TW202128422A - 三明治結構體及其製造方法 - Google Patents

三明治結構體及其製造方法 Download PDF

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Publication number
TW202128422A
TW202128422A TW109141075A TW109141075A TW202128422A TW 202128422 A TW202128422 A TW 202128422A TW 109141075 A TW109141075 A TW 109141075A TW 109141075 A TW109141075 A TW 109141075A TW 202128422 A TW202128422 A TW 202128422A
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Taiwan
Prior art keywords
sandwich structure
core material
iii
thermally conductive
fiber
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TW109141075A
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English (en)
Inventor
鈴木貴文
本田拓望
本間雅登
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日商東麗股份有限公司
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Publication of TW202128422A publication Critical patent/TW202128422A/zh

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Abstract

本發明之目的為提供一種兼具優異的散熱性與優異的機械特性之三明治結構體。 為了達成上述目的，本發明之三明治結構體具有以下之構成。亦即，一種三明治結構體，其係具有芯材(I)、與配置於前述芯材(I)之兩面的纖維強化材(II)之三明治結構體，其中前述芯材(I)包含面內導熱率為300W/m・K以上之片狀的導熱材(III)。

Description

三明治結構體及其製造方法
本發明係關於三明治結構體及其製造方法。
近年來，關於汽車、飛機、電子設備等之產業用製品，對於散熱性之市場需求正年年高漲。為了回應這樣的需求，而具有高導熱率的成形品被廣泛地利用於各種產業用途。其中，包含具有高導熱率的導熱材之三明治結構體又由於除了優異的散熱性，還具有優異的機械特性，所以被期待在各製品之活用。特別是導熱材與高強度材之三明治結構體係廣為研究。
專利文獻1中記載一種積層有導熱材與剛性保持材之三明治結構體的發明。認為藉由積層導熱材與剛性保持材，而可得到兼具優異的導熱性與優異的剛性之三明治結構體。
專利文獻2中記載一種三明治結構體的發明，該三明治結構體係積層具有優異的導熱性之石墨片及於該石墨片之兩面積層支撐片(support sheet)，且於該石墨片的至少一端面增設與該石墨片略同等厚度的密封間隔物(sealing spacer)。認為藉由於石墨片的周圍增設密封間隔物，而導熱性與機械的強度優異，防止石墨粉末由端面脫離，無刀狀的邊緣而操作性優異，且發揮抑制剝離的效果。
專利文獻3中記載一種將石墨片的積層體以樹脂層被覆之高導熱性殼體的發明。認為藉由將石墨片到端部為止以樹脂被覆，而能夠防止石墨薄膜間的剝落。 [先前技術文獻] [專利文獻]
[專利文獻1]國際公開第2016/002457號 [專利文獻2]日本特開2007-44994號公報 [專利文獻3]日本特開2006-95935號公報
[發明欲解決之課題]
專利文獻1中之三明治結構體係因導熱材之所有的端部露出，所以導熱材的強度不充分。又，導熱材與剛性保持材的接合強度不充分之情形，有由三明治結構體的端部開始剝離之可能性。
專利文獻2中之三明治結構體雖以密封間隔物保護石墨片的端部，然而密封間隔物之厚度的調整或密封間隔物的位置調整係煩雜，加工性低。又，密封間隔物與支撐片的接合強度不充分之情形，有由三明治結構體的端部開始剝離之可能性。
專利文獻3中之高導熱性殼體，係藉由將石墨片的表面及端部以樹脂被覆，而保護石墨片，但由於為利用樹脂的保護，所以剛性・強度低。
本發明係有鑑於上述課題而完成者，其目的在於提供一種兼具優異的散熱性與優異的機械特性之三明治結構體。 [用以解決課題之手段]
為了解決上述課題，本發明之三明治結構體具有以下之構成。
一種三明治結構體，其係具有芯材(I)、與配置於前述芯材(I)之兩面的纖維強化材(II)之三明治結構體，其中前述芯材(I)包含面內導熱率為300W/m・K以上之片狀的導熱材(III)。 [發明之效果]
若依照本發明，則即便為導熱材的強度不充分之情形、或者導熱材與保護導熱材之材料的接合不充分之情形，亦可得到兼具優異的散熱性與優異的機械特性之三明治結構體。
[用以實施發明的形態]
於以下詳細地說明本發明。
＜三明治結構體＞ 本說明書中之三明治結構體，係指於芯材之兩面配置具有比該芯材更高的彈性模數之表皮材的結構體。於本發明之三明治結構體中，芯材為包含片狀的導熱材(III)之芯材(I)，表皮材為纖維強化材(II)。又，片狀係指厚度薄且寬度寬者，係意指厚度為0.01μm以上10mm以下，且寬度與厚度之寬高比為10以上者。
芯材(I)包含片狀的導熱材(III)(以下有僅稱為導熱材(III)之情形)。此處所謂的「包含」，意指導熱材(III)係作為三明治結構體的積層結構中之芯材(I)之層的一部分而存在。
例如，下述樣態可謂芯材(I)包含導熱材(III)：如圖1的芯材(I)2覆蓋導熱材(III)4之一個端面(圖1中之右側的端面)及一方的表面(圖1中之上側的表面)之樣態；或如圖2的芯材(I)2覆蓋導熱材(III)4之兩面(兩方的表面)及所有的端面，亦即芯材(I)內包導熱材(III)之樣態。另一方面，下述樣態係自上述之「包含」的概念排除：如圖6的導熱材(III)(石墨片9)之所有的端面露出，亦即可視為僅導熱材(III)形成獨立之層之樣態。如此，藉由導熱材(III)被芯材(I)包含，而芯材(I)負擔施加於三明治結構體之應力，抑制應力往導熱材(III)的傳達，可抑制導熱材(III)的破壞。
芯材(I)較佳為覆蓋導熱材(III)的至少2個端面，更佳為進一步覆蓋導熱材(III)之兩面，進一步較佳為覆蓋導熱材(III)之兩面及所有的端面，亦即內包導熱材(III)。
此外，於本發明中，芯材(I)亦可透過接著劑或緩衝材等之其他構件而覆蓋導熱材(III)。又，亦可於芯材(I)與導熱材(III)之間有縫隙。
然而，於本發明中，較佳為導熱材(III)的至少1個端面不透過其他構件而直接接觸芯材(I)。又，較佳為導熱材(III)之至少一方的表面接觸芯材(I)。藉由導熱材(III)如此地與芯材(I)直接接觸，而由三明治結構體表面所傳來之熱可由芯材(I)往導熱材(III)迅速地傳遞。
再者，於本發明中，導熱材(III)較佳為未與芯材(I)接著。為了使導熱材(III)與芯材(I)接著，一般而言，有必要使接著劑介於彼等之間而存在，但三明治結構體中導熱材(III)所佔的比例會因接著劑的分量而減少，三明治結構體的散熱性降低。又，藉由導熱材(III)未與芯材(I)接著，而芯材(I)所負擔的施加於三明治結構體之應力的比例變大，所以抑制應力往導熱材(III)的傳達，可抑制導熱材(III)的破壞。
本發明之三明治結構體較佳為每單位寬度的彎曲剛性為0.5N・m以上，更佳為1.0N・m以上，進一步較佳為1.5N・m以上。因三明治結構體之每單位寬度的彎曲剛性越高越佳，所以針對每單位寬度的彎曲剛性的上限，並無特別限制，但通常為1000N・m左右。藉由使每單位寬度的彎曲剛性為上述之範圍，而三明治結構體成為剛性的結構體，且可合適地用於殼體等。每單位寬度的彎曲剛性可由三明治結構體的彈性模數E(Pa)、截面二次矩I(m4 )、三明治結構體的寬度b(m)，藉由下式而算出。 ・每單位寬度的彎曲剛性(N・m)=E(Pa)×I(m4 )/b(m) 又，三明治結構體的截面為矩形截面之情形，矩形截面的截面二次矩I為bh3 /12(m4 )，因此可藉由下式而算出。 ・每單位寬度的彎曲剛性(N・m)=E(Pa)×h3 (m3 )/12 就用以使每單位寬度的彎曲剛性為上述之範圍的手段而言，可舉出例如，如本發明之三明治結構體地使用纖維強化材(II)作為表皮材之方法。又，可舉出例如，使三明治結構體之厚度成為厚的之方法。
又，本發明之三明治結構體較佳為最大厚度為0.3mm以上3.0mm以下，更佳為0.5mm以上1.5mm以下。藉由使三明治結構體之厚度成為薄的，而有輕量化之效果，但比0.3mm更薄的三明治結構體有剛性不足之情形。
[導熱材(III)] 於本發明中，導熱材(III)為片狀，且其面內導熱率為300W/m・K以上。導熱材(III)之面內導熱率較佳為500w/m・K以上，進一步較佳為1000w/m・K以上。因面內導熱率越高越佳，所以針對面內導熱率的上限，並無特別限制，但已知具有2000W/m・K左右之面內導熱率的導熱材。若導熱材(III)之面內導熱率為300W/m・K以上，則熱往三明治結構體的面內方向的擴散優異，三明治結構體的散熱性為優異者。導熱材(III)之面內導熱率可利用雷射閃光法(laser flash method)，而藉由將試樣裝設於面內測定用的試樣架，且使試樣的大小為直徑20～30mm左右，使厚度為1.0mm以下來進行測定。又，對於難以吸收雷射光的材料，係將黑化膜於試樣表面上薄且均勻地製膜。對於紅外線偵測元件之測溫波長下的放射率低的材料，係於試樣背面進行同樣的處理。
導熱材(III)的材質，只要面內導熱率為300w/m・K以上，則不特別限定，可使用例如藉由對陶瓷、金屬、石墨、樹脂添加高導熱性填料而提高導熱率的高導熱性樹脂等。
再者，導熱材(III)較佳為包含選自由石墨片、金屬片及陶瓷片構成之群組的導熱片，更佳為由選自由石墨片、金屬片及陶瓷片構成之群組的導熱片所構成。就陶瓷片而言，可舉出氧化矽、氧化鋯、氧化鋁、氮化硼、碳化矽、氮化矽等之片。就金屬片而言，可舉出由鈦、鋁、鎂、鐵、銀、金、鉑、銅、鎳、或以此等金屬為主成分的合金構成之片。
因金屬片較為廉價，其中又以銅片係廉價且導熱率亦優異，所以從原料成本之觀點來看較佳。石墨片因比重小且導熱率優異，所以從使三明治結構體的輕量性、散熱性提升之觀點來看，於本發明中為特佳。
就石墨片而言，可舉出將石墨粉末與黏合劑樹脂混合成形之片、或者將膨脹石墨(expanded graphite)予以壓延之片、使用烴系氣體且藉由CVD法而使碳原子積層於基板上再經退火之片、將高分子化合物的薄膜予以石墨化之片等。其中，將高分子化合物的薄膜予以石墨化之片又由於導熱性非常高而較佳。
於本發明中，導熱材(III)較佳為包含複數的導熱片之積層結構體，更佳為係複數的導熱片之積層結構體。特別是石墨片其片內的石墨烯結構的配向係影響導熱率，一般而言，薄的石墨片係導熱率較高。所以，使用石墨片作為導熱片之情形，可藉由將複數片的積層結構體作為導熱材(III)，而提升三明治結構體的散熱性。此情形，構成導熱材(III)之複數的導熱片較佳為不透過接著劑等而互相直接接觸。藉由導熱片互相直接接觸，而可使三明治結構體中導熱材(III)所佔的比例增加，三明治結構體的散熱性提升。又，藉由導熱片彼此直接接觸，而成為熱往面外方向的擴散亦優異者。導熱片的積層片數較佳為2片以上10片以下，更佳為3片以上5片以下。若使積層片數增加，則三明治結構體的散熱性提升。另一方面，若使積層片數過度增加，則加工性變低。
導熱材(III)的平均厚度較佳為0.01μm以上2.0mm以下，更佳為5μm以上1.0mm以下，進一步較佳為15μm以上0.5mm以下。若導熱材(III)的平均厚度過小，則三明治結構體的散熱性降低，而若導熱材(III)的平均厚度過大，則三明治結構體的重量變重。導熱材(III)之平均厚度的測定方法，係使用測微器而測定導熱材(III)之9點的厚度至小數點1位為止，且將其平均值當成平均厚度。關於所測定之點，係以各測定點分別與相鄰之點或試樣端部之間隔於縱方向與橫方向上成為均等的間隔之方式，於縱及橫方向上各3點之合計9點進行測定。
[芯材(I)] 於本發明中，較佳為芯材(I)包含多孔體，更佳為芯材(I)為多孔體。藉由芯材(I)包含多孔體，而在三明治結構體的輕量性之觀點為有利。又，使芯材(I)包含導熱材(III)之際，為多孔體之芯材(I)於面外方向上被壓扁、或者膨脹，因此可無導熱材(III)之位置偏移而芯材(I)包含導熱材(III)。芯材(I)為多孔體之情形，在芯材(I)中之空隙的體積分率(volume fraction)較佳為相對於芯材(I)的表觀體積為10%以上85%以下，更佳為20%以上85%以下，從兼具輕量性與機械特性之觀點來看，進一步較佳為50%以上80%以下。
芯材(I)的材質並未特別限制，但可較佳使用例如以連續纖維或不連續纖維強化的纖維強化樹脂。此外，連續的強化纖維，意指至少於單向上長至15mm以上、較佳為100mm以上的長度而連續的強化纖維。就以連續纖維強化的纖維強化樹脂而言，可使用單向纖維強化樹脂或織物纖維強化樹脂。就以不連續纖維強化的纖維強化樹脂而言，短纖維強化樹脂或長纖維強化樹脂之任一者皆可使用。又，就非纖維強化樹脂而言，亦可使用樹脂片或樹脂發泡體等。
無論是纖維強化樹脂或非纖維強化樹脂，芯材(I)包含樹脂之情形，對於該樹脂並無特別限制，可為熱硬化樹脂，亦可為熱塑性樹脂。熱塑性樹脂可舉出例如選自下述之熱塑性樹脂：「聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚對苯二甲酸三亞甲酯(PTT)、聚萘二甲酸乙二酯(PEN)、液晶聚酯等之聚酯、或聚乙烯(PE)、聚丙烯(PP)、聚丁烯等之聚烯烴、或聚甲醛(POM)、聚醯胺(PA)、聚苯硫醚(PPS)等之聚芳硫醚、聚酮(PK)、聚醚酮(PEK)、聚醚醚酮(PEEK)、聚醚酮酮(PEKK)、聚醚腈(PEN)、聚四氟乙烯等之氟系樹脂」等之結晶性樹脂、「苯乙烯系樹脂、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)、聚苯醚(PPE)、聚醯亞胺(PI)、聚醯胺醯亞胺(PAI)、聚醚醯亞胺(PEI)、聚碸(PSU)、聚醚碸、聚芳酯(PAR)」等之非晶性樹脂，另有酚系樹脂、苯氧樹脂，還有聚苯乙烯系、聚烯烴系、聚胺甲酸酯系、聚酯系、聚醯胺系、聚丁二烯系、聚異戊二烯系、氟系樹脂、及丙烯腈系等之熱塑彈性體等、或此等之共聚物及改質物等。其中，從所得之三明治結構體的輕量性之觀點來看，又較佳為聚烯烴。特別是芯材(I)包含多孔體之情形，由於使輕量效果加乘，而較佳為聚烯烴。又，從強度之觀點來看，較佳為聚醯胺。特別是芯材(I)由纖維強化樹脂構成之情形，從強化纖維與樹脂的界面接合強度之觀點來看，較佳為聚醯胺。又，熱硬化性樹脂可舉出例如不飽和聚酯樹脂、乙烯酯樹脂、環氧樹脂、酚樹脂(可溶酚醛樹脂)、脲樹脂、三聚氰胺樹脂、聚醯亞胺樹脂、馬來醯亞胺樹脂、苯并
Figure 109141075-A0304-12-0059-1
Figure 109141075-A0304-12-0000-4
樹脂等、或摻合此等之2種類以上的樹脂等之熱硬化性樹脂。其中，特別是芯材(I)由纖維強化樹脂構成之情形，從強化纖維與樹脂的界面接合強度之觀點來看，又可較佳使用環氧樹脂。
再者，於樹脂中亦可因應其用途而添加雲母、滑石、高嶺土、水滑石、絹雲母、皂土、硬矽鈣石、海泡石、膨潤石、蒙脫石、矽灰石、氧化矽、碳酸鈣、玻璃珠、玻璃薄片、玻璃微球(glass microballoon)、黏土、二硫化鉬、氧化鈦、氧化鋅、氧化銻、多磷酸鈣、石墨、硫酸鋇、硫酸鎂、硼酸鋅、硼酸亞鈣、硼酸鋁鬚晶、鈦酸鉀鬚晶及高分子化合物等之填充材、金屬系、金屬氧化物系、碳黑及石墨粉末等之導電性賦予材、溴化樹脂等之鹵素系阻燃劑、三氧化銻或五氧化銻等之銻系阻燃劑、多磷酸銨、芳香族磷酸酯(aromatic phosphate)及紅磷等之磷系阻燃劑、有硼酸金屬鹽、羧酸金屬鹽及芳香族磺醯亞胺金屬鹽等之有機酸金屬鹽系阻燃劑、硼酸鋅、鋅、氧化鋅及鋯化合物等之無機系阻燃劑、三聚氰酸、異三聚氰酸、三聚氰胺、三聚氰胺三聚氰酸鹽(melamine cyanurate)、三聚氰胺磷酸鹽及氮化胍等之氮系阻燃劑、PTFE等之氟系阻燃劑、聚有機矽氧烷等之聚矽氧系阻燃劑、氫氧化鋁或氫氧化鎂等之金屬氫氧化物系阻燃劑、還有其他的阻燃劑、氧化鎘、氧化鋅、氧化銅(I)、氧化銅(II)、氧化鐵(II)、氧化鐵(III)、氧化鈷、氧化錳、氧化鉬、氧化錫及氧化鈦等之阻燃助劑、顏料、染料、助滑劑、脫模劑、增容劑(compatibilizer)、分散劑、雲母、滑石及高嶺土等之結晶成核劑、磷酸酯等之塑化劑、熱穩定劑、抗氧化劑、防著色劑、紫外線吸收劑、流動性改質劑、發泡劑、抗菌劑、減振劑、除臭劑、滑動性改質劑、及聚醚酯醯胺等之抗靜電劑等。尤其，於用途為電氣・電子設備、汽車、飛機等時，有要求阻燃性之情形，較佳添加磷系阻燃劑、氮系阻燃劑、無機系阻燃劑。 上述阻燃劑，為了阻燃效果的表現、以及與所使用之樹脂的機械特性或成形時的樹脂流動性等保持良好的特性平衡，而相對於樹脂100質量份，較佳為使阻燃劑為1～20質量份。更佳為1～15質量份。
從三明治結構體的輕量性之觀點來看，芯材(I)的比重較佳為0.01～1.5。更佳為0.1～1.3，進一步較佳為0.3～1.1。比重之測定，可切下芯材(I)，且依據ISO1183(1987)或ISO0845(1988)來測定。
芯材(I)為纖維強化材料之情形，對於所包含之強化纖維的種類並無特別限制，可使用例如碳纖維、玻璃纖維、聚芳醯胺(aramid)纖維、氧化鋁纖維、碳化矽纖維、硼纖維、金屬纖維、天然纖維、礦物纖維等，此等亦可併用1種或2種以上。其中，從比強度、比剛性高及輕量化效果之觀點來看，又可較佳使用PAN系、瀝青系、嫘縈系等之碳纖維。又，從提高所得之三明治結構體的經濟性之觀點來看，可較佳使用玻璃纖維，尤其從機械特性與經濟性的平衡來看，較佳為併用碳纖維與玻璃纖維。再者，從提高所得之三明治結構體的衝擊吸收性或賦形性之觀點來看，可較佳使用聚芳醯胺纖維，尤其從機械特性與衝擊吸收性的平衡來看，較佳為併用碳纖維與聚芳醯胺纖維。又，從提高所得之三明治結構體的導電性之觀點來看，亦可使用被覆有鎳或銅或鐿等之金屬的強化纖維或瀝青系的碳纖維。
從機械特性提升之觀點來看，強化纖維較佳為以上漿劑進行表面處理。就上漿劑而言，可舉出多官能環氧樹脂、丙烯酸系聚合物、多元醇、聚乙亞胺等，具體而言可舉出甘油三環氧丙基醚、二甘油聚環氧丙基醚、聚甘油聚環氧丙基醚、山梨醇聚環氧丙基醚、阿拉伯糖醇聚環氧丙基醚、三羥甲基丙烷三環氧丙基醚、新戊四醇聚環氧丙基醚等之脂肪族多元醇的聚環氧丙基醚、聚丙烯酸、丙烯酸與甲基丙烯酸之共聚物、丙烯酸與馬來酸之共聚物、或者此等之2種以上的混合物、聚乙烯醇、甘油、二甘油、聚甘油、山梨醇、阿拉伯糖醇、三羥甲基丙烷、新戊四醇、在1分子中包含較多胺基的聚乙亞胺等，此等之中，從在1分子中包含許多反應性高的環氧基，且水溶性高而塗布容易來看，又可較佳使用甘油三環氧丙基醚、二甘油聚環氧丙基醚、聚甘油聚環氧丙基醚。
於本發明中之芯材(I)包含多孔體之情形中，特佳為多孔體由纖維強化樹脂構成。纖維強化樹脂的強化纖維可為連續纖維，亦可為不連續纖維，但較佳為不連續纖維，更佳為不連續纖維形成三維的網絡，並且具有不連續纖維彼此的交點藉由樹脂而結合之結構。因不連續纖維彼此係藉由樹脂接合，而芯材(I)的剪力彈性模數變高，三明治結構體的剛性變高。以下，針對此樣態進行說明。
於纖維強化樹脂中，不連續纖維較佳係作為少於500條的細纖度股線(strand)而存在，更佳係以被分散為單纖維狀而存在為佳。不連續纖維的纖維長較佳為1～50mm，更佳為3～30mm。若為1mm以上，則可效率良好地發揮利用不連續纖維的補強效果。又，若為50mm以下，則可良好地保持不連續纖維的分散。
不連續纖維的單纖維彼此藉由樹脂而結合之結合部分的個數之比例，係相對於不連續纖維彼此交叉之全交叉部分的個數為50%以上，更佳為70%以上，進一步較佳為90%以上。
從兼具機械特性與成形性之觀點來看，不連續纖維的質量比例，較佳為相對於芯材(I)的全體而為5～60質量%，更佳為10～50質量%，進一步較佳為15～40質量%。
於纖維強化樹脂中，不連續纖維係以其表面的30%以上、更佳為50%以上、進一步較佳為80%以上被樹脂所被覆為佳。可藉由成為該被覆率，而提高芯材(I)的剛性。被覆率係藉由下述進行測定：以掃描式電子顯微鏡(SEM)觀察芯材(I)的截面，且區別強化纖維與樹脂。
[纖維強化材(II)] 於本發明中，纖維強化材(II)係包含彈性模數比芯材(I)更高之強化纖維的構件，其構成三明治結構體的表皮材。
纖維強化材(II)的材質只要具有比芯材(I)更大的彈性模數，則未特別限制，可為以連續纖維強化的纖維強化樹脂、或亦可為以不連續纖維強化的纖維強化樹脂。就以連續纖維強化的纖維強化樹脂而言，可使用單向纖維強化樹脂或織物纖維強化樹脂。就以不連續纖維強化的纖維強化樹脂而言，短纖維強化樹脂或長纖維強化樹脂之任一者皆可使用。從三明治結構體的機械特性之觀點來看，較佳為使用連續纖維強化材，其中又更佳為使用單向纖維強化材。另一方面，從三明治結構體的賦形性之觀點來看，可合適地使用不連續纖維強化材料。又，纖維強化樹脂的基質樹脂並無特別限制，熱硬化性樹脂、熱塑性樹脂之任一者皆可使用，可使用與上述之芯材(I)之說明中所例示者同樣的樹脂。再者，亦可使基質樹脂含有添加劑，就添加劑而言，可舉出上述之芯材(I)之說明中所例示的添加劑。
對於纖維強化材(II)中所包含之強化纖維的種類並無特別限制，可使用與上述之芯材(I)之說明中所例示者同樣的強化纖維。
從兼具機械特性與成形性之觀點來看，纖維強化材(II)中之強化纖維的質量比例，較佳為相對於纖維強化材(II)100質量%而為30～90質量%，更佳為40～80質量%，進一步較佳為50～70質量%。亦可為將上述的上限與下限之任一者予以組合的範圍。
於本發明之三明治結構體中，較佳為纖維強化材(II)包含碳纖維強化樹脂，更佳為由碳纖維強化樹脂構成。碳纖維強化樹脂由碳纖維與基質樹脂構成。因由碳纖維強化樹脂構成，而變得容易得到輕量性及剛性、強度優異的三明治結構體。碳纖維之中，又更佳為彈性模數、導熱率高的高的瀝青系碳纖維。藉由使用瀝青系碳纖維，而可期待三明治結構體之剛性、散熱性的提升。
此外，纖維強化材(II)亦可為積層有複數片如上述的構件的積層結構。
＜三明治結構體之製造方法＞ 本發明之三明治結構體可較佳藉由以下所示之[1]～[3]中的任一之方法製造。
方法[1]：一種三明治結構體之製造方法，其係製造本發明之三明治結構體之方法，其中依序包含：在導熱材(III)的至少1個表面及至少1個端面配置芯材(I)的前驅物而進行熱壓之步驟；及在前述芯材(I)之兩面接合前述纖維強化材(II)之步驟。
方法[2]：一種三明治結構體之製造方法，其係製造本發明之三明治結構體之方法，其中依序包含：在導熱材(III)的至少1個表面及至少1個端面配置芯材(I)的前驅物之步驟；在前述芯材(I)的前驅物之兩面配置纖維強化材(II)的前驅物之步驟；及進行熱壓之步驟。
方法[3]：一種三明治結構體之製造方法，其係製造本發明之三明治結構體之方法，其中依序包含：在導熱材(III)的至少1個表面及至少1個端面配置芯材(I)的前驅物而進行熱壓之步驟；及在芯材(I)之兩面配置纖維強化材(II)的前驅物之步驟；及進行熱壓之步驟。
於方法[1]～[3]中，「在導熱材(III)的至少1個表面及至少1個端面配置芯材(I)的前驅物」，係指芯材(I)的前驅物被以覆蓋導熱材(III)的至少1個表面及至少1個端面之方式配置。
於方法[1]～[3]中，較佳為芯材(I)的前驅物被配置在導熱材(III)之兩面。又，於方法[1]～[3]中，芯材(I)的前驅物更佳為被配置於導熱材(III)的至少2個端面，進一步較佳為進一步被配置於導熱材(III)之兩面，特佳為被配置於導熱材(III)之兩面及所有的端面，亦即內包導熱材(III)。
所謂芯材(I)的前驅物，例如芯材(I)為纖維強化樹脂之情形，係包含強化纖維及樹脂的預浸體。又，芯材(I)為非纖維強化樹脂之情形，可舉出包含發泡劑的樹脂片、或樹脂片的積層體等。
為本發明之較佳樣態之一的芯材(I)包含多孔體且多孔體由纖維強化樹脂構成之情形，芯材(I)的前驅物例如可藉由將熱塑性樹脂的薄膜或不織布壓縮至不連續強化纖維氈並且使其含浸而製造。不連續強化纖維氈，係例如將不連續的強化纖維預先分散為股線狀、較佳為略單纖維狀、更佳為單纖維狀而製造。更具體而言，可舉出以空氣流將不連續的強化纖維分散而片化的氣流成網(air-laid)法、或將不連續的強化纖維一邊機械性地梳整一邊形成片的梳理(carding)法等之乾式製程、利用將不連續的強化纖維於水中攪拌而進行抄紙的Radlite法之濕式製程等。
作為使不連續的強化纖維更接近單纖維狀的手段，於乾式製程可例示：設置開纖棒之手段、使開纖棒振動之手段、使梳理機的齒距精細化之手段、調整梳理機的旋轉速度之手段等。又，於濕式製程可例示：調整不連續的強化纖維之攪拌條件的手段、使分散液之強化纖維濃度稀薄化的手段、調整分散液之黏度的手段、於移送分散液之際抑制渦流的手段等。特別是，不連續強化纖維氈較佳為以濕式法製造，可藉由增加投入纖維之濃度、或調整分散液之流速(流量)與網狀輸送帶(mesh conveyor)之速度，而輕易調整不連續強化纖維氈中之強化纖維的比例。例如，相對於分散液之流速而減慢網狀輸送帶之速度，藉此而所得之不連續強化纖維氈中的纖維之配向變得不易朝向拉取方向，能夠製造體積大的不連續強化纖維氈。就不連續強化纖維氈而言，可由不連續的強化纖維單體所構成，亦可不連續的強化纖維與粉末形狀或纖維形狀的基質樹脂成分混合、或不連續的強化纖維與有機化合物或無機化合物混合、或不連續的強化纖維彼此以樹脂成分固定。
使熱塑性樹脂的薄膜或不織布含浸至不連續強化纖維氈之際的壓力，較佳係使其為0.5MPa以上30MPa以下，更佳係使其為1MPa以上5MPa以下為佳。若壓力比0.5MPa更小，則有熱塑性樹脂未含浸至不連續強化纖維氈之情形，又若比30MPa更大，則芯材的前驅物之厚度的調整變得困難。使熱塑性樹脂的薄膜或不織布含浸之際的溫度，較佳為熱塑性樹脂的熔點或者玻璃轉移點以上的溫度，更佳為於熔點或者玻璃轉移點加上10℃的溫度以上，進一步較佳為於熔點或者玻璃轉移點加上20℃的溫度以上。此外，使熱塑性樹脂的薄膜或不織布含浸之際的溫度，比起熱塑性樹脂的熔點或者玻璃轉移點而溫度過高時，有發生熱塑性樹脂的分解或劣化之情形，因此較佳為於熱塑性樹脂的熔點或者玻璃轉移點加上150℃的溫度以下。
就用以實現使熱塑性樹脂的薄膜或不織布含浸至不連續強化纖維氈之方法的設備而言，可合適地使用壓縮成形機、雙帶壓機。壓縮成形機為批次式，藉由使其為將加熱用與冷卻用的2台以上並列的間歇式加壓系統，而可圖謀生產性的提升。雙帶壓機為連續式，因可輕易進行連續性的加工，所以連續生產性優異。
所謂纖維強化材(II)的前驅物，通常為包含強化纖維及樹脂的預浸體。可舉出例如：以連續纖維強化的單向纖維預浸體或織物纖維預浸體；或者積層有強化纖維片與樹脂片的積層體等。
方法[1]～[3]皆具有進行熱壓之步驟。於此步驟中，可藉由在導熱材(III)的至少1個表面及至少1個端面配置芯材(I)的前驅物，以芯材(I)的前驅物之膨脹溫度或接合所必須之溫度進行熱壓，而使芯材包含導熱材。就熱壓的設備而言，可合適地使用壓縮成形機。壓縮成形機為批次式，藉由使其為將加熱用與冷卻用的2台以上並列的間歇式加壓系統，而可圖謀生產性的提升。
方法[1]係在芯材(I)的成形過程，使芯材(I)包含導熱材(III)之後，在所成形的芯材(I)之兩面接合纖維強化材(II)之方法。就使芯材(I)與纖維強化材(II)接合的手段而言，並未特別限定，但例如有將芯材(I)與纖維強化材(II)藉由熱板熔接、振動熔接、超音波熔接、雷射熔接、電阻熔接、感應加熱熔接、或者接著劑等進行接合之方法。可較佳地用於芯材(I)與纖維強化材(II)的成形溫度或成形壓力等之成形條件大幅相異之情形等。
方法[2]係同時實施芯材(I)與纖維強化材(II)的成形及接合之方法。可較佳地用於芯材(I)與纖維強化材(II)的成形溫度或成形壓力等之成形條件相近之情形等。因可同時進行芯材(I)與纖維強化材(II)的成形・接合，所以從生產性之觀點來看較佳。
方法[3]係在芯材(I)的成形過程，使芯材(I)包含導熱材(III)之後，在所成形的芯材(I)之兩面配置纖維強化材(II)的前驅物而進行熱壓之方法。因可同時進行芯材(I)與纖維強化材(II)的接合以及纖維強化材(II)的成形，所以從生產性之觀點來看較佳。
＜殼體＞ 本發明之殼體係使用本發明之三明治結構體而成。藉由利用本發明之三明治結構體，而可得到兼具優異的力學特性與輕量性之殼體。又，即使於量產性之觀點，利用加壓成形等之高週期(high cycle)成形的成形亦為可能，因而較佳。
本發明之殼體，例如可藉由利用上述之三明治結構體之製造方法來製作所欲的殼體之形狀的三明治結構體而獲得。 [實施例]
以下，由實施例來進一步詳細地說明本發明。
(1)三明治結構體的彎曲強度、彎曲彈性模數測定 將所製作之三明治結構體的彎曲試驗片，按照ISO178法(1993)，測定彎曲特性。以彎曲試驗片之最表面的纖維方向為彎曲方向，設為測定數n=5，將平均值作為彎曲強度及彎曲彈性模數。就測定裝置而言，係使用Instron Japan(股)製「INSTRON」(註冊商標)5565型萬能材料試驗機。
(2)三明治結構體的散熱性評價 如圖3所示，於所製作之三明治結構體1的背面四角貼附10mm×10mm之厚度3mm的橡膠製間隔物6，並設置於實驗台。於所設置之三明治結構體的表面一角設置50mm×25mm的微陶瓷加熱器5(Sakaguchi E.H(股)製，微陶瓷加熱器MS-2(商品名))，於一定電流・一定電壓下，將加熱器以10W進行加熱。從加熱器加熱開始起15分鐘後加熱器溫度成為一定時的加熱器溫度，依照下述基準評價散熱性。 A：加熱器溫度低於100℃(散熱性非常高) B：加熱器溫度100℃以上且低於120℃(散熱性高) C：加熱器溫度120℃以上(散熱性低) (參考例1)碳纖維束的製作 由以聚丙烯腈為主成分的聚合物進行紡絲、燒製處理，得到總絲數12000條的碳纖維連續束。藉由浸漬法而對該碳纖維連續束賦予上漿劑，且在120℃之溫度的加熱空氣中進行乾燥，得到碳纖維束。此碳纖維束之特性如下所述。
單纖維徑：7μm 每單位長度的質量：0.8g/m 密度：1.8g/cm3 拉伸強度：4.2GPa 拉伸彈性模數：230GPa 上漿種類：聚氧乙烯油基醚 上漿附著量：1.5質量% (參考例2)碳纖維氈的製作 將參考例1的碳纖維束以匣式切斷器(cartridge cutter)切成纖維長6mm，得到經切斷的碳纖維束。製作界面活性劑(NACALAI TESQUE(股)製，聚氧乙烯月桂基醚(商品名))0.1質量%的水分散液，將此分散液與經切斷的碳纖維束投入抄紙機，製作碳纖維氈。
抄紙機具備分散槽、抄紙槽、還有連接分散槽與抄紙槽的輸送部。分散槽附有攪拌機，能夠分散所投入的分散液與經切斷的碳纖維束。抄紙槽具備於底部具有抄紙面的網狀輸送帶，且於網狀輸送帶連接能搬運所抄紙而成之碳纖維氈的輸送帶。抄紙係使分散液中的纖維濃度為0.05質量%來進行。將所抄紙而成之碳纖維氈以200℃的乾燥爐進行乾燥。接著，於藉由輸送帶所搬運之碳氈的上面部，噴灑黏合劑(NIPPON SHOKUBAI(股)製，「POLYMENT」(註冊商標)SK-1000)之3質量%的水分散液作為黏合劑。吸取過剩的黏合劑，以200℃的乾燥爐進行乾燥，得到碳纖維氈。所得之碳纖維氈的單位面積質量為50g/m2 。
(參考例3)聚丙烯樹脂薄膜的製作 摻合90質量%之未改質聚丙烯樹脂(Prime Polymer(股)製，「Prime Polypro」(註冊商標)J105G)、與10質量%之酸改質聚丙烯樹脂(Mitsui Chemicals(股)製，「ADMER」(註冊商標)QE510)。以擠出機將此摻合品熔融捏合之後，由T字模擠出。然後，藉由以60℃的冷卻輥拉取，將樹脂冷卻固化，而得到聚丙烯樹脂薄膜。
(參考例4)環氧樹脂薄膜的製作 使用塗布機將環氧樹脂(基本樹脂：雙氰胺(dicyandiamide)/二氯苯基甲基脲硬化系環氧樹脂)塗布於脫模紙上，而得到環氧樹脂薄膜。
(參考例5)單向預浸體的製作 將參考例1的碳纖維束單向排列為片狀，將2片參考例4的環氧樹脂薄膜從碳纖維束之兩面重疊，藉由加熱加壓而使樹脂含浸，得到單向預浸體，其碳纖維的單位面積質量為110g/m2 ，厚度0.1mm，基質樹脂的質量分率為30質量%。
(實施例1) 使用參考例2的碳纖維氈、參考例3的聚丙烯樹脂薄膜、參考例5的單向預浸體、以及石墨片(Panasonic(股)製，「PGS」(註冊商標)EYGS182307，面內導熱率1000W/m・K)，製作三明治結構體。將碳纖維氈、聚丙烯樹脂薄膜、及單向預浸體調整成50mm×150mm之尺寸，將石墨片調整成40mm×140mm之尺寸之後，按照[單向預浸體0°/單向預浸體90°/聚丙烯樹脂薄膜/碳纖維氈/石墨片/碳纖維氈/聚丙烯樹脂薄膜/單向預浸體90°/單向預浸體0°]的順序，以表面之單向預浸體的纖維方向成為試樣的縱軸方向之方式進行積層。此時，石墨片配置於積層體的中央。將此積層體以脫模薄膜夾住，且進一步以工具板夾住。將彼等投入盤面溫度為180℃的加壓成形機，藉由以3MPa進行加熱加壓10分鐘，而進行預浸體的硬化與聚丙烯樹脂對碳纖維氈的含浸。其次，於工具板之間插入厚度1mm的間隔物，投入盤面溫度為40℃的加壓成形機，以表面壓力3MPa進行冷卻加壓至積層體冷卻，藉此而得到芯材被配置於導熱材的周圍之三明治結構體。以測微器測定試樣的厚度的結果，厚度為1.0mm。藉由於工具板之間插入厚度1.0mm的間隔物，而含浸有聚丙烯樹脂之碳纖維氈回彈，芯材成為多孔體。此外，本實施例中之試樣由於為平板，所以厚度一定。因此，在試樣之任一點所測定的厚度成為最大厚度。關於其他的實施例、比較例亦相同。
又，彎曲試驗片除了將碳纖維氈、聚丙烯樹脂薄膜、及單向預浸體調整成50mm×40mm之尺寸，將石墨片調整成40mm×30mm之尺寸以外，係同樣地進行預成形、加壓成形，得到芯材被配置於導熱材的周圍之三明治結構體的彎曲試驗片。將所得之三明治結構體的截面圖示於圖4。所得之三明治結構體如圖4，係於芯材2之兩面具有由單向纖維強化材0° 7及單向纖維強化材90° 8構成的纖維強化材層。又，石墨片9為兩面及所有的端面被芯材覆蓋之結構，係由芯材所保護之結構。因此，所得之三明治結構體的機械特性優異，並無石墨片的剝離或石墨片碎片的散落。又，因包含石墨片，所以散熱性亦優異。
(實施例2) 除了將石墨片的積層片數變更為4片，且按照[單向預浸體0°/單向預浸體90°/聚丙烯樹脂薄膜/碳纖維氈/石墨片/石墨片/石墨片/石墨片/碳纖維氈/聚丙烯樹脂薄膜/單向預浸體90°/單向預浸體0°]的順序進行積層以外，係與實施例1同樣地進行預成形、加壓成形，得到芯材被配置於導熱材的周圍之三明治結構體、與三明治結構體的彎曲試驗片。將所得之三明治結構體的截面圖示於圖5。因石墨片被芯材保護，所以所得之三明治結構體的機械特性優異。又，因包含複數的石墨片，所以散熱性亦非常優異。
(比較例1) 除了將石墨片的尺寸調整成50×150mm之尺寸以外，係與實施例1同樣地進行預成形、加壓成形，得到導熱材之所有的端部露出之三明治結構體。又，彎曲試驗片製作時除了將石墨片調整成50mm×40mm之尺寸以外，係與實施例1同樣地進行預成形、加壓成形，得到導熱材之所有的端部露出之三明治結構體的彎曲試驗片。將所得之三明治結構體的截面圖示於圖6。所得之三明治結構體因石墨片之所有的端部露出，所以在石墨片的層間發生剝離。
(比較例2) 除了將石墨片的尺寸調整成50×150mm之尺寸以外，係與實施例2同樣地進行預成形、加壓成形，得到導熱材之所有的端部露出之三明治結構體。又，彎曲試驗片製作時除了將石墨片調整成50mm×40mm之尺寸以外，係與實施例2同樣地進行預成形、加壓成形，得到導熱材之所有的端部露出之三明治結構體的彎曲試驗片。將所得之三明治結構體的截面圖示於圖7。由於所得之三明治結構體的強度非常低，且於加壓成形後在石墨片與石墨片之間發生剝離，所以無法實施彎曲試驗、散熱性評價。
(比較例3) 除了未積層石墨片以外，係與實施例1同樣地進行預成形、加壓成形，得到不包含導熱材的三明治結構體。又，彎曲試驗片製作時亦同樣地除了未積層石墨片以外，係與實施例1同樣地進行預成形、加壓成形，得到不包含導熱材之三明治結構體的彎曲試驗片。將所得之三明治結構體的截面圖示於圖8。所得之三明治結構體因不包含導熱材，所以散熱性低。
[表1]
　 實施例1 實施例2 比較例1 比較例2 比較例3
試樣厚度 [mm] 1.0 1.0 1.0 1.0 1.0
導熱材 1片石墨片 4片石墨片 1片石墨片 4片石墨片 -
導熱材端部狀態 芯材於端部 的周圍 芯材於端部 的周圍 所有的 端部露出 所有的 端部露出 -
彎曲強度 [MPa] 732 702 186 - 883
彎曲彈性模數 [GPa] 60 58 55 - 61
每單位寬度的彎曲剛性 [N･m] 5.0 4.8 4.6 - 5.1
加熱器溫度 [℃] 109 99 107 - 136
散熱性 [-] B A B - C
石墨片的層間剝離 [-] 無 無 有 有 -
[產業上利用之可能性]
本發明之三明治結構體可兼具優異的散熱性與優異的機械特性。因此，能夠作為電氣・電子設備、機器人、二輪車、汽車、飛機之結構構件等而應用於廣泛的產業領域。特別是，可較佳應用於要求高散熱性的電子設備等之殼體。
1:三明治結構體 2:芯材(I) 3:纖維強化材(II) 4:導熱材(III) 5:加熱器 6:橡膠製間隔物 7:單向纖維強化材0° 8:單向纖維強化材90° 9:石墨片
圖1為呈示本發明之三明治結構體的一實施形態之示意圖。 圖2為呈示本發明之三明治結構體的別的實施形態之示意圖。 圖3為呈示散熱性評價的狀況之示意圖。 圖4為實施例1中製作之三明治結構體的截面示意圖。 圖5為實施例2中製作之三明治結構體的截面示意圖。 圖6為比較例1中製作之三明治結構體的截面示意圖。 圖7為比較例2中製作之三明治結構體的截面示意圖。 圖8為比較例3中製作之三明治結構體的截面示意圖。
1:三明治結構體
2:芯材(I)
3:纖維強化材(II)
4:導熱材(III)

Claims (15)

  1. 一種三明治結構體，其係具有芯材(I)、與配置於該芯材(I)之兩面的纖維強化材(II)之三明治結構體，其中該芯材(I)包含面內導熱率為300W/m・K以上之片狀的導熱材(III)。
  2. 如請求項1之三明治結構體，其中該芯材(I)覆蓋該導熱材(III)的至少2個端面。
  3. 如請求項2之三明治結構體，其中該芯材(I)覆蓋該導熱材(III)之兩面及所有的端面。
  4. 如請求項1至3中任一項之三明治結構體，其中該導熱材(III)包含選自由石墨片、金屬片及陶瓷片構成之群組的導熱片。
  5. 如請求項4之三明治結構體，其中該導熱材(III)包含複數的該導熱片之積層結構體。
  6. 如請求項1至5中任一項之三明治結構體，其中該導熱材(III)未與該芯材(I)接著。
  7. 如請求項1至6中任一項之三明治結構體，其中該芯材(I)包含多孔體。
  8. 如請求項7之三明治結構體，其中該多孔體係由纖維強化樹脂構成。
  9. 如請求項1至8中任一項之三明治結構體，其中該纖維強化材(II)包含碳纖維強化樹脂。
  10. 如請求項1至9中任一項之三明治結構體，其每單位寬度的彎曲剛性為0.5N・m以上。
  11. 如請求項1至10中任一項之三明治結構體，其最大厚度為0.3mm以上3.0mm以下。
  12. 一種殼體，其係使用如請求項1至11中任一項之三明治結構體而成。
  13. 一種三明治結構體之製造方法，其係製造如請求項1至11中任一項之三明治結構體之方法，其中依序包含：在該導熱材(III)的至少1個表面及至少1個端面配置芯材(I)的前驅物而進行熱壓之步驟；及在該芯材(I)之兩面接合該纖維強化材(II)之步驟。
  14. 一種三明治結構體之製造方法，其係製造如請求項1至11中任一項之三明治結構體之方法，其中依序包含：在該導熱材(III)的至少1個表面及至少1個端面配置芯材(I)的前驅物之步驟；在該芯材(I)的前驅物之兩面配置纖維強化材(II)的前驅物之步驟；及進行熱壓之步驟。
  15. 一種三明治結構體之製造方法，其係製造如請求項1至11中任一項之三明治結構體之方法，其中依序包含：在該導熱材(III)的至少1個表面及至少1個端面配置芯材(I)的前驅物而進行熱壓之步驟；及在芯材(I)之兩面配置纖維強化材(II)的前驅物之步驟；及進行熱壓之步驟。
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