TWI665240B - 預浸體及貼覆金屬之積層板、印刷配線板 - Google Patents

預浸體及貼覆金屬之積層板、印刷配線板 Download PDF

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Publication number
TWI665240B
TWI665240B TW104127908A TW104127908A TWI665240B TW I665240 B TWI665240 B TW I665240B TW 104127908 A TW104127908 A TW 104127908A TW 104127908 A TW104127908 A TW 104127908A TW I665240 B TWI665240 B TW I665240B
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Taiwan
Prior art keywords
mass
resin
prepreg
parts
acrylate copolymer
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TW104127908A
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English (en)
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TW201625722A (zh
Inventor
松本匡陽
人士
米本神夫
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日商松下知識產權經營股份有限公司
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Abstract

本發明之預浸體具有纖維基材及含浸於纖維基材的熱硬化性樹脂組成物。熱硬化性樹脂組成物含有：含環氧樹脂的熱硬化性樹脂、硬化劑、無機填料、及重量平均分子量為10×104以上，未達45×104的丙烯酸酯共聚物。無機填料的含量，相對於熱硬化性樹脂與硬化劑的合計100質量份為150質量份以上。丙烯酸酯共聚物的含量，相對於熱硬化性樹脂與硬化劑的合計100質量份為大於30質量份、90質量份以下。

Description

預浸體及貼覆金屬之積層板、印刷配線板
本發明關於一種印刷配線板之製造所使用的預浸體及貼覆金屬之積層板、印刷配線板。
印刷配線板一直都被廣泛使用在電器用品、通訊機器、計算機等各種領域。這種印刷配線板，是藉由將所需要枚數的預浸體重疊，進一步配置金屬箔，加熱加壓成形使其層合而一體化，而製作出貼覆金屬的積層板，然後對表面的金屬箔實施圖型化加工形成導體配線而製造完成。上述預浸體可藉由使含有既定材料的樹脂組成物含浸於玻璃布等的纖維基材而得到。
近年來電子技術的急速發展，電器用品也正在往薄型化‧小型化開發，隨著如此，印刷配線板逐漸需要具有優異的成形性，同時可抑制彎曲的發生。為了抑制印刷配線板發生彎曲，降低構成印刷配線板的絕緣層的熱膨脹率(CTE：coefficient of thermal expansion)被認為是重要的事項。
用來達成絕緣層的低熱膨脹率化的手段，可列舉例如 使構成絕緣層的樹脂組成物中含有高含量的二氧化矽等的無機填料的方法。但是如上述般使無機填料高填充化的樹脂組成物，會有成形性降低的傾向，以及對積層板或印刷配線板的品質造成不良影響的的顧慮。例如在加熱加壓成形的製造步驟之中，樹脂組成物(預浸體)所含有的樹脂成分與填料發生分離而導致條紋或分布不均，或在絕緣層中一部分的樹脂缺損，而產生會造成空隙的細斑(thin spots)。
另外，一般而言，若樹脂組成物(預浸體)中的無機填料含量變多，則可有效使樹脂硬化物(絕緣層)低CTE化，但是含浸於纖維基材的樹脂層反而會變脆，在預浸體的表面發生浮粉，或在處理預浸體的邊緣時等容易掉屑。亦即，使用預浸體製造印刷酚線板時，會將預浸體切割成既定尺寸，或將不需要的邊緣切掉然後使用，若樹脂組成物中含有高含量的無機填料，則在切斷加工時，無機填料或樹脂片等的粉屑容易飛散。而且，這種粉屑在後來的成形步驟中會附著在預浸體與層合配置的金屬箔的表面等，所製造出的印刷配線板會有出現凹痕的顧慮。
相反地，若樹脂組成物中的無機填料含量變少，則如上述般的掉屑會受到抑制，但是反而會無法充分得到降低CTE的效果。
附帶一提，日本特開2009-253138號公報揭示了一種使由環氧樹脂與重量平均分子量為45×104~85×104的丙烯酸樹脂所構成的樹脂成分中含有無機填充材70~90重量 %而成的複合板。在日本特開2009-253138號公報中，揭示了藉由提高無機填充材的含量，降低熱膨脹係數，而且添加丙烯酸樹脂來改善複合板的可撓性，在板材切斷加工時防止了切屑的發生。
本發明提供一種預浸體及貼覆金屬之積層板，可確保良好的成形性，同時可兼顧抑制掉屑的與低CTE化。
本發明所關連的預浸體具有纖維基材、及含浸於纖維基材的熱硬化性樹脂組成物。熱硬化性樹脂組成物含有：含有環氧樹脂的熱硬化性樹脂、硬化劑、無機填料、及重量平均分子量(Mw)為10×104以上未達45×104的丙烯酸酯共聚物。無機填料的含量，相對於熱硬化性樹脂與硬化劑的合計100質量份為150質量份以上。丙烯酸酯共聚物的含量，相對於熱硬化性樹脂與硬化劑的合計100質量份為大於30質量份、90質量份以下。
本發明所關連的貼覆金屬的積層板，具有上述預浸體的硬化物之絕緣層、及設置於該絕緣層上的金屬箔。
在上述預浸體中，熱硬化性樹脂組成物，相對於熱硬化性樹脂與硬化劑的合計100質量份，含有無機填料150質量份以上，含有Mw為10×104以上，未達45×104的丙烯酸酯共聚物大於30質量份，90質量份以下。像這樣，在本發明的預浸體中填充了許多無機填料，因此硬化物的CTE變小。另外，由於併用了無機填料以及丙烯酸酯共聚 物，因此藉由丙烯酸酯共聚物所具有的彈性率可使應力緩和。因此，與僅摻合無機填料的情況相比，硬化物的CTE變得更小。此外，藉由使丙烯酸酯共聚物的含量在上述範圍，儘管含有大量無機填料，在切斷時等也能夠抑制掉屑。另外，還可抑制細斑等的發生，確保良好的成形性。所以，使用此預浸體所製造出的貼覆金屬的積層板或印刷配線板，其絕緣層的CTE小，因此彎曲會受到抑制，而且還可防止預浸體的掉屑造成的凹痕。
2A‧‧‧熱硬化性樹脂組成物(樹脂組成物)
4A‧‧‧纖維基材
10‧‧‧預浸體
12‧‧‧絕緣層
14‧‧‧金屬箔
16‧‧‧導體圖型
20‧‧‧貼覆金屬之積層板
30‧‧‧印刷配線板
圖1為由本發明之實施形態所得到的預浸體之概略剖面圖。
圖2表示由本發明之實施形態所得到的貼覆金屬的積層板的一例之概略剖面圖。
圖3表示由本發明之實施形態所得到的印刷配線板的一例之概略剖面圖。
在說明本發明之實施形態之前，先對於以往的複合板或預浸體的問題點作簡單說明。日本特開2009-253138號公報所記載的複合板並不含纖維基材，而為與含有纖維基材的預浸體不同的物品。所以，對於製造印刷配線板時的成形性等特性的要求條件也不同。另外，日本特開2009-253138號公報所揭示的丙烯酸樹脂的重量平均分子量較 大，且摻合量較低。因此，認為難以同時解決預浸體產生細斑等的成形性問題與掉屑的問題。
以下針對由本發明之實施形態所得到的預浸體作說明。圖1為由本實施形態所得到的預浸體10的概略剖面圖。預浸體10具有纖維基材4A、及含浸於纖維基材4A的熱硬化性樹脂組成物(以下稱為樹脂組成物)2A。
樹脂組成物2A含有：含有環氧樹脂的熱硬化性樹脂、硬化劑、無機填料、及重量平均分子量(Mw)為10×104以上未達45×104的丙烯酸酯共聚物。然後，藉由使樹脂組成物2A含浸於纖維基材4A，並加熱乾燥至成為半硬化狀態(亦稱為B階段狀態)，可形成印刷配線板用的預浸體10。
熱硬化性樹脂可採用至少含有環氧樹脂的樹脂。熱硬化性樹脂亦可為含有環氧樹脂與其他熱硬化性樹脂的混合物，或可只含有環氧樹脂。
環氧樹脂只要是形成印刷配線板用的各種基板材料時所能夠使用的環氧樹脂，則不受特別限定。具體而言，可列舉萘型環氧樹脂、甲酚酚醛型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、脂環式環氧樹脂、脂肪族鏈狀環氧樹脂、苯酚酚醛型環氧樹脂、烷基苯酚酚醛型環氧樹脂、芳烷基型環氧樹脂、聯苯酚型環氧樹脂、二環戊二烯型環氧樹脂、參羥基苯基甲烷型環氧化合物、酚類與具有酚性羥基的芳香族醛的縮合物的環氧化物、雙酚的二縮水甘油醚化物、萘二醇的二縮水甘油醚 化物、酚類之縮水甘油醚化物、醇類的二縮水甘油醚化物、三縮水甘油基異氰尿酸酯等。另外，除了以上列舉的物質以外，還可使用各種縮水甘油醚型環氧樹脂、縮水甘油基胺型環氧樹脂、縮水甘油基酯型環氧樹脂、氧化型環氧樹脂，其他還有磷變性環氧樹脂等。環氧樹脂可單獨使用1種，或可併用2種以上。尤其從硬化性優異的觀點看來，宜使用一分子中具有2個以上的環氧基的環氧樹脂。
在熱硬化性樹脂中含有環氧樹脂以外的熱硬化性樹脂的情況下，其種類並不受特別限制。可列舉例如多官能氰酸酯樹脂、多官能馬來醯亞胺-氰酸酯樹脂、多官能性馬來醯亞胺樹脂、不飽和聚苯醚樹脂、乙烯基酯樹脂、尿素樹脂、鄰苯二甲酸二烯丙酯樹脂、黑色素樹脂、胍胺樹脂、不飽和聚酯樹脂、三聚氰胺-尿素共縮合樹脂等。這些環氧樹脂以外的熱硬化性樹脂，可單獨使用1種或併用2種以上。
硬化劑可採用過去以來一般使用的硬化劑，只要因應熱硬化性樹脂的種類適當地選定即可。在熱硬化性樹脂中含有環氧樹脂，因此只要是能夠作為環氧樹脂的硬化劑來使用的物質，則並無特別限制。可列舉例如二胺系硬化劑、2官能以上的硬化劑等。二胺系硬化劑可使用1級胺或2級胺。2官能以上的硬化劑，可列舉2官能以上的酚化合物、酸酐系硬化劑、二氰二醯胺、聚苯醚化合物(PPE)等。這些硬化劑可單獨使用1種或併用2種以上。
硬化劑尤其適合使用2官能以上的酚樹脂。這種2官能以上的酚樹脂可列舉例如酚醛型酚樹脂、萘型酚樹脂、甲酚酚醛樹脂、芳香族烴甲醛樹脂變性酚樹脂、二環戊二烯酚加成型樹脂、苯酚芳烷基樹脂、甲酚芳烷基樹脂、萘酚芳烷基樹脂、聯苯基變性苯酚芳烷基樹脂、苯酚三羥甲基甲烷樹脂、四羥苯基乙烷樹脂、萘酚酚醛樹脂、萘酚-酚共縮酚醛樹脂、萘酚-甲酚共縮酚醛樹脂、聯苯基變性酚樹脂、胺基三嗪變性酚樹脂、聯苯酚、乙二醛四苯酚樹脂、雙酚A酚醛樹脂、雙酚F酚醛樹脂等。該等可單獨使用1種或併用2種以上。
為了降低樹脂組成物2A的硬化物的CTE，而以較高的含量使其含有無機填料。無機填料具體的含量，相對於熱硬化性樹脂與硬化劑的合計100質量份為150質量份以上。為了進一步降低CTE，宜定為200質量份以上。含有愈多無機填料，愈能夠期待降低CTE。但是，若無機填料的含量增加，則樹脂組成物2A中的樹脂成分比率降低。伴隨於此，加熱成形時，熔融樹脂的流動性降低，發生容易細斑或樹脂分離等現象，成形性降低，而且會有掉屑的顧慮。
所以，無機填料可容許的含量會有限度，在以往的樹脂組成物的樹脂設計的範圍中，一般而言認為上限是相對於樹脂成分100質量份，無機填料為400質量份左右。在本實施形態的情況，從成形性的觀點看來，無機填料的含量的上限係以400質量份以下為佳，360質量份以下為較 佳。此外，在本實施形態中，藉由使樹脂組成物2A含有丙烯酸酯共聚物，也會有提升成形性的效果，因此無機填料的含量可以高於400質量份，並且有可能達450~500質量份。
無機填料的種類並未受到特別限定。可使用例如二氧化矽、硫酸鋇、氧化矽粉、二氧化矽碎塊、燒成滑石、經鉬酸鋅處理的滑石、鈦酸鋇、氧化鈦、黏土、氧化鋁、雲母、水鋁礦、硼酸鋅、錫酸鋅、其他金屬氧化物或金屬水合物，此外還有氫氧化鋁、碳酸鈣、氫氧化鎂、矽酸鎂、玻璃短纖維、硼酸鋁晶鬚、碳酸矽晶鬚等。該等可單獨使用1種，或可併用2種以上。無機填料的形狀或尺寸並不受特別限制，例如亦可併用不同尺寸的無機填料。從提高無機填料的填充率的觀點看來，例如併用粒徑1μm以上的填料以及粒徑未達1μm的奈米級微小填料亦為適合。亦可藉由偶合劑等對這些無機填料實施表面處理。
無機填料可降低樹脂組成物2A的硬化物的CTE，同時可良好地保持電子特性或耐熱性、熱傳導性等的其他特性的觀點看來，宜含有二氧化矽。此情況下，無機填料的含量，相對於二氧化矽的總質量宜過半，尤其宜為80質量%以上。
樹脂組成物2A含有Mw為10×104以上、未達45×104之丙烯酸酯共聚物。這種丙烯酸酯共聚物，在樹脂組成物2A的硬化物因為熱膨脹而受到應力時，可發揮緩和此膨脹的作用(膨脹緩和作用)。一般而言，丙烯酸橡膠粒子 等會在樹脂組成物中以粒狀的形態存在。另一方面，丙烯酸酯共聚物與丙烯酸橡膠粒子等有所不同，在有機溶劑中，與其他樹脂成分一起調製成樹脂清漆時，會以不定形而且與其他樹脂成分相溶的狀態混合。
丙烯酸酯共聚物，是由至少含有丙烯酸酯所形成的重複構造單元(丙烯酸酯單元)的分子所形成。丙烯酸酯所形成的重複構造單元，意指使丙烯酸酯單體聚合時所形成的重複構造單元。丙烯酸酯共聚物的分子中含有多種不同的丙烯酸酯所形成的重複構造單元，甚至還可含有丙烯酸酯以外的單體所形成的重複構造單元。或者，丙烯酸酯共聚物的分子，亦可由多種不同的丙烯酸酯所形成的重複構造單元構成。另外，丙烯酸酯共聚物可含有1種丙烯酸酯所形成的重複構造單元，以及該丙烯酸酯以外的單體所形成的重複構造單元。
在丙烯酸酯之中，直接鍵結於酯鍵中的碳的取代基，可列舉烷基或經取代的烷基。在經取代的烷基中，烷基的任一氫原子都可被其他官能基取代。在烷基的情況，可為直鏈狀或具有分支，另外還可為脂環式烷基。此外，上述取代基可為芳香族。丙烯酸酯的具體例子，例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸異丙酯、丙烯酸丁酯、丙烯酸異丁酯、丙烯酸第三丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸環己酯、丙烯酸辛酯、丙烯酸癸酯、丙烯酸月桂酯、丙烯酸苄酯等，然而並不受該等所限定。
丙烯酸酯以外的單體可例示丙烯腈。另外，其他還可 列舉丙烯醯胺、丙烯酸、甲基丙烯酸、甲基丙烯酸酯、苯乙烯、乙烯、丙烯、丁二烯等、丙烯酸酯以外的乙烯基系單體。丙烯酸酯共聚物亦可含有2種以上不同的丙烯酸酯以外的單體所形成的重複構造單元。
構成丙烯酸酯共聚物的重複構造單元可隨機排列，或相同種類的重複構造單元可各自成為嵌段。亦即丙烯酸酯共聚物可為隨機共聚物或嵌段共聚物。另外，丙烯酸酯共聚物只要在不阻礙其效果的程度，亦可為具有分支的接枝共聚物或交聯體。
丙烯酸酯共聚物可藉由例如使既定單體進行自由基聚合而得到，然而並不受這種製造方法所限定。
丙烯酸酯共聚物亦可進一步在聚合物分子的末端、側鏈或主鏈具有官能基。此官能基尤其宜為與環氧樹脂及硬化劑的至少任一者具有反應性的官能基。這種官能基可例示例如環氧基、羥基、羧基、胺基、醯胺基。藉由使上述官能基鍵結於丙烯酸酯共聚物，可與例如樹脂組成物2A中所含有的其他成分發生反應，而編入熱硬化性樹脂的硬化系統構造。因此可提升耐熱性、相溶性、耐藥品性等的性能。上述列舉的官能基之中，以環氧基為特佳。在聚合物一個分子中亦可具有多個官能基。此外，亦可將具有如上述般的官能基的情況稱為以如上述般的官能基變性，例如可將具有環氧基的情況稱為環氧變性。
尤其丙烯酸酯共聚物宜具有表現出橡膠彈性的分子構造。此情況下，可進一步提高膨脹緩和作用的效果。例如 含有來自丙烯酸丁酯的重複構造單元與來自丙烯腈的重複構造單元的丙烯酸酯共聚物，可表現出橡膠彈性。另外，其他，含有來自丁二烯的重複構造單元，也能夠表現出橡膠彈性。
丙烯酸酯共聚物可溶於有機溶劑，而且在與樹脂組成物2A的其他成分在有機溶劑中混合而調製成樹脂清漆時，會與可溶於溶劑的其他樹脂成分均勻混合。此丙烯酸酯共聚物(以下稱為丙烯酸樹脂)，在調製清漆時，能夠以固體物的方式溶解於有機溶劑來使用，或以預先溶解於有機溶劑的液狀方式來使用。以這種方式，丙烯酸樹脂溶解於有機溶劑，並與其他樹脂成分均勻混合，容易發揮上述膨脹緩和作用。另外還認為，在加熱成形時的流動狀態時，容易抑制樹脂成分與填料分離。有機溶劑可例示丙酮、甲基乙基酮、環己酮等的酮系溶劑、甲苯、二甲苯等的芳香族系溶劑、醋酸乙酯等的酯系溶劑等、該等可單獨使用1種，或可併用2種以上。
藉由使丙烯酸酯共聚物含有樹脂組成物2A，容易適當控制樹脂組成物2A的黏度。因此，由樹脂組成物2A所形成的基板材料(預浸體10或後述貼覆金屬的積層板20)中，來自樹脂組成物2A的樹脂成分與無機填料變得不易分離，成形性良好。另外，藉由使樹脂組成物2A含有丙烯酸酯共聚物，亦可降低預浸體的CTE。這是因為藉由丙烯酸酯共聚物發揮上述膨脹緩和作用，熱膨脹會被丙烯酸酯共聚物吸收的緣故。
丙烯酸酯共聚物的Mw為10×104以上，未達45×104，宜為10×104以上，35×104以下。藉由定在此範圍，如後述般，相對於熱硬化性樹脂與硬化劑的合計100質量份，摻合大於30質量份，可確保良好的成形性。藉此，確保良好的成形性，同時可兼顧將預浸體10切斷時的掉屑的抑制以及樹脂組成物2A的硬化物CTE的降低。另外，在有機溶劑中的溶解性或其摻合量和樹脂組成物2A熔融黏度的調整之間，容易取得平衡。像這樣，若使用分子量較小的丙烯酸酯共聚物，則與使用45×104以上這種分子量較大的丙烯酸酯共聚物的情況相比，可含有較多無機填料，能夠抑制樹脂組成物2A的熔融黏度過度上昇。若丙烯酸酯共聚物的Mw在45×104以上，則在增加摻合量時，會有發生細斑等現象，而使成形性降低的顧慮。因此，丙烯酸酯共聚物摻合量的提高會有所限制，而難以兼顧CTE的降低與確保成形性。另一方面，若丙烯酸酯共聚物的Mw小於10×104，則會有丙烯酸酯共聚物產生的彈性變低，對於低CTE化的貢獻降低的顧慮。而且，預浸體10會有無法充分得到掉屑防止效果的顧慮。此外，此處所謂的Mw，是指藉由例如凝膠滲透層析並以聚苯乙烯換算所測得的值。
樹脂組成物2A中，除了含有熱硬化性樹脂、硬化劑、無機填料、丙烯酸酯共聚物之外，只要不阻礙本發明之效果，亦可因應必要含有其他成分。其他成分可摻合例如稀釋用的有機溶劑、咪唑等的硬化促進劑、抗氧化劑、 用來提升無機填料的混合性的濕潤分散劑或偶合劑、光安定劑、黏度調整劑、阻燃劑、著色劑、消泡劑等。稀釋用的有機溶劑可採用例如丙酮、甲基乙基酮、環己酮等的酮系溶劑、甲苯、二甲苯等的芳香族系溶劑、二甲基甲醯胺等的氮含有溶劑等。
樹脂組成物2A，可藉由分別將含有環氧樹脂的熱硬化性樹脂、硬化劑、無機填料，及丙烯酸酯共聚物，因應必要適當添加的添加劑等的其他成分摻合在有機溶劑中而調製。
丙烯酸酯共聚物的含量，相對於熱硬化性樹脂與硬化劑的合計100質量份為大於30質量份，且在90質量份以下。如前述般，一般而言，愈增加樹脂組成物中的無機填料含量，愈能夠降低硬化物的CTE，但是反而容易發生掉屑，而為所謂的互償關係。因此，為了兼顧低CTE與掉屑的抑制，只採用無機填料作為降低CTE的手段時，則會有極限。相對於此，在本實施形態中，藉由在上述含量範圍內含有無機填料以及丙烯酸酯共聚物，藉由這些相乘效果，可達到更低的CTE化。同時，在將無機填料定為150質量份以上的高含量的情況，也能夠抑制掉屑。若丙烯酸酯共聚物的含量在30質量份以下，則會有預浸體的掉屑抑制效果降低的顧慮，而且對於低CTE化的貢獻會變低。另一方面，若丙烯酸酯共聚物的含量大於90質量份，則會有成形時產生細斑等的顧慮。
預浸體10可藉由使樹脂組成物2A含浸於纖維基材 4A，加熱乾燥使其成為半硬化狀態(B階段狀態)而形成。使其成為半硬化狀態時的溫度條件或時間可定為例如120~190℃，3~15分鐘。
纖維基材4A並未受到特別限定，可使用如平織等方式般，縱線及橫線大致正交的方式所織成的基材。可使用例如玻璃布等的無機纖維織布、芳綸布、聚酯布等由有機纖維所構成的纖維基材。纖維基材4A的厚度並無特別限制，宜為10~200μm。
接下來針對由本實施形態所得到的貼覆金屬的積層板作簡單說明。圖2表示由本實施形態所得到的貼覆金屬的積層板20的一例的概略剖面圖。
貼覆金屬的積層板20，可藉由取1枚預浸體10或將多枚重疊，並將金屬箔14重疊在其兩面或單面，加熱加壓成形使其層合而一體化來製，作。亦即，貼覆金屬的積層板20具有預浸體10的硬化物的絕緣層12、及設置於絕緣層12上的金屬箔14。金屬箔14可使用例如銅箔等。貼覆金屬的積層板20，可藉由使用例如多段真空壓延或雙帶壓機等，將預浸體10與金屬箔14的層合體加熱、加壓而成形。
以上的方式所形成的預浸體10或貼覆金屬的積層板20，是使用樹脂組成物2A所形成，因此如上述般，CTE低而且不易發生掉屑。而且這種預浸體10不易彎曲。另外，樹脂成分與無機填料的分離(樹脂分離)或細斑也不易發生，在切斷時，樹脂成分及無機填料的粉粒幾乎不會 飛散。因此，有效利用作為用來製作沒有主要由粉屑附著造成的凹痕之高性能印刷配線板的基板材料。
接下來，針對由本實施形態所得到的印刷配線板作簡單說明。圖3表示由本實施形態所得到的印刷配線板30的一例的概略剖面圖。
印刷配線板30，是藉由對貼覆金屬的積層板20的金屬箔14加工，設置導體圖型16而形成。亦即，印刷配線板30具有預浸體10的硬化物的絕緣層12、及設置於絕緣層12上的導體圖型16。導體圖型16可藉由例如減去法等來形成。另外，後來藉由在印刷配線板30上實裝半導體元件，並且加以密封，可製造出FBGA(Fine pitch Ball Grid Array)等的封裝。另外，還可藉由使用這種封裝作為子封裝，並將多個子封裝層合，而製造出PoP(Package on Package)等的封裝。
印刷配線板30是由低CTE且不易掉屑的基板材料所構成。因此，印刷配線板30不易彎曲，而且幾乎沒有觀察到凹痕。
以下使用較具體的例子，對本實施形態所產生的效果作說明。
準備下述所揭示的熱硬化性樹脂、硬化劑、無機填料、丙烯酸酯共聚物、添加劑(分散劑、偶合劑、抗氧化劑)，將這些原料以表1、表2所表示的摻合量(質量份)混合，調製出樹脂清漆(熱硬化性樹脂組成物)。各原料的細節如以下所述。
<熱硬化性樹脂>
‧多官能環氧樹脂(日本化藥股份有限公司製「EPPN-502H」)
<硬化劑>
‧萘骨架酚樹脂(DIC股份有限公司製「HPC-95000」)
‧苯酚酚醛樹脂(DIC股份有限公司製「TD-2090」)
此外，上述2種硬化劑任一者皆為2官能以上的酚樹脂。
<丙烯酸酯共聚物>
‧丙烯酸酯共聚物(環氧變性丙烯酸樹脂，Nagase ChemteX股份有限公司製「SG-P3mw1」，Mw：25×104)
‧丙烯酸酯共聚物(環氧變性丙烯酸樹脂，Nagase ChemteX股份有限公司製「SG-P3」，Mw：85×104)
<無機填料>
‧二氧化矽A(Admatechs股份有限公司製「SC-4500SQ」)
‧二氧化矽B(Admatechs股份有限公司製「SC-2500SEJ」)
‧氫氧化鎂(堺化學工業股份有限公司製「MGZ-6R」)
<添加劑>
‧分散劑(BYKJapan股份有限公司製「W903」)
‧偶合劑(信越聚矽氧股份有限公司製「KBE-9007」)
‧抗氧化劑(三光股份有限公司製「HCA」)
使依照表1、表2所示的配方組成所調製出的樹脂清漆含浸於作為纖維基材的玻璃布(日東紡績股份有限公司製「2117」，厚度95μm)，並使硬化後的厚度成為100μm，然後藉由在145℃下加熱乾燥2分鐘至成為半硬化狀態，而製造出預浸體。
將4枚的上述預浸體重疊，在其兩面層合作為金屬箔而且厚度為12μm的銅箔，在真空條件下，以6.0MPa加壓，同時在200℃下加熱120分鐘，使其成形。以這種方式，在積層板貼覆金屬，而製造出貼銅積層板。
使用以這種方式製作出的各樣品的預浸體或貼銅積層板，評估各種物性(掉屑、細斑、CTE)。在表1、表2中一併揭示了各樣品的物性評估的結果。
此外，各種物性的評估是藉由以下所揭示的方法來進行。
<掉屑>
將各樣品的預浸體以切割工具切斷時，藉由目視觀察的是否掉屑。
<細斑>
藉由蝕刻除去各樣品之貼銅積層板表面的銅箔，以目視觀察表面有無細斑，將沒有細斑的情況定判定「OK」，有細斑的情況判定為「NG」。
(CTE(拉伸))
對於藉由蝕刻除去各樣品的貼銅積層板的表面的銅箔所得到的評估用檢體，在未達絕緣層中的樹脂硬化物的玻璃轉移溫度的溫度下，測定縱方向的熱膨脹係數。測定是依據JIS C 6481(相當於IPC-TM-650 2.4.24.5)，並依據TMA法(Thermo-mechanical analysis)來進行，測定是使用熱分析裝置(Seiko Instruments Inc.公司製「TMA/SS6000」)。
表1所示的樣品EA~EC任一者的CTE值皆低於表2所示的樣品CD，而且也沒有觀察到掉屑或細斑。樣品ED的CTE值也低於樣品CE，而且也沒有觀察到掉屑或細斑。
尤其可知，若將丙烯酸酯共聚物以外的組成相同的樣品EA~EC加以比較，則丙烯酸酯共聚物的含量愈多，愈有效降低CTE。
另一方面，樣品CA沒有觀察到細斑，然而丙烯酸酯共聚物的含量少，因此觀察到掉屑，CTE也高。另外，樣品CB沒有觀察到掉屑，然而丙烯酸酯共聚物的含量多，因此觀察到細斑，由於無法得到良好的樣品片，所以無法測定CTE。使用重量平均分子量高的丙烯酸酯共聚物的樣品CC雖然沒有觀察到掉屑，然而卻發生細斑。
由以上結果可知，樣品EA~EC使用了由本實施形態所得到的樹脂組成物2A來形成預浸體、貼覆金屬的積層板，因此可維持低CTE，同時可抑制掉屑。因此可製作出不易彎曲，而且沒有凹痕的高品質印刷配線板。
如以上所述方式，可從本發明所得到的基板材料(預浸體及使用其之貼覆金屬之積層板)製作出印刷配線板。此印刷配線板是由低CTE且不易掉屑的基板材料所構成。因此，印刷配線板不易彎曲，而且幾乎沒有觀察到凹痕。所以，較容易適用於目標為薄型化或小型化的電器用品等。因此，以這種方式所形成的印刷配線板，可使用於例如通訊、測量機器、OA機器或其周邊終端機等各種用途。

Claims (6)

  1. 一種預浸體，其係具備：纖維基材、及含浸於前述纖維基材的熱硬化性樹脂組成物，前述熱硬化性樹脂組成物係含有：含環氧樹脂的熱硬化性樹脂、硬化劑、無機填料、及重量平均分子量為10×104以上，未達45×104的丙烯酸酯共聚物，前述無機填料的含量，相對於前述熱硬化性樹脂與前述硬化劑的合計100質量份為150質量份以上，前述丙烯酸酯共聚物的含量，相對於前述熱硬化性樹脂與前述硬化劑的合計100質量份為大於30質量份、90質量份以下，前述無機填料係含2種以上尺寸不同的無機填料，再者前述無機填料的至少1種為二氧化矽，前述二氧化矽的含量相對於前述無機填料總量之質量為80質量%以上96質量%以下。
  2. 如申請專利範圍第1項之預浸體，其中前述丙烯酸酯共聚物具有對於前述環氧樹脂及前述硬化劑的至少任一者具有反應性之官能基。
  3. 如申請專利範圍第1項之預浸體，其中前述硬化劑係選自二胺系硬化劑、2官能以上的酚化合物、酸酐系硬化劑、二氰二醯胺、聚苯醚化合物之群的至少1種。
  4. 如申請專利範圍第1項之預浸體，其中前述硬化劑為2官能以上的酚樹脂。
  5. 一種貼覆金屬之積層板，其係具備絕緣層及設置於前述絕緣層上的金屬箔，該絕緣層為如申請專利範圍第1項之預浸體的硬化物。
  6. 一種印刷配線板，其係具備絕緣層及設置於前述絕緣層上的導體圖型，該絕緣層為如申請專利範圍第1項之預浸體的硬化物。
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