電阻無限大,即表示電氣斷路,而認為有錫裂發生。比較例3的平均EEW小於400g/eq,甚至小於200g/eq,因此其Tg較高,質地較脆,容易發生錫裂。比較例4採用球形氧化鋁,為了高導熱率,使用的體積百分比高達67vol%,導致材料較脆而易錫裂。比較例1和2的錫裂測試的電阻正常,但在經96小時的高壓蒸煮測試下,金屬層剝離強度的降低率超過40%或50%。比較例1
和2的EEW都超過2000g/eq,因此會有較低的Tg和較小的交鏈密度,使得高壓蒸煮測試的金屬層剝離強度的降低率過大。顯然比較例1~4沒有辦法同時達到沒有錫裂和高壓蒸煮金屬層剝離強度的降低率小於30%,而本發明之實施例1~5都可以通過錫裂測試,且同時其高壓蒸煮測試金屬層剝離強度降低率可小於30%。
上述的錫裂測試係先製作長寬2.5cm×1.5cm的測試片20,該測試片20為如同散熱基板包含金屬基底、導熱電絕緣層和金屬層的層疊結構。之後將表面金屬層蝕刻出圖案,其俯視圖如圖2所示。金屬層蝕刻後包含焊墊21和測試墊22,其間有導線連接。之後將電阻晶片23兩端利用錫膏24焊接於兩側的焊墊21,如圖3的側面示意圖。為簡化圖式,圖3並未繪出測試墊22和其相關連接線路。電阻晶片23焊接於測試片20後,利用該二個測試墊22進行電阻量測。電阻晶片23選用YAGEO公司型號PYU-RC0805,晶片尺寸2.0mm×1.2mm,電阻規格330±5%kΩ。錫膏則採用TAMURA公司型號TLF-204-171A的焊錫產品。之後將包含電阻晶片23的測試片20放入冷熱循環箱於-40℃維持7分鐘之後升溫至125℃也維持7分鐘形成一循環(cycle),後續降溫至-40℃重啟循環。經過2000次循環
後,再次量測其電阻。如果經過2000次循環後量測到電阻無限大,即認為錫膏24中有錫裂產生。
表4中實施例6~9和比較例5和6的高分子聚合物都是使用平均環氧當量1248的環氧樹脂,添加量均為100重量份。導熱填料使用破碎形氧化鋁,其佔導熱電絕緣層中的體積百分比為50%。實施例6~7硬化劑使用AJICURETM MY-24,添加量是3.5重量份。實施例8硬化劑使用AJICURETM PN-50,添加量也是3.5重量份。MY-24和PN-50屬於胺加成物(amine adduct)潛變型硬化劑。本發明之胺加成物潛變型硬化劑係使用咪唑化合物(imidazole compound)、含有3級胺基的化合物(tertiary amino group-containing compound)或醯肼化合物(hydrazide compound)與環氧化合物(epoxy compound)或異氰酸酯化合物(isocyanate compound)反應而成,例如AJICURETM PN-23、AJICURETM PN-40、AJICURETM PN-50、AJICURETM MY-24、AJICURETM MY-H、FujicureTM FXR-1030、AJICURETM VDH、AJICURETM UDH等。其他可使用的潛變型硬化劑還包含醯肼(hydrazide)、二醯肼(dihydrazide)、二氰胺複合物(Dicy)、己二酸二醯肼(adipic acid dihydrazide)、以及間苯二甲酸二醯肼(isophthalic dihydrazide)等種類的潛變型硬化劑。實施例9硬化劑使用AJICURETM AH-154,屬於二氰胺複合物(Dicy)的潛變型硬化劑,添加量是1重量份。比較例5的硬化劑使用Huntsman公司的JEFFAMINE® D-400,添加量是9.2重量份。比較例6的硬化劑使用Lindau公司的甲基六氫鄰苯二甲酸酐(MHHPA),添加量是12重量份。D-400和MHHPA屬於非潛變型硬化劑。實施例6~9和比較例5和6的導熱率都是2W/m.K。因硬化劑不同,實施例6~9的Tg約在60℃至85℃之間,而比較例5和6分別為約20℃和95℃,其中顯示胺加成物潛變型硬化劑相較於二氰胺複合物(Dicy)潛變型硬化劑,可以得到
較低的Tg,而更適於本發明的應用。散熱基板的金屬層選用一般的銅箔或金屬層包含一鍍層,該鍍層材料可以為鋅、鉻、鎳或其組合,且鍍層部份接觸該導熱電絕緣層。具有鍍層的金屬層例如是實施例7、8和實施例9的鍍鎳銅箔,該鍍鎳銅箔中鍍鎳部份接觸該導熱電絕緣層。同樣進行前述的錫裂測試及高壓蒸煮測試。實施例6~9都沒有錫裂問題,且其高壓蒸煮金屬層剝離強度降低率小於30%,其中使用鍍鎳銅箔的實施例7、8和9有更好的高壓蒸煮金屬層剝離強度降低率,可以小於15%,或進一步小於10%。比較例5雖然沒有錫裂,但高壓蒸煮金屬層剝離強度降低率高達58%。比較例6則有錫裂問題。另外,因為MY-24、PN-50和AH-154屬於潛變型硬化劑,其有效使用期(pot life)可達90天或120天,然而比較例5和6的有效使用期只有不到1天或約24天。該有效使用期係導熱電絕緣層材料在30℃下,其黏度增加為2倍的時間(增加1倍)。依此結果可知實施例6~9的散熱基板在30℃環境下經過3個月(90天)後其黏度增加都不會超過1倍。
本發明之導熱電絕緣層中之高分子聚合物選用至少二種不同環氧當量的環氧樹脂,並搭配潛變型硬化劑,將該高分子聚合物之玻璃轉換溫度控制在較低溫的40~90℃,可有效避免散熱基板固定連接晶片的焊錫有時會因在高低溫環境中使用而膨脹收縮進而產生錫裂的問題。直鏈型環氧樹脂相較於側
鏈型環氧樹脂較軟,不似其較脆硬,故也有助於防止錫裂。此外,本發明特別選用的非圓球形導熱填料之平均粒徑和比表面積的乘積在7.5~15μm.m2/g,因為整體導熱填料的表面積增大,可以減少導熱填料的使用比例而降低材料的硬度,因而有助於防止錫裂發生。
本發明之技術內容及技術特點已揭示如上,然而本領域具有通常知識之技術人士仍可能基於本發明之教示及揭示而作種種不背離本發明精神之替換及修飾。因此,本發明之保護範圍應不限於實施例所揭示者,而應包括各種不背離本發明之替換及修飾,並為以下之申請專利範圍所涵蓋。
Claims (14)
- 一種散熱基板,包括:一金屬基底;一導熱電絕緣層,設置於該金屬基底上,該導熱電絕緣層包含高分子聚合物以及散佈於該高分子聚合物中之非圓球形導熱填料,該高分子聚合物包含至少二種不同環氧當量的直鏈型環氧樹脂,該非圓球形導熱填料之平均粒徑和比表面積的乘積在7.5~15μm.m2/g,該導熱電絕緣層之玻璃轉換溫度在40~90℃,該導熱電絕緣層的導熱率在1~6W/m.K;以及一金屬層,設置於該導熱電絕緣層上;其中該金屬基底、導熱電絕緣層及金屬層為層疊結構。
- 根據請求項1之散熱基板,其中該非圓球形導熱填料佔該導熱電絕緣層的體積百分比35~65%。
- 根據請求項1之散熱基板,其中該非圓球形導熱填料係選自氧化鋁、氮化鋁、氮化硼、碳化矽或其組合。
- 根據請求項1之散熱基板,其中該非圓球形導熱填料包含破碎形導熱填料。
- 根據請求項1之散熱基板,其中該至少二種不同環氧當量的直鏈型環氧樹脂的平均環氧當量為400~2000g/eq。
- 根據請求項1之散熱基板,其中該至少二種不同環氧當量的直鏈型環氧樹脂的平均環氧當量為800~1500g/eq。
- 根據請求項1之散熱基板,其中該至少二種不同環氧當量的直鏈型環氧樹脂中至少一種直鏈型環氧樹脂的EEW為100~500g/eq,且佔該高分子聚合物的重量百分比大於20%。
- 根據請求項1之散熱基板,其中該金屬層包含一鍍層,該鍍層材料可以為鋅、鉻、鎳或其組合,且鍍層部份接觸該導熱電絕緣層。
- 根據請求項1之散熱基板,其中該金屬層包含鍍鎳銅箔,且鍍鎳部份接觸該導熱電絕緣層。
- 根據請求項9之散熱基板,其中該散熱基板經高壓蒸煮2atm、121℃飽和蒸氣96小時處理,金屬層的剝離強度降低率在30%之內。
- 根據請求項1之散熱基板,其中該導熱電絕緣層另包含潛變型硬化劑。
- 根據請求項11之散熱基板,其中該潛變型硬化劑包含胺加成物、醯肼、二醯肼、二氰胺複合物、己二酸二醯肼、以及間苯二甲酸二醯肼中至少一成分。
- 根據請求項12之散熱基板,其中該胺加成物係使用咪唑化合物、含有3級胺基的化合物或醯肼化合物與環氧化合物或異氰酸酯化合物反應而成。
- 根據請求項11之散熱基板,其中該散熱基板在30℃環境下經過3個月後其黏度增加不超過1倍。
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TW106124509A TWI627717B (zh) | 2017-07-21 | 2017-07-21 | 散熱基板 |
CN201711205388.9A CN109285819A (zh) | 2017-07-21 | 2017-11-27 | 散热基板 |
US15/827,897 US20190023960A1 (en) | 2017-07-21 | 2017-11-30 | Thermally conductive board |
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TW106124509A TWI627717B (zh) | 2017-07-21 | 2017-07-21 | 散熱基板 |
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CN113455111A (zh) * | 2019-02-22 | 2021-09-28 | 株式会社棚泽八光社 | 配线板 |
TWI782477B (zh) * | 2021-04-09 | 2022-11-01 | 艾姆勒科技股份有限公司 | 絕緣金屬基板結構 |
CN114771038B (zh) * | 2022-05-06 | 2023-12-08 | 南通汉瑞通信科技有限公司 | 一种散热基板及其制备设备 |
Citations (2)
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JPH08193139A (ja) * | 1995-01-17 | 1996-07-30 | Nippon Steel Chem Co Ltd | プリント配線板用プリプレグ及びそれを用いた金属張積層板 |
JP2014183300A (ja) * | 2013-03-21 | 2014-09-29 | Shindo Denshi Kogyo Kk | 発熱部品配線板及び発熱部品搭載モジュール |
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CN101072468A (zh) * | 2006-05-11 | 2007-11-14 | 冠品化学股份有限公司 | 软性印刷电路板基板 |
US20110217462A1 (en) * | 2006-09-26 | 2011-09-08 | Polytronics Technology Corp. | Methods for manufacturing insulated heat conductive substrate and insulated heat conductive composite substrate |
JP5133673B2 (ja) * | 2007-12-12 | 2013-01-30 | 株式会社巴川製紙所 | 接着フィルム及びその製造方法 |
CN103827221B (zh) * | 2011-09-08 | 2017-05-03 | 日立化成株式会社 | 树脂组合物、树脂片、树脂片固化物、带有树脂的金属箔以及散热构件 |
JP5788760B2 (ja) * | 2011-10-19 | 2015-10-07 | 日東電工株式会社 | 熱伝導性シート、led実装用基板およびledモジュール |
EP2867277B1 (en) * | 2012-06-29 | 2018-04-25 | Dow Global Technologies LLC | An epoxy resin blend dispersion and a process for preparing the dispersion |
CN103937259B (zh) * | 2014-04-04 | 2017-02-15 | 东莞市柏力有机硅科技有限公司 | 一种氧化石墨烯改性复合型导热硅橡胶及其制备方法 |
TWM507138U (zh) * | 2015-03-25 | 2015-08-11 | Polytronics Technology Corp | 散熱電路板 |
-
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- 2017-07-21 TW TW106124509A patent/TWI627717B/zh active
- 2017-11-27 CN CN201711205388.9A patent/CN109285819A/zh active Pending
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JPH08193139A (ja) * | 1995-01-17 | 1996-07-30 | Nippon Steel Chem Co Ltd | プリント配線板用プリプレグ及びそれを用いた金属張積層板 |
JP2014183300A (ja) * | 2013-03-21 | 2014-09-29 | Shindo Denshi Kogyo Kk | 発熱部品配線板及び発熱部品搭載モジュール |
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