TW201833201A - 導熱性漿料以及電子裝置 - Google Patents

導熱性漿料以及電子裝置 Download PDF

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TW201833201A
TW201833201A TW106137305A TW106137305A TW201833201A TW 201833201 A TW201833201 A TW 201833201A TW 106137305 A TW106137305 A TW 106137305A TW 106137305 A TW106137305 A TW 106137305A TW 201833201 A TW201833201 A TW 201833201A
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thermally conductive
conductive paste
meth
acrylate
conductive filler
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TW106137305A
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TWI670306B (zh
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牧原康二
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日商住友電木股份有限公司
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    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

本發明的導熱性漿料為包含熱固性樹脂和導熱性填料者，潤濕擴展面積的比例為90%以上，將導熱性填料的平均粒徑D50設為D，將除去了導熱性填料之該導熱性漿料在室溫25℃中之黏度設為η，將該導熱性漿料中之導熱性填料的沉降程度設為S=D2/η時，S為8[10-12‧m3‧s/kg]以上且900[10-12‧m3‧s/kg]以下。

Description

導熱性漿料以及電子裝置
本發明係關於一種導熱性漿料以及電子裝置。
在至今為止的用於接著半導體芯片和框架之導熱性漿料中，以提高導熱性為目的進行了各種開發。作為該種技術，有在專利文獻1中記載的技術。依該文獻，記載有銀為90質量%之含有丙烯酸樹脂之高導熱性漿料(專利文獻1的實施例等)。
專利文獻1：日本特開2004-140170號公報
然而，明確了在上述文獻中記載的導熱性漿料中，從保存穩定性以及操作性的觀點來看有改善的空間。
本發明人著眼於導熱性漿料的狀態，按照每一情況進行了研究，明確了在保存後的導熱性漿料中，會發生導熱性填料的分離，在使用時之導熱性漿料中會發生拉線。
例如，若以提高導熱率為目的而提高導熱性漿料中之導熱性填料的含量，則要求加大銀尺寸且減小樹脂的分子量，以防止導熱性漿料的高黏度化。因此，在導熱性漿料中，有時導熱性填料易分離。
另一方面，若以抑制導熱性填料的分離為目的來增大樹脂的分子量，則相反地有時在使用時會發生拉線。
如此，可知導熱性漿料的狀態在不同的情況亦即保存情況和使用情況中， 成為權衡關係。
依據該種見解進行深入研究之結果，本發明人發現能夠根據導熱性漿料的潤濕擴展程度來評價導熱性漿料的保存時狀態，能夠根據導熱性漿料的沉降程度來評價導熱性漿料的使用時的狀態。並且，發現藉由提高導熱性漿料的潤濕擴展程度並且將導熱性填料的沉降程度設為最佳值，能夠提高保存穩定性以及操作性，從而完成了本發明。
依本發明，提供一種導熱性漿料，其包含熱固性樹脂和導熱性填料，在前述導熱性漿料中，以下述測量方法算出之潤濕擴展面積的比例為90%以上，將前述導熱性填料的平均粒徑D50設為D，將除去了前述導熱性填料之該導熱性漿料在室溫25℃中之黏度設為η，將該導熱性漿料中之前述導熱性填料的沉降程度設為S=D2/η時，S為8[10-12‧m3‧s/kg]以上且900[10-12‧m3‧s/kg]以下。
(潤濕擴展面積的測量方法)
在引線框的表面上將該導熱性漿料以對角線狀交叉之方式進行塗佈。接著，在室溫25℃中靜置8小時。接著，將2mm×2mm的矽裸片(silicon bare chip)在前述引線框上經由該導熱性漿料安裝後，算出該導熱性漿料對於前述矽裸片的表面之上述潤濕擴展面積的比例。
又，依本發明，提供一種具備上述導熱性漿料的硬化物之電子裝置。
依本發明，提供一種保存穩定性以及操作性優異之導熱性漿料以及使用了該導熱性漿料之電子裝置。
上述之目的、以及其他目的、特徵以及優點藉由以下所敘述之較佳實施形態以及隨附之以下圖式而進一步變得明確。
10‧‧‧接著層
20‧‧‧半導體元件
30‧‧‧基板
40‧‧‧接合線
50‧‧‧模製樹脂
60‧‧‧焊球
100‧‧‧半導體裝置
圖1係表示本實施形態之半導體裝置的一例之剖面圖。
以下，利用圖式對實施形態進行說明。另外，在所有的圖式中，對相同的構成要素賦予相同元件符號，適當省略說明。
本實施形態的導熱性漿料能夠包含熱固性樹脂和導熱性填料。
在本實施形態的導熱性漿料中，能夠將以下述測量方法算出之潤濕擴展面積的比例設為90%以上。又，在將本實施形態的導熱性漿料中之導熱性填料的沉降程度設為S=D2/η時，能夠將S設為8[10-12‧m3‧s/kg]以上且900[10-12‧m3‧s/kg]以下。
在本實施形態中，將導熱性填料的平均粒徑D50設為D，將除去了導熱性填料之該導熱性漿料在室溫25℃中之黏度設為η。
又，在本實施形態中，作為潤濕擴展面積的測量方法，能夠利用如下方法。首先，在引線框的表面上將該導熱性漿料以對角線狀交叉之方式進行塗佈。接著，在室溫25℃中靜置8小時。接著，將具有2mm×2mm的表面之矽裸片在引線框上經由該導熱性漿料安裝後，算出該導熱性漿料對於矽裸片的表面積之上述潤濕擴展面積的比例(%)。
本發明人發現，藉由將導熱性漿料的潤濕擴展面積用作指標，能夠適當地評價導熱性漿料的保存時的狀態，藉由將以導熱性填料的粒徑和樹脂黏度之間的關係表示之導熱性填料的沉降指數用作指標，能夠適當地評價導熱性漿料的使用時的狀態。
依據該種見解進行深入研究之結果，本發明人明確了藉由將潤濕擴展面積的比例設為90%以上，並以導熱性填料的沉降程度S成為8[10-12‧m3‧s/kg]以上且900[10-12‧m3‧s/kg]以下之方式進行適當的控制，能夠抑制導熱性填料的分離，並且能夠抑制導熱性填料的拉線，而且能夠提高保存穩定性以及操作性，從而 完成了本發明。
依本實施形態的導熱性漿料，能夠在保存時以及使用時維持適當的漿料狀態，因此能夠將導熱性和金屬密接性等特性設為所希望者。又，依本實施形態，即使在保存後亦能夠實現遵循設計的導熱性漿料的特性。
在本實施形態中，例如藉由適當地選擇導熱性漿料中所含之各成分的種類和摻合量、導熱性漿料的製備方法等，能夠控制上述潤濕擴展面積以及沉降程度S。在該等之中，作為用於將上述潤濕擴展面積以及沉降程度S設為所希望的數值範圍之要素，例如可舉出使用低分子量單體作為丙烯酸化合物或熱固性樹脂、以及縮小導熱性填料的粒徑或含量等。
依本實施形態，能夠實現導熱性以及保存穩定性優異之導熱性漿料。
本實施形態的導熱性漿料能夠用於將印刷電路基板等基材和半導體元件等電子零件進行接合之接著層。亦即，由本實施形態的導熱性漿料的硬化物構成的樹脂接著層能夠用作晶片黏著材(die attach material)。藉由使用本實施形態的導熱性漿料的硬化物，導熱性填料適當地分散，因此能夠實現電子零件的散熱性優異，電子零件與基材的金屬密接性(吸濕後的金屬密接性)優異之晶片黏著材。
又，即使在本實施形態的導熱性漿料中的導熱性填料的含量低時，亦能夠維持高導熱率。亦即，即使在導熱性填料含量低的導熱性漿料中亦能夠實現高導熱率。作為一例，即使在該導熱性填料的含量為80質量%以下時，導熱率亦能夠實現5W/mK以上，更佳能夠實現10W/mK以上。
以下，對本實施形態的導熱性漿料的成分進行說明。
(熱固性樹脂)
作為在導熱性漿料中所含之熱固性樹脂，能夠使用藉由加熱來形成3維網眼 結構之一般的熱固性樹脂。在本實施形態中，熱固性樹脂並無特別的限定，例如能夠包含選自氰酸酯樹脂、環氧樹脂、在1個分子內具有2個以上的自由基聚合性的碳-碳雙鍵之樹脂以及順丁烯二醯亞胺樹脂之一種或兩種以上。在該等之中，從提高導熱性漿料的接著性之觀點來看，特佳包含環氧樹脂。
作為用作熱固性樹脂之環氧樹脂，能夠使用在1個分子內具有2個以上的環氧丙基之單體、低聚物、聚合物整體，其分子量或分子結構沒有特別的限定。作為本實施形態中之環氧樹脂，例如可舉出聯苯型環氧樹脂；雙酚A型環氧樹脂、雙酚F型環氧樹脂、四甲基雙酚F型環氧樹脂等雙酚型環氧樹脂；芪型環氧樹脂；苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂；三酚基甲烷型環氧樹脂、烷基改質三酚基甲烷型環氧樹脂等多官能環氧樹脂；具有伸苯基骨架之苯酚芳烷基型環氧樹脂、具有伸聯苯基骨架之苯酚芳烷基型環氧樹脂等芳烷基型環氧樹脂；二羥基萘基型環氧樹脂、將二羥基萘基的二聚體進行環氧丙基醚化而得到之環氧樹脂等萘酚型環氧樹脂；三聚異氰酸三環氧丙酯、單烯丙基二環氧丙基三聚異氰酸酯等含有三核之環氧樹脂；二環戊二烯改質苯酚型環氧樹脂等橋環狀烴化合物改質苯酚型環氧樹脂。又，作為環氧樹脂，例如還能夠使用將在1個分子內含有2個以上的環氧丙基之化合物中的雙酚A、雙酚F、聯苯酚等雙酚化合物或者該等的衍生物、氫化雙酚A、氫化雙酚F、氫化聯苯酚、環己二醇、環己烷二甲醇、環己烷二乙醇等具有脂環結構之二醇或該等的衍生物、丁二醇、己二醇、辛二醇、壬二醇、癸二醇等脂肪族二醇或該等的衍生物等進行環氧化之2官能者、具有三羥基苯基甲烷骨架、胺基苯酚骨架之3官能者。作為熱固性樹脂之環氧樹脂，能夠包含從上述例示者中選擇之一種或兩種以上。
在該等之中，從提高塗佈作業性或接著性之觀點來看，更佳包含雙酚型環氧樹脂，特佳包含雙酚F型環氧樹脂。又，在本實施形態中，從更有效地提高塗 佈作業性之觀點來看，更佳包含在室溫(25℃)中為液狀之液狀環氧樹脂。
用作熱固性樹脂之氰酸酯樹脂沒有特別的限定，例如能夠包含選自1,3-二氰氧基苯、1,4-二氰氧基苯、1,3,5-三氰氧基苯、1,3-二氰氧基萘、1,4-二氰氧基萘、1,6-二氰氧基萘、1,8-二氰氧基萘、2,6-二氰氧基萘、2,7-二氰氧基萘、1,3,6-三氰氧基萘、4,4’-二氰氧基聯苯、雙(4-氰氧基苯基)甲烷、雙(3,5-二甲基-4-氰氧基苯基)甲烷、2,2-雙(4-氰氧基苯基)丙烷、2,2-雙(3,5-二溴-4-氰氧基苯基)丙烷、雙(4-氰氧基苯基)醚、雙(4-氰氧基苯基)硫醚、雙(4-氰氧基苯基)碸、三(4-氰氧基苯基)亞磷酸酯、三(4-氰氧基苯基)磷酸酯、藉由酚醛清漆樹脂和鹵化氰的反應而獲得之氰酸酯類、以及具有藉由將該等多官能氰酸酯樹脂的氰酸酯基進行三量化而形成之三環之預聚物中之一種或兩種以上。上述預聚物能夠藉由例如將礦酸、路易斯酸等酸、醇鈉、三級胺類等鹼或碳酸鈉等鹽類作為觸媒使上述多官能氰酸酯樹脂單體聚合來獲得。
作為在1個分子內具有2個以上用作熱固性樹脂之自由基聚合性的碳-碳雙鍵之樹脂，例如能夠使用在1個分子內具有2個以上(甲基)丙烯醯基之自由基聚合性丙烯酸樹脂。在本實施形態中，作為上述丙烯酸樹脂，係分子量為500~10000之聚醚、聚酯、聚碳酸酯或聚(甲基)丙烯酸酯，且能夠包含具有(甲基)丙烯酸基之化合物。另外，作為熱固性樹脂使用在1個分子內具有2個以上自由基聚合性的碳-碳雙鍵之樹脂時，導熱性漿料例如能夠包含熱自由基聚合起始劑等聚合起始劑。
用作熱固性樹脂之順丁烯二醯亞胺樹脂沒有特別的限定，例如能夠包含選自N,N’-(4,4’-二苯甲烷)雙順丁烯二醯亞胺、雙(3-乙基-5-甲基-4-順丁烯二醯亞胺苯基)甲烷、2,2-雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]丙烷等雙順丁烯二醯亞胺樹脂中之一種或兩種以上。
又，本實施形態之熱固性樹脂作為具有聯苯骨架之樹脂能夠包含 具有聯苯骨架之環氧樹脂(聯苯型環氧樹脂)。藉此，能夠提高導熱性漿料的導熱性以及金屬密接性。
具有聯苯骨架之環氧樹脂只要為在其分子結構內具有聯苯骨架且具有2個以上的環氧基者，則其結構沒有特別的限定，例如可舉出將聯苯酚或其衍生物以環氧氯丙烷進行了處理之2官能環氧樹脂、具有伸聯苯基骨架之苯酚芳烷基型環氧樹脂以及具有伸聯苯基骨架之萘酚芳烷基型環氧樹脂等，可將該等單獨使用，混合使用亦無妨。在該等之中，尤其在1個分子內具有2個環氧基者成為耐熱性的提高變得優異者，因此較佳。作為該種環氧樹脂，可舉出聯苯型環氧樹脂、四甲基聯苯型環氧樹脂等將聯苯酚衍生物以環氧氯丙烷進行了處理之2官能環氧樹脂；具有伸聯苯基骨架之苯酚芳烷基型環氧樹脂中環氧基為2個者(有時若苯酚核體數為2則會顯現)；具有伸聯苯基骨架之萘酚芳烷基型樹脂中環氧基為2個者等。
作為本實施形態的熱固性樹脂的重量平均分子量，例如可為100以上且500以下，較佳為150以上且450以下，更佳為200以上且400以下。
在本實施形態中，導熱性漿料中之熱固性樹脂的含量相對於導熱性漿料總體例如較佳為5質量%以上，更佳為6質量%以上，進而較佳為7質量%以上。藉此能夠提高導熱性漿料的流動性，實現塗佈作業性的進一步提高。另一方面，導熱性漿料中之熱固性樹脂的含量相對於導熱性漿料總體例如較佳為30質量%以下，更佳為25質量%以下，進而較佳為15質量%以下。藉此，能夠提高使用導熱性漿料形成之接著層的耐回焊(reflow)性和耐濕性。
(丙烯酸化合物)
本實施形態的導熱性漿料能夠包含丙烯酸化合物。作為本實施形態之丙烯酸化合物，較佳包含(甲基)丙烯酸單體。在本實施形態中，(甲基)丙烯酸單體表示丙烯酸單體、甲基丙烯酸單體或該等的混合物，表示具有至少1個以上的 官能基(丙烯酸基或甲基丙烯酸基)之單體。
在本實施形態中，(甲基)丙烯酸單體可為具有2個以上的官能基之單體。藉此，能夠提高金屬密接性。
本實施形態之(甲基)丙烯酸單體為與單體聚合之丙烯酸聚合物不同者，係具有至少1個以上的乙烯性不飽和雙鍵之單體。作為該(甲基)丙烯酸單體的分子量沒有特別的限定，例如下限值可為150以上，較佳為160以上，更佳為180以上，另一方面，上限值可為2000以下，較佳為1000以下，更佳為600以下。
又，作為2官能(甲基)丙烯酸單體，例如可舉出丙三醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇二(甲基)丙烯酸酯、二(甲基)丙烯酸鋅、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、四亞甲基二醇二(甲基)丙烯酸酯等。該等可單獨使用，亦可將2種以上組合使用。
本實施形態之(甲基)丙烯酸單體除了(甲基)丙烯酸單體以外，還能夠包含其他丙烯酸化合物。作為其他丙烯酸化合物，例如可以使用單官能丙烯酸酯、多官能丙烯酸酯、單官能甲基丙烯酸酯、多官能甲基丙烯酸酯、丙烯酸胺酯、甲基丙烯酸胺酯、環氧丙烯酸酯、環氧甲基丙烯酸酯、聚酯丙烯酸酯或尿素丙烯酸酯等單體、低聚物、該等的混合物。該等可使用1種或2種以上。
作為其他丙烯酸化合物，例如可舉出(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸3-羥丁酯、(甲基)丙烯酸4-羥丁酯、1,2-環己二醇單(甲基)丙烯酸酯、1,3-環己二醇單(甲基)丙烯酸酯、1,4-環己二醇單(甲基)丙烯酸酯、1,2-環己烷 二甲醇單(甲基)丙烯酸酯、1,3-環己烷二甲醇單(甲基)丙烯酸酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、1,2-環己烷二乙醇單(甲基)丙烯酸酯、1,3-環己烷二乙醇單(甲基)丙烯酸酯、1,4-環己烷二乙醇單(甲基)丙烯酸酯、丙三醇單(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯、新戊四醇單(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯等具有羥基之(甲基)丙烯酸酯或使該等具有羥基之(甲基)丙烯酸酯和二羧酸或其衍生物進行反應而獲得之具有羧基之(甲基)丙烯酸酯等。作為在此能夠使用之二羧酸，例如可舉出草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、順丁烯二酸、反丁烯二酸、酞酸、四氫酞酸、六氫酞酸以及該等的衍生物。
又，作為其他丙烯酸化合物，例如還能夠使用(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸二十二烷基酯、(甲基)丙烯酸2-乙基己酯、其他的(甲基)丙烯酸烷基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸芐酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸環氧丙酯、三羥甲基丙烷三(甲基)丙烯酸酯、單(甲基)丙烯酸鋅、(甲基)丙烯酸二甲胺乙酯、(甲基)丙烯酸二乙胺乙酯、新戊二醇(甲基)丙烯酸酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸2,2,3,3,4,4-六氟丁酯、(甲基)丙烯酸全氟辛酯、(甲基)丙烯酸全氟辛乙酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸乙氧基二乙二醇酯、甲氧基聚亞烷基二醇單(甲基)丙烯酸酯、辛氧基聚亞烷基二醇單(甲基)丙烯酸酯、 月桂氧基聚亞烷基二醇單(甲基)丙烯酸酯、硬脂氧基聚亞烷基二醇單(甲基)丙烯酸酯、烯丙氧基聚亞烷基二醇單(甲基)丙烯酸酯、壬基苯氧基聚亞烷基二醇單(甲基)丙烯酸酯、N,N’-亞甲基雙(甲基)丙烯醯胺、N,N’-伸乙基雙(甲基)丙烯醯胺、1,2-二(甲基)丙烯醯胺乙二醇、二(甲基)丙烯醯氧基甲基三環癸烷、N-(甲基)丙烯醯氧基乙基順丁烯二醯亞胺、N-(甲基)丙烯醯氧基乙基六氫鄰苯二甲醯亞胺、N-(甲基)丙烯醯氧基乙基鄰苯二甲醯亞胺、n-乙烯基-2-吡咯啶酮、苯乙烯衍生物、α-甲基苯乙烯衍生物等。
在本實施形態中，(甲基)丙烯酸單體的含量的下限值相對於導熱性漿料總體例如為1質量%以上，較佳為3質量%以上，更佳為5質量%以上。藉此，能夠提高噴出穩定性和金屬密接性。又，還能夠降低黏度。(甲基)丙烯酸單體的含量的上限值相對於導熱性漿料總體例如為15質量%以下，較佳為12質量%以下，更佳為10質量%以下。藉此，能夠實現導熱性漿料的諸特性的平衡。
(導熱性填料)
本實施形態的導熱性漿料能夠包含導熱性填料。
作為導熱性填料，只要為導熱性優異之填料則沒有特別的限定，例如能夠包含金屬、氧化物或氮化物。
作為上述金屬填料，例如可舉出銀粉、金粉、銅粉等金屬粉。作為上述氧化物填料，例如可舉出滑石、燒製黏土、未燒製黏土、雲母、玻璃等矽酸鹽；氧化鈦、氧化鋁、氧化鎂、勃姆石、氧化矽、熔融矽石等氧化物粒子或氫氧化鋁、氫氧化鎂、氫氧化鈣等氫氧化物粒子。作為上述氮化物填料，例如可舉出氮化鋁、氮化硼、氮化矽、氮化碳等氮化物粒子。
又，作為本實施形態的導熱性填料，可包含硫酸鋇、硫酸鈣、亞硫酸鈣等硫酸鹽或亞硫酸鹽；硼酸鋅、偏硼酸鋇、硼酸鋁、硼酸鈣、硼酸鈉等硼酸鹽；鈦酸鍶、鈦酸鋇等鈦酸鹽等其他無機填充材料。
可將該等單獨使用亦可以組合2種以上來使用。
又，作為本實施形態的導熱性填料，從導電性的觀點來看，較佳含有選自由銀、銅、氧化鋁組成的群之一種以上。又，藉此能夠提高長期作業性。
作為本實施形態的導熱性填料的形狀，可舉出薄片形狀、球形狀等。其中，從導熱性漿料的流動性的觀點來看，較佳為球形狀。
又，導熱性填料的平均粒徑D50的下限值例如可為0.1μm以上，較佳為0.3μm以上，更佳為0.5μm以上。藉此，能夠提高導熱性漿料的導熱率。另一方面，導熱性填料的平均粒徑D50的上限值例如可為10μm以下，較佳為8μm以下，更佳為5μm以下。藉此，能夠提高導熱性漿料的保存穩定性。
又，導熱性填料的平均粒徑D95的下限值例如可為1μm以上，較佳為2μm以上，更佳為3μm以上。藉此，能夠提高導熱性漿料的導熱率。另一方面，導熱性填料的平均粒徑D95的上限值例如可為15μm以下，較佳為13μm以下，更佳為10μm以下。藉此，能夠提高導熱性漿料的保存穩定性。
另外，導熱性填料的平均粒徑例如能夠藉由雷射繞射散射法或動態光散射法等進行測量。
在本實施形態中，導熱性漿料中之導熱性填料的含量相對於導熱性漿料總體例如較佳為50質量%以上，更佳為60質量%以上。藉此，能夠對使用導熱性漿料形成之接著層更有效地提高低熱膨脹性或耐濕可靠性、耐回焊性。另一方面，導熱性漿料中之導熱性填料的含量相對於導熱性漿料總體例如為88質量%以下，較佳為83質量%以下，更佳為80質量%以下。藉此，能夠提高導熱性漿料的流動性，提高塗佈作業性和接著層的均勻性。
(硬化劑)
導熱性漿料例如能夠包含硬化劑。藉此，能夠提高導熱性漿料的硬化性。硬化劑例如能夠包含選自脂肪族胺、芳香族胺、二氰二胺、二醯肼化合物、酸 酐以及苯酚化合物中之一種或兩種以上。在該等之中，從提高製造穩定性之觀點而言，特佳包含二氰二胺以及苯酚化合物中之至少一者。
作為用作硬化劑之二醯肼化合物，可舉出己二酸二醯肼、十二烷酸二醯肼、間苯二甲酸二醯肼、對羥苯甲酸二醯肼等羧酸二醯肼等。又，作為用作硬化劑之酸酐，可舉出酞酸酐、四氫酞酸酐、六氫酞酸酐、內亞甲基四氫酞酸酐、十二烯基琥珀酸酐、順丁烯二酸酐和聚丁二烯的反應物、順丁烯二酸酐和苯乙烯的共聚物等。
用作硬化劑之苯酚化合物係在1個分子內具有2個以上的酚性羥基之化合物。更佳1個分子內的酚性羥基的數量為2~5，特佳1個分子內的酚性羥基數為2個或3個。藉此，能夠更有效地提高導熱性漿料的塗佈作業性，並且能夠在硬化時形成交聯結構而成為導熱性漿料的硬化物特性優異者。上述苯酚化合物例如能夠包含選自雙酚F、雙酚A、雙酚S、四甲基雙酚A、四甲基雙酚F、四甲基雙酚S、二羥基二苯醚、二羥基二苯甲酮、四甲基聯苯酚、亞乙基雙酚、甲基亞乙基雙(甲基苯酚)、亞環己基雙酚、聯苯酚等雙酚類及其衍生物、三(羥基苯基)甲烷、三(羥基苯基)乙烷等3官能酚類及其衍生物、藉由苯酚酚醛清漆、甲酚酚醛清漆等酚類和甲醛進行反應而獲得之化合物中以2核體或3核體為主者及其衍生物中之一種或兩種以上。在該等之中，更佳包含雙酚類，特佳包含雙酚F。
又，本實施形態之硬化劑中，作為具有聯苯骨架之樹脂能夠包含具有聯苯骨架之酚醛樹脂(phenolic resin，苯酚化合物)。藉此，能夠提高導熱性漿料的導熱性以及金屬密接性。
作為具有聯苯骨架之酚醛樹脂，只要為在其分子結構內具有聯苯骨架且具有2個以上的酚基者，則其結構沒有特別的限定。
在本實施形態中，導熱性漿料中之硬化劑的含量相對於導熱性漿 料總體較佳為0.5質量%以上，更佳為1.0質量%以上。藉此，能夠更有效地提高導熱性漿料的硬化性。另一方面，導熱性漿料中之硬化劑的含量相對於導熱性漿料總體較佳為10質量%以下，更佳為7質量%以下。藉此，能夠提高使用導熱性漿料形成之接著層的低熱膨脹性、耐回焊性、耐濕性。
在本實施形態中，具有聯苯骨架之樹脂的含量的下限值相對於導熱性漿料總體例如為1質量%以上，較佳為1.5質量%以上，更佳為2質量%以上。藉此，能夠提高導熱性。具有聯苯骨架之樹脂的含量的上限值相對於導熱性漿料總體例如為15質量%以下，較佳為10質量%以下，更佳為7質量%以下。藉此，能夠實現導熱率和黏度等導熱性漿料的諸特性的平衡。
在本實施形態中，具有聯苯骨架之樹脂以及(甲基)丙烯酸單體的含量的下限值相對於導熱性漿料總體例如為3質量%以上，較佳為5質量%以上，更佳為6質量%以上。藉此，能夠提高導熱性以及金屬密接性。具有聯苯骨架之樹脂以及(甲基)丙烯酸單體的含量的上限值相對於導熱性漿料總體例如為20質量%以下，較佳為18質量%以下，更佳為15質量%以下。藉此，能夠實現導熱率和硬化特性等導熱性漿料的諸特性的平衡。
在本實施形態中，(甲基)丙烯酸單體的含量的下限值相對於具有聯苯骨架之樹脂以及(甲基)丙烯酸單體的總量100質量%例如為30質量%以上，較佳為50質量%以上，更佳為60質量%以上。藉此，能夠提高導熱性以及金屬密接性。(甲基)丙烯酸單體的含量的上限值相對於具有聯苯骨架之樹脂以及(甲基)丙烯酸單體的總量100質量%例如為95質量%以下，較佳為90質量%以下，更佳為88質量%以下。藉此，能夠實現導熱率和硬化特性等導熱性漿料的諸特性的平衡。
在本實施形態中，具有聯苯骨架之酚醛樹脂以及(甲基)丙烯酸單體的含量的下限值相對於導熱性漿料總體例如為3質量%以上，較佳為5質量% 以上，更佳為6質量%以上。藉此，能夠提高導熱性以及金屬密接性。具有聯苯骨架之酚醛樹脂以及(甲基)丙烯酸單體的含量的上限值相對於導熱性漿料總體例如為20質量%以下，較佳為18質量%以下，更佳為15質量%以下。藉此，能夠實現導熱率和硬化特性等導熱性漿料的諸特性的平衡。
(硬化促進劑)
導熱性漿料例如能夠包含硬化促進劑。
使用環氧樹脂作為熱固性樹脂時，作為硬化促進劑，例如能夠使用促進環氧樹脂和硬化劑的交聯反應者。該種硬化促進劑例如能夠包含選自由咪唑類、三苯基膦或四苯基膦的鹽類、二氮雜二環十一烯等胺系化合物及其鹽類、第三丁基異丙苯過氧化物、二異丙苯過氧化物、α,α’-雙(第三丁基過氧基間異丙基)苯、2,5-二甲基-2,5-二(第三丁基過氧基)己烷、2,5-二甲基-2,5-二(第三丁基過氧基)已炔-3等有機過氧化物組成的群之一種或兩種以上。在該等之中，適合使用2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2-苯基-4,5-二羥甲基咪唑、2-C11H23-咪唑、2-甲基咪唑和2,4-二胺基-6-乙烯基三的加成物等咪唑化合物。其中特佳融點為180℃以上的咪唑化合物。
使用氰酸酯樹脂作為熱固性樹脂時，作為硬化促進劑，例如能夠使用包含選自辛酸鋅、辛酸錫、環烷酸鈷、環烷酸鋅、乙醯丙酮鐵等有機金屬錯合物、氯化鋁、氯化錫、氯化鋅等金屬鹽、三乙胺、二甲基芐基胺等胺類中之一種或兩種以上者。
在本實施形態中，導熱性漿料中之硬化促進劑的含量相對於導熱性漿料總體較佳為0.05質量%以上，更佳為0.1質量%以上。藉此，能夠提高導熱性漿料的硬化性。另一方面，導熱性漿料中之硬化促進劑的含量相對於導熱性漿料總體較佳為1質量%以下，更佳為0.8質量%以下。藉此，能夠更有效地提高 導熱性漿料的流動性。
(反應性稀釋劑)
導熱性漿料例如能夠包含反應性稀釋劑。
反應性稀釋劑例如能夠包含選自苯基環氧丙基醚、甲酚環氧丙基醚、第三丁基苯基環氧丙基醚等單官能芳香族環氧丙基醚類、脂肪族環氧丙基醚類中之一種或兩種以上。藉此，能夠更有效地提高塗佈作業性，並且實現接著層的平坦化。
在本實施形態中，導熱性漿料中之反應性稀釋劑的含量相對於導熱性漿料總體較佳為3質量%以上，更佳為4質量%以上。藉此，能夠更有效地提高導熱性漿料的塗佈作業性和接著層的平坦性。另一方面，導熱性漿料中之反應性稀釋劑的含量相對於導熱性漿料總體較佳為20質量%以下，更佳為15質量%以下。藉此，能夠抑制塗佈作業中之液體滴落的產生，實現塗佈作業性的提高。又，亦能夠提高導熱性漿料的硬化性。
又，本實施形態的導熱性漿料可不包含溶劑。此處所謂之溶劑表示不具有參與導熱性漿料中所含之熱固性樹脂的交聯反應之反應性基之非反應性溶劑。不包含表示實質上不包含，指相對於導熱性漿料總體之非反應性溶劑的含量為0.1質量%以下之情況。
另一方面，本實施形態的導熱性漿料亦可包含非反應性溶劑。
作為上述非反應性溶劑，例如可舉出以包含丁基二丙二醇、戊烷、己烷、庚烷、環己烷以及十氫化萘等為例之烷烴或環烷之烴溶劑、甲苯、二甲苯、苯、均三甲苯等芳香族溶劑、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、甲基甲氧基丁醇、α-松油醇、β-松油醇、己二醇、芐醇、2-苯乙醇、異十六醇、異十八醇、月桂醇、 乙二醇、丙二醇或丙三醇等醇類；丙酮、甲基乙基酮、甲基異丁酮、環己酮、二丙酮醇(4-羥基-4-甲基-2-戊酮)、2-辛酮、異佛爾酮(3,5,5-三甲基-2-環己烯-1-酮)或二異丁基酮(2,6-二甲基-4-庚酮)等酮類；乙酸乙酯、乙酸丁酯、鄰苯二甲酸二乙酯、鄰苯二甲酸二丁酯、乙醯氧基乙烷、丁酸甲酯、己酸甲酯、辛酸甲酯、癸酸甲酯、乙酸甲賽璐蘇、乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯、1,2-二乙醯氧基乙烷、磷酸三丁酯、磷酸三甲苯酯或磷酸三戊酯等酯類；四氫呋喃、二丙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、丙二醇二甲醚、乙氧基乙醚、1,2-雙(2-二乙氧基)乙烷或1,2-雙(2-甲氧基乙氧基)乙烷等醚類；乙酸2-(2-丁氧基乙氧基)乙烷等酯醚類；2-(2-甲氧基乙氧基)乙醇等醚醇類；正烷烴、異烷烴、十二烷基苯、松節油、煤油或輕油等烴類；乙腈或丙腈等腈類；乙醯胺或N,N-二甲基甲醯胺等醯胺類；低分子量的揮發性矽油或揮發性有機改質矽油。可將該等單獨使用，亦可組合2種以上來使用。
導熱性漿料可以根據需要包含其他添加劑。作為其他添加劑，可舉出環氧矽烷、巰基矽烷、胺基矽烷、烷基矽烷、脲基矽烷、乙烯基矽烷、硫化物矽烷等矽烷偶合劑、以鈦酸酯偶合劑、鋁偶合劑、鋁/鋯偶合劑等為例之偶合劑、碳黑等著色劑、聚矽氧油、矽氧橡膠等固形低應力化成分、水滑石等無機離子交換體、消泡劑、界面活性劑、各種聚合抑制劑以及抗氧化劑等。導熱性漿料能夠包含該等添加劑中之一種或兩種以上。
本實施形態的導熱性漿料例如可為漿料狀。
在本實施形態中，導熱性漿料的製備方法沒有特別的限定，例如能夠將上述之各成分進行預混合後，利用3個輥進行混練，進而進行真空脫泡，獲得漿料狀的樹脂組成物。此時，例如藉由在減壓下進行預混合等適當地調整製備條件，能夠有助於提高導熱性漿料中之長期作業性。
對本實施形態的電子裝置(半導體裝置100)進行說明。
圖1係表示本實施形態之電子裝置(半導體裝置100)的一例之剖面圖。
本實施形態的電子裝置(半導體裝置100)為具備本實施形態的導熱性漿料的硬化物者。該硬化物例如如圖1所示，能夠用作將基材(基板30)和電子零件(半導體元件20)進行接著之接著層10。
本實施形態的半導體裝置100例如能夠具備基板30、在基板30上經由接著層10裝載之半導體元件20。半導體元件20和基板30例如藉由接合線40電連接。半導體元件20和接合線40例如藉由將環氧樹脂組成物等進行硬化而形成之模製樹脂50而密封。
基板30例如為引線框或有機基板。在圖1中例示出基板30為有機基板之情況。此時，在基板30中裝載有半導體元件20之表面和與其相反之一側的背面形成有例如複數個焊球60。
在本實施形態之半導體裝置100中，接著層10藉由將上述中例示之導熱性漿料進行硬化而形成。因此，能夠穩定地製造半導體裝置100。
在本實施形態中，例如在MAP(Mold Array Package，模具陣列封裝)成形品的製造中亦能夠應用導熱性漿料。此時，利用噴射分配器法(jet-dispenser method)將導熱性漿料對基板上之複數個區域進行塗佈，藉此在基板上形成複數個接著層後，成為在各接著層上裝載有半導體元件。藉此，能夠進一步實現生產效率的提高。作為MAP成形品，例如可舉出MAP-BGA(Ball Grid Array，球柵陣列)或MAP-QFN(Quad Flat Non-Leaded Package，四方扁平無引腳封裝)。
〔實施例〕
以下，參閱實施例對本發明進行詳細地說明，但本發明並不受該等實施例的記載的任何限定。
(導熱性漿料的製備)
對各實施例以及各比較例分別按照表1所示之配比來摻合各成分，進行了在常壓下5分鐘、在70cmHg的減壓下15分鐘的預混合。接著，利用3個輥進行混練、脫泡而獲得了導熱性漿料。另外，表1中之各成分的詳細內容如下述。又，表1中的單位係質量%。
(熱固性樹脂)
熱固性樹脂1：雙酚F型環氧樹脂(Nippon Kayaku Co.,Ltd.製，SB-403S)
熱固性樹脂2：具有聯苯骨架之環氧樹脂(在室溫25℃中係固體，Mitsubishi Chemical Co.,Ltd.製，YX-4000K，重量平均分子量Mw：354)
(硬化劑)
硬化劑1：具有聯苯骨架之酚醛樹脂(在室溫25℃中係固體，Honshu Chemical Industry Co.,Ltd.製，聯苯酚)
硬化劑2：具有雙酚F骨架之酚醛樹脂(在室溫25℃中係固體，DIC Corporation製，DIC-BPF)
硬化劑3：雙氰胺(ADEKA Corporation製，EH-3636AS)
(導熱性填料)
導熱性填料1：銀粉(Fukuda Metal Foil & Powder Co.,Ltd.製，AgC-2611，薄片狀)
導熱性填料2：銀粉(DOWA Electronics Materials Co.,Ltd.製，AG2-1C，球狀)
導熱性填料3：銀粉(Fukuda Metal Foil & Powder Co.,Ltd.製，AgC-221A，薄片狀)
導熱性填料的D50、D95藉由雷射繞射散射法進行了測量。
(丙烯酸化合物)
丙烯酸化合物1：(甲基)丙烯酸單體(1,6-己二醇二甲基丙烯酸酯，Kyoeisha Chemical Co.,Ltd.製，LIGHT ESTER 1.6HX)
丙烯酸化合物2：(甲基)丙烯酸單體(乙二醇二甲基丙烯酸酯，Kyoeisha Chemical Co.,Ltd.製，LIGHT ESTER EG)
丙烯酸化合物3：(甲基)丙烯酸單體(甲基丙烯酸2-乙基己酯，Kyoeisha Chemical Co.,Ltd.製，LIGHT ESTER EH)
(偶合劑)
偶合劑1：二(三乙氧基矽烷)四硫化物(OSAKA SODA CO.,LTD.製，CABRUS4)
(硬化促進劑)
硬化促進劑1：有機過氧化物(Kayaku Akzo Corporation製，Perkadox BC)
硬化促進劑2：咪唑系(2-苯基-4,5-二羥甲基咪唑，SHIKOKU CHEMICALS CORPORATION製，2PHZ)
(溶劑)
溶劑1：乙二醇單丁基醚乙酸酯(Tokyo Chemical Industry Co.,Ltd.製，BCSA)
溶劑2：丁基二丙二醇(Nippon Nyukazai Co.,LTd.製，BFTG)
(反應性稀釋劑)
反應性稀釋劑1：單環氧單體(第三丁基苯基環氧丙基醚，Nippon Kayaku Co.,Ltd.製，SBT-H)
對所獲得之導熱性漿料進行了如下評價。將評價結果示於表1。
(η：不包含導熱性填料的樹脂黏度)
不使用導熱性填料，使用上述表1所示之摻合組成、摻合比率，製作了不含有導熱性填料之導熱性漿料P。利用Brookfield黏度計(HADV-3Ultra，主軸CP-51(角度1.565°，半徑1.2cm))，在25℃、100rpm的條件下測量了剛剛製作後的導熱性漿料P中之黏度(η)。黏度的單位係Pa‧S。將評價結果示於表1。
將表1中的導熱性漿料中之導熱性填料的沉降程度設為了S=D2/η。在沉降程度S中，將導熱性填料的平均粒徑D50設為D，將除去了導熱性填料之導熱性漿料P的上述黏度設為了η。
(導熱率)
使用所獲得之導熱性漿料製作了1cm見方、厚度1mm的盤狀的試驗片。(硬化條件係175℃、4小時。其中係從室溫經過60分鐘升溫至175℃。)依據藉由雷射閃光法(t1/2法)測量之熱擴散係數(α)、藉由DSC法測量之比熱(Cp)、遵照JIS-K-6911測量之密度(ρ)算出導熱率(=α×Cp×ρ)，將5W/m‧K以上的情況視作合格。導熱率的單位係W/m‧K。將評價結果示於表1。
(室溫保存性)
在5cc的注射器(Musashi Co.,Ltd.製)中放入所獲得之導熱性漿料，蓋住中塞、外塞後，設置在注射器架上並在25℃的恆溫槽中進行了48小時的處理。之後，目視確認外觀，確認了有無導熱性漿料的分離。在表1中，將無分離的情況以○表示，將有分離之情況以×表示。將評價結果示於表1。
(潤濕擴展性)
在銅製的引線框的表面上將所獲得之導熱性漿料以對角線狀交叉之方式進行了塗佈。接著，在室溫25℃中靜置了8小時。接著，將具有2mm×2mm的表面之矽裸片(厚度0.525mm)經由該導熱性漿料在引線框上以50g、50ms的荷重安裝後，以X射線裝置進行了觀察。藉由將以X射線觀察而獲得之圖像進行二值 化，算出了相對於矽裸片的表面積100%之該導熱性漿料的潤濕擴展面積的比例(%)。將評價結果示於表1。
(噴出穩定性(拉線發生率))
將放入到5cc的注射器(Musashi Co.,Ltd.製)之所獲得之導熱性漿料設置於Shotmaster300(Musashi Co.,Ltd.製)，以噴出壓力100kPa、噴出時間100ms實施了打點塗佈(280打點)。之後，目視確認塗佈形狀並非圓形者的數量(拉線數)，計算出相對於280打點之比例並作為了拉線發生率(%)。將評價結果示於表1。
(吸濕後晶片抗切強度)
使用所獲得之導熱性漿料，將鍍銀(Ag)片(縱×橫×厚度：2mm×2mm×0.35mm)安裝在鍍銀框支持體(SHINKO ELECTRIC INDUSTRIES CO.,LTD製，在銅引線框上實施了鍍銀者)上，利用烘箱以175℃、60分鐘(從25℃至175℃以升溫速度5℃/分鐘)的硬化溫度曲線(profile)進行硬化而製成了樣品1。
又，使用所獲得之導熱性漿料，將鍍金(Au)片(縱×橫×厚度：2mm×2mm×0.35mm)安裝在鍍金片(縱×橫×厚度：5mm×5mm×0.35mm)上，利用烘箱以175℃、60分鐘(從25℃至175℃以升溫速度5℃/分鐘)的硬化溫度曲線進行硬化而製成了樣品2。
將所獲得之樣品1、2在85℃、濕度85%的條件下進行了72小時吸濕處理後，測量了260℃中之熱時晶片抗切強度(單位：N/1mm2)。將評價結果示於表1。
得知實施例1~7的導熱性漿料與比較例2相比，室溫保存性(保存穩定性)優異，與比較例1、2相比，噴出穩定性(操作性)優異。又，得知實施例1~7的導熱性漿料的導熱性和晶片抗切強度(金屬密接性)亦優異。
該申請主張基於2016年10月31日申請之日本申請特願2016-213664號之優先權，將其揭示之全部內容編入於此。

Claims (15)

  1. 一種導熱性漿料，包含熱固性樹脂和導熱性填料，其中，以下述測量方法算出之潤濕擴展面積的比例為90%以上，將前述導熱性填料的平均粒徑D 50設為D，將除去了前述導熱性填料之該導熱性漿料在室溫25℃中之黏度設為η，將該導熱性漿料中之前述導熱性填料的沉降程度設為S=D 2/η時，S為8[10 -12‧m 3‧s/kg]以上且900[10 -12‧m 3‧s/kg]以下，(潤濕擴展面積的測量方法)在引線框的表面上將該導熱性漿料以對角線狀交叉之方式進行塗佈，接著，在室溫25℃中靜置8小時，接著，將2mm×2mm的矽裸片(silicon bare chip)在前述引線框上經由該導熱性漿料安裝後，算出該導熱性漿料對於前述矽裸片的表面之上述潤濕擴展面積的比例。
  2. 如申請專利範圍第1項之導熱性漿料，其中，該導熱性漿料的硬化物的導熱率為5W/mK以上。
  3. 如申請專利範圍第1項之導熱性漿料，其中，前述導熱性填料的平均粒徑D 50為0.1μm以上且10μm以下。
  4. 如申請專利範圍第1項之導熱性漿料，其中，前述導熱性填料的D 95為15μm以下。
  5. 如申請專利範圍第1項之導熱性漿料，其中，前述導熱性填料包含金屬、氧化物或氮化物。
  6. 如申請專利範圍第1項之導熱性漿料，其中，前述導熱性填料的含量相對於該導熱性漿料總體為50質量%以上且88質量%以下。
  7. 如申請專利範圍第1項之導熱性漿料，其中，前述熱固性樹脂的重量平均分子量為100以上且500以下。
  8. 如申請專利範圍第1項之導熱性漿料，其中，前述熱固性樹脂包 含具有聯苯骨架之樹脂。
  9. 如申請專利範圍第1項之導熱性漿料，其中，前述熱固性樹脂包含環氧樹脂。
  10. 如申請專利範圍第1項之導熱性漿料，其包含硬化劑。
  11. 如申請專利範圍第1項之導熱性漿料，其包含丙烯酸化合物。
  12. 如申請專利範圍第1項之導熱性漿料，其包含反應性稀釋劑。
  13. 如申請專利範圍第1項之導熱性漿料，其包含硬化促進劑。
  14. 如申請專利範圍第1項之導熱性漿料，其不包含溶劑。
  15. 一種電子裝置，其具備申請專利範圍第1至14項中任一項之導熱性漿料的硬化物。
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