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TW201230912A - Process for the production of laminates - Google Patents

Process for the production of laminates Download PDF

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Publication number
TW201230912A
TW201230912A TW100127223A TW100127223A TW201230912A TW 201230912 A TW201230912 A TW 201230912A TW 100127223 A TW100127223 A TW 100127223A TW 100127223 A TW100127223 A TW 100127223A TW 201230912 A TW201230912 A TW 201230912A
Authority
TW
Taiwan
Prior art keywords
insulating layer
prepreg
manufactured
layer
laminate
Prior art date
Application number
TW100127223A
Other languages
Chinese (zh)
Other versions
TWI578871B (en
Inventor
Hirohisa Narahashi
Shigeo Nakamura
Original Assignee
Ajinomoto Kk
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Publication date
Application filed by Ajinomoto Kk filed Critical Ajinomoto Kk
Publication of TW201230912A publication Critical patent/TW201230912A/en
Application granted granted Critical
Publication of TWI578871B publication Critical patent/TWI578871B/en

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B32B2037/268—Release layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

A method of manufacturing a laminated plate is provided to enable a laminated plate to have a conduct layer with excellent stripping strength on the surface of a flat insulating layer by maintaining a glass transition temperature and tensile modulus without an extra metallic-film removing process. A method of manufacturing a laminated plate comprises next steps. One or more sheets of prepreg are arranged between supports. The prepreg is cured to form an insualting layer by heating and pressing under a reduced pressure. The supports are removed. The surface of the insulating layer is harmonized. A metallic film layer is formed on the surface of the insulating layer by electroless plating. For non-volatile components of 100mass% of curable resin composition, inorganic fillers are contained by 40-80 mass%. The glass transition temperature of the insulating layer is 150-270DEG C and tensile modulus thereof is 10-35GPa.

Description

201230912 六、發明說明： 【發明所屬之技術領域】 本發明係關於特定之層合板的製造方法，且進一步關 於使用所得之層合板之電路基板的製造方法。 【先前技術】 芯材的電路形成方法，係有將金屬箔層合板的多餘金 屬箔部分予以蝕刻，並應用剩餘的金屬箔部分來直接形成 電路之減成法，以及去除金屬箔層合板的全部金屬箔，並 將絕緣層上所形成之來自金屬箔的凹凸用作爲定錨以進行 無電解電鍍，然後藉由電解電鍍來形成導體層之半加成法 (專利文獻1)。然而，當在絕緣層表面上形成凹凸時， 藉由蝕刻來去除電路形成時所不需要的導體層及電鍍遮蔽 層時，難以去除凹凸中的金屬，另一方面，在可充分去除 之條件進行蝕刻時，必要部分之導體層的溶解變得顯著， 而產生阻礙細微配線化之問題。此外，專利文獻1中，由 於夾持B-stege樹脂組成物薄片，故對於基板的小型化較爲 不利。 此外，係有人開發出採用在金屬箔上形成有黏著輔助 劑層之附有黏著輔助劑的金屬箔之銅箔層合板（專利文獻 2)。然而，由於設置有黏著輔助劑層，故對於基板的小 型化較爲不利，且亦須進行去除金屬箔之步驟，並且於可 靠度試驗後在電鍍界面與黏著輔助劑層之界面產生膨脹， 或是在黏著輔助劑層之與預浸材層之界面產生膨脹，而有 -5- 201230912 無法確保充分的可靠度之問題。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕日本特開2003-332734號公報 〔專利文獻2〕日本特開2006-2 1 8855號公報 【發明內容】 (發明所欲解決之課題） 本發明之課題在於提供一種不須透過去除金屬箔之多 餘步驟，來形成可一邊維持玻璃轉移溫度與拉伸彈性率， 且同時在平滑絕緣層表面上形成剝離強度佳之導體層之層 合板的製造方法。 (用以解決課題之手段） 本發明者們係爲了解決上述課題而進行精心探討，結 果發現到可藉由特定之層合板的製造方法來達成上述課題 本發明之特徵如下所述。 [1] 一種層合板的製造方法，其特徵係包含：（A)於 支撐體之間配置1片以上的預浸材，並藉由在減壓下進行 加熱及加壓使預浸材硬化而形成絕緣層之步驟， (B) 去除支撐體之步驟， (C) 對絕緣層表面進行粗化處理之步驟’以及 (D) 藉由無電解電鍍於絕緣層表面上形成金屬膜層 -6- 201230912 之步驟；且 相對於前述預浸材中之硬化性樹脂組成物中的非揮發 份100質量％，含有無機塡充材40質量％以上80質量％以下 > 前述絕緣層的玻璃轉移溫度爲150°C以上270°C以下， 拉伸彈性率爲lOGPa以上35GPa以下； 在前述（C)對絕緣層表面進行粗化處理之步驟後之 絕緣層的算術平均粗糙度爲O.lnm以上600nm以下； 在前述（D)藉由無電解電鍍於絕緣層表面上形成金 屬膜層之步驟後之絕緣層與金屬膜層的剝離強度爲 〇.45kgf/cm 以上 10kgf/cm 以下。 （ [2] 如上述[1]之層合板的製造方法，其中支撐體爲脫 模塑膠膜。 [3] 如上述[1]或[2]之層合板的製造方法，其中預浸材 是由硬化性樹脂組成物與薄片狀纖維基材所構成。 [4] 如上述[3]之層合板的製造方法，其中預浸材中的 薄片狀纖維基材’係含有選自玻璃纖維、有機纖維、玻璃 不織布、有機不織布之1種或2種以上。 [5] 如上述[4]之層合板的製造方法，其中薄片狀纖維 基材爲厚度1〜200μιη的玻璃纖維。 [6] 如上述[1]至[5]之層合板的製造方法，其中預浸材 中的硬化性樹脂組成物含有環氧樹脂及硬化劑。 [7] 如上述[6]之層合板的製造方法，其中預浸材中的 硬化性樹脂組成物爲萘型環氧樹脂及萘酣系硬化劑。 201230912 [8] 如上述[1]至[7]之層合板的製造方法，其係在 150〜250 °C、60〜150分鐘的條件下硬化預浸材而形成絕緣 層。 [9] 如上述[1]至[8]之層合板的製造方法，其中進一步 包含（E)形成貫通孔之步驟。 [10] 如上述[9]之層合板的製造方法，其中在（b )去 除支撐體之步驟前，進行（E)形成貫通孔之步驟。 [11] 如上述[1]至[10]之層合板的製造方法，其中進一 步包含（F)藉由電解電鍍以形成導體層之步驟。 [1 2 ]—種多層印刷配線基板’其係使用藉由如上述[j ] 至[11]之製造方法所得之層合板。 [13]—種半導體裝置，其係使用藉由如上述[丨]至！^" 之製造方法所得之層合板。 發明之效果： 藉由本發明之特定之層合板的製造方法，可得到一種 不須透過去除金屬范之多餘步驟，來形成可一邊維持玻璃 轉移溫度與拉伸彈性率’且同時在平滑絕緣層表面上形成 剝離強度佳之導體層之層合板。 【實施方式】 以下依循較佳實施形態來詳細說明本發明。 本發明是一種層合板的製造方法，其特徵係包含：（ A)於支撐體之間配置1片以上的預浸材，並藉由在減壓下 -8 - 201230912 進行加熱及加壓使預浸材硬化而形成絕緣層之步驟， (B)去除支撐體之步驟， (C )對絕緣層表面進行粗化處理之步驟，以及 (D)藉由無電解電鍍於絕緣層表面上形成金屬膜層 之步驟。 [(A)步驟]] <預浸材> 本發明中所使用之預浸材，較佳是由硬化性樹脂組成 物與薄片狀纖維基材所構成，可使硬化性樹脂組成物含浸 於薄片狀纖維基材並進行加熱乾燥而得。硬化性樹脂組成 物並不特別限定，均可使用。當中較佳是含有（a)環氧 樹脂之組成物，尤佳是含有（a )環氧樹脂、（b )硬化劑 、（c )熱可塑性樹脂之組成物。 (a )環氧樹脂，例如可列舉出雙酚A型環氧樹脂、聯 苯型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、雙酚F 型環氧樹脂、含磷環氧樹脂、雙酚S型環氧樹脂、脂環型 環氧樹脂、脂肪族鏈狀環氧樹脂、酚-酚醛型環氧樹脂、 甲酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、具有丁二 烯結構之環氧樹脂、雙酚的二縮水甘油醚化物、萘二醇的 二縮水甘油醚化物、酚類的縮水甘油醚化物、及醇類的二 縮水甘油醚化物、以及此等環氧樹脂的烷基取代體、鹵化 物及加氫物等。此等可使用1種或2種以上。 當中，就耐熱性提升、絕緣可靠度提升、與金屬膜之 -9- 201230912 密著性的提升之觀點來看’較佳爲雙酚A型環氧樹脂、萘 酚型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂、具有丁 二稀結構之環氧樹脂，尤佳爲萘型環氧樹脂。具體而言， 例如可列舉出液狀雙酚A型環氧樹脂（三菱化學股份有限 公司製「Epikote 828EL」）、萘型2官能環氧樹脂（DIC 股份有限公司製「HP4032」、「HP4032D」）、萘型4官 能環氧樹脂（DIC股份有限公司製「HP4700」）、萘酚型 環氧樹脂（東都化成股份有限公司製「ESN-475V」）、 具有丁二烯結構之環氧樹脂（Daicel化學工業股份有限公 司製「PB-3600」）、具有聯苯結構之環氧樹脂（日本化 藥股份有限公司製「NC3000H」、「NC3000L」、三菱化 學股份有限公司製「YX4000」）等。 (b )硬化劑’例如可列舉出胺系硬化劑、胍系硬化 劑、咪唑系硬化劑 '含有三嗪骨架的酚系硬化劑、酚系硬 化劑、含有三嗪骨架的萘酚系硬化劑、萘酚系硬化劑 '酸 酐系硬化劑或此等經環氧加成化或微膠囊化者、活性酯系 硬化劑、苯並噁嗪系硬化劑、氰酸酯樹脂等。就提升電鍍 的剝離強度之觀點來看，硬化劑較佳爲於分子結構中具有 氮原子者，當中較佳爲含有三嗪骨架的酚系硬化劑、含有 三嗪骨架的萘酚系硬化劑，特佳爲含有三嗪骨架的酚-酚 醛樹脂。就耐熱性提升、絕緣可靠度提升、與金屬膜之密 著性的提升之觀點來看，較佳爲萘酚系硬化劑。此等可使 用1種或2種以上。 酚系硬化劑、萘酚系硬化劑的具體例，例如可列舉出 -10- 201230912 MEH-7700、MEH-7810、MEH-7851 (明和化成股份有限公 司製）、ΝΗΝ、CBN、GPH (日本化藥股份有限公司製） ' SN170、SN180、SN190、SN475、SN48 5、SN495、 SN3 75、SN3 95 (東都化成股份有限公司製）、TD2090 ( D 1C股份有限公司製）等。含有三嗪骨架的酚系硬化劑的 具體例，可列舉出LA3018 ( DIC股份有限公司製）等。含 有三嗪骨架的酚-酚醛硬化劑的具體例，可列舉出LA7052 、LA7054、LA1356 (DIC股份有限公司製）等。 活性酯系硬化劑，一般可適當地使用酚酯類、硫酚酯 類、N-羥胺酯類、雜環羥基化合物的酯類等之於1分子中 具有2個以上之反應活性高的酯基之化合物。該活性酯化 合物，較佳是藉由羧酸化合物及/或硫羧酸化合物與羥基 化合物及/或硫醇化合物之縮合反應所得者。尤其就耐熱 性等觀點來看，較佳是由羧酸化合物與酚化合物或萘酚化 合物所得之活性酯化合物。羧酸化合物，例如可列舉出苯 甲酸、乙酸、琥珀酸、馬來酸、衣康酸、鄰苯二甲酸、間 苯二甲酸、對苯二甲酸、焦蜜石酸等。酚化合物或萘酚化 合物，可列舉出對苯二酚、間苯二酚、雙酚A、雙酚F、雙 酚S、酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酣S、 酚、鄰甲酚、間甲酚、對甲酚、兒茶酚、α-萘酚、萘 酚、1,5 -二羥基萘、l，6 -二羥基萘、2,6-二羥基萘、二羥基 二苯基酮、三羥基二苯基酮、四羥基二苯基酮、根皮三酚 、三羥基苯、二環戊二烯二酚、酚-酚醛等。活性酯化合 物可使用1種或2種以上。活性酯化合物可使用日本特開 -11 - 201230912 2004-277460號公報所揭示之活性酯化合物，或是市售品 。市售之活性酯化合物，例如，含有二環戊二烯二酚結構 者可列舉出EXB-9451、EXB-9460 ( DIC股份有限公司製） 、酚-酚醛的乙醯化物可列舉出DC808、酚-酚醛的苯甲醯 化物可列舉出YLH 1 026 (三菱化學股份有限公司製）等。 苯並噁嗪系硬化劑的具體例，可列舉出F-a、P-d (四 國化成股份有限公司製）、HFB2006M (昭和高分子股份 有限公司製）等。 (a )環氧樹脂與（b )硬化劑之調配比率，爲酚系硬 化劑或萘酚系硬化劑時，較佳是以環氧樹脂的環氧基數爲 1時之硬化劑的酚性羥基數成爲0.4〜2.0的範圍之比率，尤 佳是成爲0.5〜1.0的範圍之比率。反應基的比率位於此範圍 外時，硬化物的機械強度或耐水性會有降低之傾向。 (c )熱可塑性樹脂，是以對硬化後的組成物賦予適 度的可撓性等爲目的所調配者，例如可列舉出苯氧樹脂、 聚乙烯縮醛樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚 醚颯樹脂、聚颯樹脂等。此等可使用1種或2種以上。該熱 可塑性樹脂，當以硬化性樹脂組成物中的非揮發份爲1 0 0 質量％時，較佳係以〇 . 5〜6 0質量％的比率來調配，尤佳爲 3 ~5 0質量％的比率。當熱可塑性樹脂的調配比率未達0.5質 量％時，由於樹脂組成物的黏度降低，故有難以形成均一 硬化性樹脂組成物層之傾向，超過60質量％時，樹脂組成 物的黏度變得過高，會有不易埋入基板上的配線圖型之傾 向。 -12- 201230912 苯氧樹脂的具體例，例如可列舉出東都化成股份有限 公司製的FX280、FX293、三菱化學股份有限公司製的 YX8100 、 YL6954 、 YL6974 、 YL7213 、 YL6794 、 YL7553 、YL7482等。 聚乙烯縮醛樹脂較佳爲聚乙烯丁醛樹脂，聚乙烯丁醛 樹脂的具體例，例如可列舉出電氣化學工業股份有限公司 製的 Denka Butyral 4000-2、 5000-A、 6000-C、 6000-EP 、 積水化學工業股份有限公司製的S-REC BH系列、BX系列 、KS系列、BL系列、BM系列等。 聚醯亞胺樹脂的具體例，例如可列舉出新日本理化股 份有限公司製的聚醯亞胺「Liquacoat SN20」及「 Liquacoat PN20」。此外，使2官能性羥基墨端的聚丁二烯 、二異氰酸酯化合物及四質子酸酐反應而得之線狀聚醯亞 胺（日本特開2006-37083號公報所記載者），含有聚矽氧 烷骨架之聚醯亞胺（日本特開2002-12667號公報、曰本特 開2000-319386號公報所記載者）等之改質聚醯亞胺。 聚醯胺醯亞胺樹脂的具體例，可列舉出東洋紡績股份 有限公司製的聚醯胺醯亞胺「Vylomax HR11NN」及「 Vylomax HR1 6NN」。此外，可列舉出日立化成工業股份 有限公司製之含有聚矽氧烷骨架之聚醯胺醯亞胺「KS9 100 」、「KS93 00」等之改質聚醯胺醯亞胺。 聚醚颯樹脂的具體例，可列舉出住友化學股份有限公 司製的聚醚颯「PES5003P」等。 聚颯樹脂的具體例，可列舉出solvay Advanced -13- 201230912201230912 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a specific laminate, and further relates to a method for producing a circuit board using the obtained laminate. [Prior Art] The circuit forming method of the core material is a method of reducing the excess metal foil portion of the metal foil laminate, and applying the remaining metal foil portion to directly form a circuit, and removing all the metal foil laminates. A metal foil, and a concavity and convexity from the metal foil formed on the insulating layer is used as a anchor to perform electroless plating, and then a semi-additive method of forming a conductor layer by electrolytic plating (Patent Document 1). However, when irregularities are formed on the surface of the insulating layer, it is difficult to remove the metal in the unevenness by etching to remove the conductor layer and the plating shielding layer which are not required for circuit formation, and on the other hand, under conditions which can be sufficiently removed At the time of etching, the dissolution of the necessary portion of the conductor layer becomes remarkable, and the problem of hindering fine wiring is caused. Further, in Patent Document 1, since the B-stege resin composition sheet is sandwiched, it is disadvantageous in downsizing the substrate. Further, a copper foil laminate using a metal foil with an adhesion aid formed on a metal foil with an adhesion aid layer has been developed (Patent Document 2). However, since the adhesive auxiliary layer is provided, it is disadvantageous for miniaturization of the substrate, and the step of removing the metal foil is also required, and expansion is performed at the interface between the plating interface and the adhesive auxiliary layer after the reliability test, or It is caused by the expansion of the interface between the adhesion aid layer and the prepreg layer, and there is a problem that the reliability is not ensured by -5 to 201230912. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] JP-A-2003-332734 (Patent Document 2) JP-A-2006-2 1 8855 (Summary of the Invention) An object of the invention is to provide a method for producing a laminate which can maintain a glass transition temperature and a tensile modulus while maintaining a glass transition temperature and a tensile modulus while forming a conductive layer having a good peeling strength on the surface of a smooth insulating layer without removing unnecessary steps of removing the metal foil. . (Means for Solving the Problems) The present inventors have intensively studied to solve the above problems, and have found that the above problems can be attained by a specific method for producing a laminate. The features of the present invention are as follows. [1] A method for producing a laminated board, comprising: (A) disposing one or more prepregs between the supports, and curing the prepreg by heating and pressurizing under reduced pressure; a step of forming an insulating layer, (B) a step of removing the support, (C) a step of roughening the surface of the insulating layer', and (D) forming a metal film layer-6 by electroless plating on the surface of the insulating layer. And a glass transition temperature of the insulating layer is 40% by mass or more and 80% by mass or less based on 100% by mass of the non-volatile content in the curable resin composition in the prepreg. 150° C. or more and 270° C. or less, the tensile elastic modulus is 10 GPa or more and 35 GPa or less; and the arithmetic mean roughness of the insulating layer after the step of roughening the surface of the insulating layer (C) is 0.1 nm or more and 600 nm or less. The peeling strength of the insulating layer and the metal film layer after the step of forming the metal film layer on the surface of the insulating layer by electroless plating in the above (D) is 〇45 kgf/cm or more and 10 kgf/cm or less. (2) The method for producing a laminate according to the above [1], wherein the support is a release plastic film. [3] The method for producing a laminate according to the above [1] or [2], wherein the prepreg is [4] The method for producing a laminate according to the above [3], wherein the flaky fiber substrate in the prepreg contains a fiber fiber selected from the group consisting of glass fiber and organic fiber. [5] The method for producing a laminate according to the above [4], wherein the sheet-like fibrous base material is a glass fiber having a thickness of from 1 to 200 μm. [6] The method for producing a laminate according to the above [5], wherein the curable resin composition in the prepreg contains an epoxy resin and a hardener. [7] The method for producing a laminate according to the above [6], wherein the prepreg is The curable resin composition in the material is a naphthalene type epoxy resin and a naphthoquinone type hardener. [2012] [8] The method for producing a laminate according to the above [1] to [7], which is at 150 to 250 ° C, The prepreg is hardened under 60 to 150 minutes to form an insulating layer. [9] Fabrication of laminates according to [1] to [8] above The method further comprising the step of forming a through-hole according to the above [9], wherein the step (B) of forming the through-hole is performed before the step of (b) removing the support. [11] The method for producing a laminate according to the above [1] to [10], further comprising (F) a step of forming a conductor layer by electrolytic plating. [1 2 ] - Multilayer printed wiring substrate A laminate obtained by the production method of the above [j] to [11] is used. [13] A semiconductor device using a laminate obtained by the above-described [丨] to !^" manufacturing method Effect of the Invention: By the method for producing a specific laminate of the present invention, an unnecessary step of removing the metal can be obtained to form a glass transition temperature and a tensile modulus while maintaining a smooth insulating layer. The present invention will be described in detail below with reference to preferred embodiments. The present invention is a method for producing a laminate, which comprises: (A) a support One step or more of prepreg is disposed, and the prepreg is hardened by heat and pressure under decompression -8 - 201230912 to form an insulating layer, (B) the step of removing the support, (C) a step of roughening the surface of the insulating layer, and (D) a step of forming a metal film layer on the surface of the insulating layer by electroless plating. [(A) Step]] <Prepreg Material> Used in the present invention The prepreg is preferably composed of a curable resin composition and a sheet-like fibrous base material, and is obtained by impregnating a sheet-like fibrous base material with a curable resin composition and heating and drying the same. The curable resin composition is not particularly limited and can be used. Among them, a composition containing (a) an epoxy resin is preferable, and a composition containing (a) an epoxy resin, (b) a hardener, and (c) a thermoplastic resin is particularly preferable. (a) The epoxy resin may, for example, be a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a bisphenol F type epoxy resin, or a phosphorus containing ring. Oxygen resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol-phenolic epoxy resin, cresol novolac epoxy resin, bisphenol A phenolic epoxy resin An epoxy resin having a butadiene structure, a diglycidyl ether compound of bisphenol, a diglycidyl ether compound of naphthalenediol, a glycidyl ether compound of a phenol, and a diglycidyl ether of an alcohol, and the like An alkyl group, an halide, a hydrogenated product, or the like of an epoxy resin. These may be used alone or in combination of two or more. Among them, in terms of heat resistance improvement, insulation reliability improvement, and adhesion of metal film -9-201230912, it is preferable to be bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type. Epoxy resin, biphenyl type epoxy resin, epoxy resin having a dibutyl structure, and preferably a naphthalene type epoxy resin. Specific examples include a liquid bisphenol A type epoxy resin ("Epikote 828EL" manufactured by Mitsubishi Chemical Corporation) and a naphthalene type bifunctional epoxy resin (HP4032" and "HP4032D" manufactured by DIC Corporation. ), a naphthalene type tetrafunctional epoxy resin ("HP4700" manufactured by DIC Corporation), a naphthol type epoxy resin ("ESN-475V" manufactured by Tohto Kasei Co., Ltd.), and an epoxy resin having a butadiene structure ( "PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), epoxy resin having a biphenyl structure ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., "NC3000L", "YX4000" manufactured by Mitsubishi Chemical Corporation). (b) The curing agent' is, for example, an amine-based curing agent, an oxime-based curing agent, an imidazole-based curing agent, a phenol-based curing agent containing a triazine skeleton, a phenol-based curing agent, and a naphthol-based curing agent containing a triazine skeleton. A naphthol-based curing agent, an acid anhydride-based curing agent, or an epoxy-addition or microencapsulation, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate resin, or the like. From the viewpoint of improving the peel strength of plating, the hardener is preferably a nitrogen atom in a molecular structure, and among them, a phenolic hardener containing a triazine skeleton and a naphthol hardener containing a triazine skeleton are preferable. Particularly preferred is a phenol-phenolic resin containing a triazine skeleton. From the viewpoint of improvement in heat resistance, improvement in insulation reliability, and improvement in adhesion to a metal film, a naphthol-based curing agent is preferred. These may be used alone or in combination of two or more. Specific examples of the phenolic curing agent and the naphthol-based curing agent include, for example, -10-201230912 MEH-7700, MEH-7810, MEH-7851 (made by Minghe Chemical Co., Ltd.), bismuth, CBN, and GPH (Japanese). Pharmaceutical Co., Ltd.) 'SN170, SN180, SN190, SN475, SN48 5, SN495, SN3 75, SN3 95 (manufactured by Tohto Kasei Co., Ltd.), TD2090 (manufactured by D 1C Co., Ltd.), etc. Specific examples of the phenolic curing agent containing a triazine skeleton include LA3018 (manufactured by DIC Corporation). Specific examples of the phenol-phenolic curing agent containing a triazine skeleton include LA7052, LA7054, and LA1356 (manufactured by DIC Corporation). As the active ester-based curing agent, two or more ester groups having high reactivity in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, can be suitably used. Compound. The active ester compound is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound. Particularly, from the viewpoint of heat resistance and the like, an active ester compound obtained from a carboxylic acid compound and a phenol compound or an naphthol compound is preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyrogolite. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methyl group. Bismuth S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6 - Dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, cadaverin, trihydroxybenzene, dicyclopentadiene diol, phenol-phenolic aldehyde, and the like. One or two or more kinds of the active ester compounds can be used. As the active ester compound, an active ester compound disclosed in JP-A-11-201230912, 2004-277460, or a commercially available product can be used. Commercially available active ester compounds, for example, those having a structure of dicyclopentadiene diphenol, EXB-9451, EXB-9460 (manufactured by DIC Corporation), and acetonitrile of phenol-phenolic aldehydes include DC808 and phenol. The benzyl hydrazide of the phenolic aldehyde is YLH 1 026 (made by Mitsubishi Chemical Corporation). Specific examples of the benzoxazine-based curing agent include F-a, P-d (manufactured by Shikoku Chemicals Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), and the like. When the ratio of the epoxy resin to the curing agent (b) is a phenolic curing agent or a naphthol-based curing agent, the phenolic hydroxyl group of the curing agent when the epoxy group has an epoxy group number of 1 is preferably used. The ratio of the number to the range of 0.4 to 2.0 is particularly preferably a ratio of a range of 0.5 to 1.0. When the ratio of the reactive group is outside this range, the mechanical strength or water resistance of the cured product tends to decrease. (c) The thermoplastic resin is formulated for the purpose of imparting appropriate flexibility to the cured composition, and examples thereof include a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, and a polyfluorene. Amine amide resin, polyether oxime resin, polyfluorene resin, and the like. These may be used alone or in combination of two or more. When the non-volatile content in the curable resin composition is 100% by mass, the thermoplastic resin is preferably blended at a ratio of 5 to 60% by mass, particularly preferably 3 to 50% by mass. %The ratio. When the blending ratio of the thermoplastic resin is less than 0.5% by mass, the viscosity of the resin composition is lowered, so that it is difficult to form a uniform curable resin composition layer. When the content exceeds 60% by mass, the viscosity of the resin composition becomes excessive. High, there is a tendency to be difficult to embed the wiring pattern on the substrate. -12- 201230912 Specific examples of the phenoxy resin include FX280, FX293 manufactured by Dongdu Chemical Co., Ltd., YX8100, YL6954, YL6974, YL7213, YL6794, YL7553, and YL7482 manufactured by Mitsubishi Chemical Corporation. The polyvinyl acetal resin is preferably a polyvinyl butyral resin, and a specific example of the polyvinyl butyral resin is, for example, Denka Butyral 4000-2, 5000-A, 6000-C, 6000 manufactured by Denki Kogyo Co., Ltd. -EP, S-REC BH series, BX series, KS series, BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd. Specific examples of the polyimine resin include, for example, polyimine "Liquacoat SN20" and "Liquacoat PN20" manufactured by Shin Nippon Chemical Co., Ltd. Further, a linear polyimine obtained by reacting a polybutadiene having a bifunctional hydroxyl ink end, a diisocyanate compound, and a tetraprotic acid anhydride (described in JP-A-2006-37083) contains polyoxyalkylene oxide. A modified polyimine such as a polyimine of the skeleton (described in JP-A-2002-12667, JP-A-2000-319386). Specific examples of the polyamidoximine resin include polyacrylamide imine "Vylomax HR11NN" and "Vylomax HR1 6NN" manufactured by Toyobo Co., Ltd. In addition, modified polyamidoquinone imines such as polyacrylamide skeletons "KS9 100" and "KS93 00" manufactured by Hitachi Chemical Co., Ltd. can be cited. Specific examples of the polyether oxime resin include polyether oxime "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of polyanthracene resins include solvay Advanced -13- 201230912

Polymers股份有限公司製的聚颯「P1700」' 「P3500」等 〇 該硬化性樹脂組成物中，就有效率地使環氧樹脂與硬 化劑硬化之觀點來看，可進一步含有（d )硬化促進劑。 此般硬化促進劑，可列舉出咪唑化合物、吡啶化合物、有 機膦系化合物等，該具體例，例如可列舉出2-甲基咪唑、 4-二甲基咪唑、三苯基膦等。此等可使用1種或2種以上》 使用（d )硬化促進劑時，相對於環氧樹脂，較佳是在 0.1〜3.0質量％的範圍來使用。 該硬化性樹脂組成物中，就降低絕緣層的熱膨脹率之 觀點來看，可進一步含有（e)無機塡充材。無機塡充材 ，例如可列舉出二氧化矽、氧化鋁、雲母、純雲母、矽酸 鹽、硫酸鋇、氫氧化鎂、氧化鈦等，較佳爲二氧化矽、氧 化鋁，特佳爲非定形二氧化矽、熔融二氧化矽、結晶二氧 化矽、合成二氧化矽、中空二氧化矽等之二氧化矽。二氧 化矽較佳爲球狀，此等可使用1種或2種以上。就降低介電 常數、介電正切、熱膨脹率之觀點來看，較佳爲使用中空 二氧化矽。中空二氧化矽是由殼部及中空部所構成，平均 空隙率較佳爲30〜80體積％。 無機塡充材之平均粒徑的上限，就提升絕緣可靠度之 觀點來看，較佳爲5μιη以下，尤佳爲4μηι以下，更佳爲3μπι 以下，又更佳爲2μηα以下，極佳爲1 ·5μιη以下，特佳爲1 μη1 以下，最佳爲〇.5μπι以下。另一方面’無機塡充材之平均 粒徑的下限，就提升分散性之觀點來看，較佳爲〇.〇1 μπι以 -14- 201230912 上’尤佳爲0·05μιη以上，更佳爲0.1μιη以上。無機塡充材 的平均粒徑’可藉由依據米氏（Mie )散射理論之雷射繞 射散射法來測定。具體而言，可藉由雷射繞射式粒度分布 測定裝置’以體積基準製作出無機塡充材的粒度分布，並 以該中位徑作爲平均粒徑來測得。測定樣本，可適當地使 用以超音波使無機塡充材在水中分散者。雷射繞射式粒度 分布測定裝置，可使用堀場製作所股份有限公司製的LA-5 00 等。 硬化性樹脂組成物中之無機塡充材的含量上限値，就 防止硬化物的機械強度降低之觀點、提升加工性之觀點、 提升電鍍密著性之觀點來看，當以硬化性樹脂組成物中的 非揮發份爲100質量°/。時，較佳爲80質量％以下，尤佳爲75 質量％以下，更佳爲70質量％以下，又更佳爲65質量％以下 。另一方面，硬化性樹脂組成物中之無機塡充材的含量下 限値，就降低熱膨脹率之觀點、將剛性賦予至預浸材之觀 點來看，當以硬化性樹脂組成物中的非揮發份爲1 〇〇質量％ 時，較佳爲40質量％以上。 無機塡充材，爲了提升耐濕性、分散性等，較佳是經 由下列表面處理劑進行處理者’亦即胺丙基甲氧矽烷、胺 丙基三乙氧矽烷、脲丙基三乙氧矽烷、N-苯基胺丙基三甲 氧矽烷、N-2 (胺乙基）胺丙基三甲氧矽烷等之胺矽烷系 偶合劑；環氧丙氧基丙基三甲氧矽烷、環氧丙氧基丙基三 乙氧矽烷、環氧丙氧基丙基甲基二乙氧矽烷、縮水甘油基 丁基三甲氧矽烷、（3,4-環氧環己基）乙基三甲氧矽烷等 -15- 201230912 之環氧矽烷系偶合劑；毓丙基三甲氧矽烷、锍丙基三乙氧 矽烷等之锍基矽烷系偶合劑；甲基三甲氧矽烷、十八烷基 三甲氧矽烷、苯基三甲氧矽烷、甲基丙烯氧基丙基三甲氧 矽烷、咪唑矽烷、三嗪矽烷等之矽烷系偶合劑；六甲基二 矽氮烷、六苯基二矽氮烷、二甲基胺基三甲氧矽烷、三矽 氮烷、環三矽氮烷、1，1，3,3,5,5-六甲基環三矽氮烷等之有 機矽氮烷化合物；丁基鈦酸酯二聚物、鈦酸辛二醇酯、雙 (三乙醇胺）鈦酸二異丙氧酯、雙乳酸鈦酸二羥酯、雙（ 乳酸銨）鈦酸二羥酯、雙（二辛基焦磷酸）鈦酸乙烯酯、 雙（二辛基焦磷酸）鈦酸氧基乙酸酯、單硬脂酸鈦酸三正 丁氧酯、鈦酸四正丁酯、鈦酸四（2-己基己基）酯、雙（ 二辛基亞膦酸）鈦酸四異丙酯、雙（二（十二烷基）亞膦 酸）鈦酸四辛酯、雙（二（十三烷基））亞膦酸鈦酸四（ 2，2·二烯丙基氧基甲基-1-丁基）酯、鈦酸異丙基三辛醯酯 、鈦酸異丙基三異丙苯基苯酯、鈦酸異丙基三異硬脂醯酯 、鈦酸異丙基異硬脂醯基二丙烯酸酯、鈦酸異丙基二甲基 丙烯酸異硬脂醯酯、鈦酸異丙基三（二辛基亞膦酸）酯、 鈦酸異丙基三（十二烷基）苯磺醯酯、鈦酸異丙基三（二 辛基焦磷酸）酯、鈦酸異丙基三（N-醯胺乙基/胺乙基） 酯的鈦酸酯系偶合劑等。此等可使用1種或2種以上。 該硬化性樹脂組成物中，亦可因應必要，在發揮本發 明之效果的範圍內調配雙馬來醯亞胺-三嗪樹脂、丙烯酸 樹脂、馬來醯亞胺化合物、雙烯丙基奈二醯亞胺化合物、 乙烯基苄樹脂、乙烯基苄醚樹脂、嵌段異氰酸酯化合物等 -16- 201230912 之環氧樹脂以外的熱硬化性樹脂。此等可使用1種或2種以 上。馬來醯亞胺可列舉出BMI1000、BMI2000、BMI3000 、BMI40 00、BMI5 000 (大和化成工業股份有限公司製） 、：BMI、BMI-70、BMI-80 ( KI化成股份有限公司製）、 ANILIX-MI( Mitsui Fine Chemicals 股份有限公司製）， 雙烯丙基奈二醯亞胺化合物可列舉出BANI-M、BANI-X ( 九善石油化學工業股份有限公司製）’乙烯基苄樹脂可列 舉出V5000 (昭和高分子股份有限公司製），乙烯基苄醚 樹脂可列舉出V1000X、V1100X (昭和高分子股份有限公 司製）等。 該硬化性樹脂組成物中，亦可因應必要，在發揮本發 明之效果的範圍內含有難燃劑。難燃劑例如可列舉出有機 磷系難燃劑、有機系之含氮的磷化合物、氮化合物、聚矽 氧烷系難燃劑、金屬羥化物等。有機磷系難燃劑可列舉出 三光股份有限公司製的HCA、HCA-HQ、HCA-NQ等之膦化 合物；昭和高分子股份有限公司製的HFB_2〇〇6M等之含磷 的苯並噁嗪化合物；Ajinomoto Fine Techno股份有限公司 製的 REOFOS 30、50、65、90、1 1 0、TPP、RPD、BAPP、 CPD ' TCP ' TXP、TBP、TOP、KP140、TIBP、北興化學 工業股份有限公司製的ppQ、Clariant股份有限公司製的 OP9 3 0、大八化學股份有限公司製的PX200等之磷酸酯化 合物；東都化成股份有限公司製的FX2 89、FX3 10等之含 磷的環氧化合物；東都化成股份有限公司製的ERF00 1等之 含磷的苯氧樹脂等。有機系之含氮的磷化合物可列舉出四 -17- 201230912 國化成股份有限公司製的SP670、SP703等之磷酸酯醯胺化 合物；大塚化學股份有限公司製的SPB100、SPE1〇〇等之 磷氮烯化合物等。金屬羥化物可列舉出Ube Materials股份 有限公司製的UD65、UD650、UD653等之氫氧化鎂、巴工 業股份有限公司製的 B·30、 B_325、 B_315、 B·308、 B-303 、UFH-20等之氫氧化鋁等。此等可使用1種或2種以上。 硬化性樹脂組成物中’亦可因應必要，在發揮本發明 之效果的範圍內，就提高硬化物機械強度的提高、應力緩 和效果等目的，可含有固體狀橡膠粒子。固體狀橡膠粒子 ，較佳是不會溶解於調製樹脂組成物時的有機溶劑，且不 會與環氧樹脂等之樹脂組成物中的成分相溶，並且在樹脂 組成物的清漆中以分散狀態所存在。此般橡膠粒子，一般 是將橡膠成分的分子量增大至不會溶解於有機溶劑或樹脂 之程度，並構成爲粒子狀來調製。橡膠粒子，例如可列舉 出核殼型橡膠粒子、交聯丙烯腈丁二烯橡膠粒子、交聯苯 乙烯丁二烯橡膠粒子、丙烯酸橡膠粒子等。核殼型橡膠粒 子，爲粒子具有核層與殼層之橡膠粒子，例如可列舉出外 層的殼層由玻璃狀聚合物，內層的核層由橡膠狀聚合物所 構成之雙層結構，或是外層的殼層由玻璃狀聚合物，中間 層由橡膠狀聚合物，核層由玻璃狀聚合物所構成之三層結 構者等。玻璃狀聚合物例如由甲基丙烯酸甲酯之聚合物等 所構成，橡膠狀聚合物例如由甲基丙烯酸丁酯聚合物（丁 基橡膠）等所構成。核殻型橡膠粒子的具體例，可列舉出 Stafiloid AC3 832、AC3 8 1 6N ( Ganz化成股份有限公司的 -18- 201230912 商品名稱）、Metablen KW-4426 ( Mitsubishi Rayon 股份 有限公司的商品名稱）。丙烯腈丁二烯橡膠（NBR)粒子 的具體例，可列舉出XER-91 (平均粒徑0·5μιη ) 、JSR股 份有限公司製）等苯乙烯丁二烯橡膠（SBR )粒子的具體 例，可列舉出XSK-500 (平均粒徑〇.5μιη，JSR股份有限公 司製）。丙烯酸橡膠粒子的具體例，可列舉出Metablen W300A (平均粒徑 Ο.ίμιη) 、W4 50A (平均粒徑 0·5μιη) (Mitsubishi Rayon股份有限公司製）等。 硬化性樹脂組成物中，可因應必要調配其他成分。其 他成分例如可列舉出聚矽氧烷粉末、尼龍粉末、氟粉末等 之塡充劑；有機皂土、皂土等之增黏劑；聚矽氧烷系、氟 系、高分子系的消泡劑或平坦化劑、咪唑系、噻唑系、三 唑系、矽烷系偶合劑等之密著性賦予劑；酞菁藍、酞菁綠 、碘綠、雙偶氮黃、碳黑等之著色劑等。 預浸材中所使用之薄片狀纖維基材，可使用選自玻璃 纖維、有機纖維、玻璃不織布、有機不織布之1種或2種以 上。當中較佳可使用玻璃織物、醯胺不織布、液晶聚合物 不織布等之薄片狀纖維基材，尤佳爲玻璃織物。薄片狀纖 維基材的厚度較佳爲1〜200μιη，尤佳爲5〜175μιη，更佳爲 10〜150μπι，又更佳爲20~125μιη，極佳爲30~100μηι。薄片 狀纖維基材的具體例，玻璃織物可列舉出Asahi Schwebel 股份有限公司製的Style 1 027MS (經線密度75根/25mm、 緯線密度75根/ 25mm、布重量20g/m2、厚度19μη〇 、Asahi Schwebel股份有限公司製的Style 1 03 7MS (經線密度70根 -19- 201230912 /25mm、緯線密度73根/25mm、布重量24g/m2、厚度28μιη )、有澤製作所股份有限公司製的1 0 7 8 (經線密度54根 /25mm、緯線密度54根/25mm、布重量48g/m2、厚度43μιη )、有澤製作所股份有限公司製的2 1 1 6 (經線密度50根 /25mm、緯線密度58根/25mm、布重量103.8g/m2、厚度 9 4μηι)等》此外，液晶聚合物不織布，可列舉出以方式從 Kuraray股份有限公司製的聚芳酯系液晶聚合物所製造之 不織布的Vecls (單位面積重量6〜15 g/m2)或以Kuraray股 份有限公司製的Vectoron作爲纖維原材之不織布等。 本發明中所使用之預浸材的製造方法並無特別限制， 較佳爲以下的方法。 預浸材可藉由一般所知的熱熔法、溶劑法等來製造。 熱熔法，係不需將樹脂組成物溶解於有機溶劑，先塗佈於 與樹脂組成物之剝離性佳之脫模紙上’然後將此疊合於或 是藉由壓模塗佈直接塗佈於薄片狀纖維基材等，來製造出 預浸材之方法。此外，溶劑法’係藉由將薄片狀纖維基材 浸漬於使樹脂組成物溶解於有機溶劑之樹脂組成物清漆中 ，而將樹脂組成物清漆含浸於薄片狀纖維基材’然後進行 乾燥之方法。此外，亦可將由層合於支撐體上之硬化性樹 脂組成物所構成之黏著膜，在加熱及加壓條件下’從薄片 狀補強基材的雙面連續地進行熱疊合而調製出。 調製清漆時之有機溶劑’例如可列舉出丙酮、丁酮、 環己酮等之酮類；乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、 丙二醇單甲醚乙酸酯、卡必醇乙酸酯等之乙酸酯類：溶纖 -20- 201230912 劑、丁基卡必醇等之卡必醇類；甲苯、二甲苯等之芳香族 烴類；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等 。此等可使用1種或2種以上。 清漆的乾燥條件並無特別限制，在模壓步驟中，硬化 性樹脂組成物必須具有流動性（Flow )及黏著性。另一方 面，當預浸材中殘留較多有機溶劑時，乃成爲硬化後產生 膨脹之原因。因此，有機溶劑於硬化性樹脂組成物之含有 比率較佳係設爲5質量％以下，尤佳爲2質量％以下。具體 的乾燥條件，雖因硬化性樹脂組成物的硬化性或清漆中的 有機溶劑量而有所不同，但在含有30〜60質量％的有機溶劑 之清漆中，較佳是在80〜180 °C下進行3〜13分鐘的乾燥。可 藉由簡單實驗來適當地設定較佳乾燥條件。 預浸材的厚度，就薄片狀纖維基材的成本及預浸材的 期望剛性之觀點來看，較佳位於20〜250μιη的範圍內’尤佳 爲40〜180μιη的範圍內，更佳爲60〜150μιη的範圍內。預浸 材的厚度，可藉由調整硬化性樹脂組成物的含浸量來控制 。此外，由於預浸材必須具有可在模壓下不會產生縫隙而 層合之流動性，所以預浸材中的硬化性樹脂組成物’該最 低熔融黏度較佳位於200〜3 0000P〇ise的範圍內’尤佳爲 1 000~20000poise 的範圍內。 <支撐體> 本發明之方法中，由於使用支撐體取代金屬箔並使預 浸材硬化，所以不需進行去除金屬箔之多餘步驟’而具有 -21 - 201230912 層合板的生產性佳，就環境面而言亦可減少廢液之優點， 且進一步具有與金屬箔相比爲低成本且容易去除之優點。 本發明中所使用之支撐體，爲具有自支撐性之膜，可適當 地使用塑膠膜。塑膠膜可列舉出聚對苯二甲酸乙二酯、聚 萘二甲酸乙二酯、聚醯亞胺、聚醯胺醯亞胺、聚醯胺、聚 四氟乙烯、聚碳酸酯等，較佳爲聚對苯二甲酸乙二酯膜、 聚萘二甲酸乙二酯膜，就便宜之觀點來看，尤佳爲聚對苯 二甲酸乙二酯膜。此外，以提升硬化後的剝離性者爲目的 ，塑膠膜較佳爲施以粗糙處理、電暈處理等表面處理後之 脫模塑膠膜，或是於支撐體表面存在有聚矽氧烷樹脂、醇 酸樹脂、氟樹脂等之其他脫模層之脫模塑膠膜。此外，亦 可對支撐體的表面施以表面處理。與預浸材接觸之該側的 支撐體表面，就與預浸材接觸時平滑地保持預浸材表面之 觀點來看，算術平均粗糙度（Ra値）較佳爲50nm以下，尤 佳爲40nm以下，更佳爲35nm以下，又更佳爲30nm以下， 極佳爲25nm以下。算術平均粗糙度（Ra値）的下限値並無 特別限定，就支撐體的實用性之觀點來看，較佳爲0.1 nm 以上，尤佳爲〇 . 5 n m以上。算術平均粗糙度（R a値）的測 定可使用一般所知的方法，例如可使用非接觸型表面粗糙 度儀（例如 Veeco Instruments 公司製的 WYKO NT3300 等） 等裝置來測定。支撐體亦可使用市售品，例如可列舉出 T60(Toray股份有限公司製、聚對苯二甲酸乙二酯膜）、 A4100(東洋紡績股份有限公司製、聚對苯二甲酸乙二酯 膜）、Q83( Teijin DuPont股份有限公司製、聚萘二甲酸 -22- 201230912 乙二酯膜）、Lintec股份有限公司製之附有醇酸型脫模劑 (AL-5 )的聚對苯二甲酸乙二酯膜、Diafoil B 1 000 ( Mitsubishi Chemical Polyester Film股份有限公司製'聚對苯 二甲酸乙二酯膜）等。 支撐體的厚度較佳爲1〇~70μηι，尤佳爲15~70μιη。厚 度過小時，處理性有惡化之傾向或支撐體層的剝離性有降 低之傾向。此外，厚度過大時，成本效益有惡化之傾向。 <使預浸材硬化而形成絕緣層> (Α)步驟中，係於支撐體之間配置1片以上的預浸材 ，並藉由在減壓下進行加熱及加壓使預浸材硬化而形成絕 緣層。當使用2片以上的預浸材時，可使用相同預浸材或 不同預浸材。使用不同預浸材時，可使用硬化性樹脂組成 物的組成、薄片狀纖維基材的材料、薄片狀纖維基材的厚 度等之中的一項或全部互爲不同者。本發明之絕緣層，可 不設置黏著劑層而直接用在層合板的製造。 此外，就作業性之觀點來看，亦可使用將預浸材貼合 於支撐體表面之附有支撐體的預浸材。支撐體與預浸材之 貼合，可藉由模壓、分批式疊合機、輥式疊合機等來進行 加熱及壓著而進行。加熱溫度，就支撐體與預浸材之黏著 性之觀點來看，較佳爲60〜140°C，尤佳爲70〜130°C。壓著 的壓力，使用分批式疊合機時，較佳位於1〜1 lkgf/cm2 ( 9.8xl04〜107.9xl04N/m2)的範圍內，尤佳爲 2〜7kgf/cm2( 19.6xl04〜68.6xl04N/m2)的範圍內。壓著時間，較佳位於 -23- 201230912 5秒~3分鐘的範圍內。使用輥式疊合機時，線壓較佳位於 l~15kgf/cm的範圍內，尤佳爲l~l〇kgf/cm的範圍內。壓力 過小時，樹脂組成物的流動性不足，與支撐體之密著性有 降低之傾向。壓力過大時，由於樹脂的滲出而有難以維持 膜厚之傾向。真空疊合機可使用市售的真空疊合機》市售 的真空疊合機，例如可列舉出名機製作所股份有限公司製 的分批式真空加壓疊合機MVLP-500、Nichigo Morton股份 有限公司製的真空濕膜塗佈機、Hitachi Industries股份有 限公司製的輥式乾式塗佈機、Hitachi AIC股份有限公司製 的真空疊合機等。 使用附有支撐體的預浸材時，係使預浸材層面相對向 重疊，或將其他的1片以上預浸材配置在附有支撐體的預 浸材之2片預浸材層間並重疊後，在減壓下進行加熱及加 壓使預浸材硬化而形成絕緣層。如上述所說明般，所插入 之預浸材’可與用作爲附有支撐體的預浸材之預浸材層的 預浸材爲相同或不同者。 藉由在減壓下進行加熱及加壓使預浸材硬化而形成絕 緣層之步驟’可使用真空熱模壓機來進行。例如可藉由從 支擦體側的兩面對加熱後的S U S板等金屬板進行模壓來進 行。 模壓條件，較佳是在1 x 1 〇·2 MPa以下的減壓下進行。 加熱及加壓可於1階段中進行。就控制樹脂的滲出之觀點 來看’較佳係將條件分爲2階段以上來進行。第1階段的模 壓’較佳是在溫度70。(：~150。(：、壓力1〜15 kgf/cm2的範圍 -24- 201230912 內、時間爲15〜45分鐘的範圍內進行。第2階段的模壓，較 佳是在溫度15〇C〜250 °C、壓力1〜140kgf/cm2的範圍內、 時間爲60~ 150分鐘的範圍內進行，尤佳是在溫度160 °C ~240 °C、壓力1〜40kgf/Cm2的範圍內、時間爲75〜130分鐘 的範圍內進行。 市售的真空熱模壓機，例如可列舉出MNPC-V-750-5 -200 (名機製作所股份有限公司製）、VH1-1603 (北川精 機股份有限公司製）等。 絕緣層之玻璃轉移溫度的下限値，就防止貫通孔端部 的龜裂，提升樹脂組成物與導體層之間的密著可靠度，降 低高溫時的翹曲以提升晶片的構裝性之觀點來看，較佳爲 1 5 0 °C以上，尤佳爲1 5 5 °C以上。此外，絕緣層之玻璃轉移 溫度的上限値，就愈高愈佳之觀點來看，較佳爲1 75 °C以 下，尤佳爲180 °C以下，更佳爲190 °C以下，又更佳爲200 °C以下，極佳爲2 3 0 °C以下，特佳爲2 5 0 t以下，最佳爲 2 7 0 °C以下。 '絕緣層的拉伸彈性率，就確保電子零件構裝時的剛性 之觀點’以及低翹曲及提升製品的耐衝擊性之觀點來看， 較佳爲lOGPa以上，尤佳爲15GPa以上。此外，絕緣層的 拉伸彈性率，就愈高愈佳之觀點來看，尤佳爲25GPa以下 ’更佳爲30GPa以下，又更佳爲35GPa以下。 [(B )步驟] (B)去除支撐體之步驟，一般是藉由手動或自動剝 -25- 201230912 離裝置來機械地剝離所進行。支撐體，較佳是在使預浸材 硬化而形成絕緣層後再剝離。當進行後述（E )形成貫通 孔之步驟時，可在（B)去除支撐體之步驟之前或之後進 行（E )形成貫通孔之步驟，就貫通孔形成時可保護絕緣 層之觀點來看，較佳是在（B)去除支撐體之步驟之前進 行（.E)形成貫通孔之步驟。 [(C)步驟] (C)步驟可使用電漿等之乾式法、依據鹼性過錳酸 溶液等之氧化劑處理所進行之濕式法等之一般所知的方法 。尤其是依據氧化劑所進行之去膠渣，就可使絕緣層表面 粗化並提升電鍍密著強度之觀點來看爲較佳。當藉由氧化 劑來進行（C )步驟時，較佳是依此順序進行依據膨潤液 的膨潤處理、依據氧化劑的粗化處理、以及依據中和劑的 中和處理。膨潤液並無特別限制，可列舉出鹼溶液、界面 活性劑溶液等，較佳爲鹼溶液，該鹼溶液尤佳爲氫氧化鈉 溶液、氫氧化鉀溶液。市售的膨潤液，例如可列舉出 Atotech Japan股份有限公司製的 Swelling Dip Securiganth P、Swelling Dip Securiganth SBU等。依據膨潤液的膨潤 處理並無特別限制，具體而言，可使3 0〜90 °C的膨潤液附 著1分鐘〜1 5分鐘。就作業性以及不會使樹脂過度膨潤之觀 點來看’較佳爲浸漬在4 0〜8 0 °C的膨潤液5秒〜1 0分鐘之方 法。氧化劑並無特別限制，例如可列舉出將過錳酸鉀或過 錳酸鈉溶解於氫氧化鈉水溶液之鹼性過錳酸溶液。依據鹼 -26- 201230912 性過錳酸溶液等的氧化劑所進行之粗化處理，較佳係在加 熱至60~8(TC之氧化劑溶液中浸漬10分鐘〜30分鐘。此外， 鹼性過錳酸溶液中性過錳酸鹽的濃度，較佳係設爲5~10質 量％。市售的氧化劑，例如可列舉出Atotech Japan股份有 限公司製的 Concentrate Compact CP、Dosing Solution Securiganth P等之鹼性過錳酸溶液。此外，中和劑較佳爲 酸性的水溶液，市售品可列舉出Atotech Japan股份有限公 司製的 Reduction Solution Securiganth P (中和液）。依 據中和劑的中和處理，可使用使3 0〜8 0 °C的中和液附著於 依據氧化劑溶液進行粗化處理後之處理面5分鐘〜30分鐘之 方法。就作業性等觀點來看，較佳係將依據氧化劑溶液進 行粗化處理後之對象物浸漬在40〜7 0°C的中和液5分鐘〜20 分鐘之方法。（C)步驟，就可去除由（E)形成貫通孔之 步驟所產生之壁面殘渣，且可進行壁面的粗化處理之觀點 來看，較佳是在（E)形成貫通孔之步驟之後進行。 該（C)步驟後的絕緣層之算術平均粗糙度（Ra値） 的上限値，就可在高平滑性下形成更細微的配線之觀點來 看，較佳爲600nm以下，尤佳爲570nm以下，更佳爲540nm 以下，又更佳爲510nm以下，極佳爲480nm以下，特佳爲 45 〇nm以下。另一方面，絕緣層之算術平均粗糙度（Ra値 )的下限値，就可得高剝離強度之觀點來看，較佳爲 Ο-lnm以上，尤佳爲〇.5nm以上，更佳爲lnm以上，又更佳 爲10nm以上，極佳爲50nm以上，特佳爲100nm以上。 201230912 [(D)步驟] (D) 藉由無電解電鍍於絕緣層表面上形成金屬膜層 之步驟，可藉由一般所知的方法來進行，例如以界面活性 劑等對絕緣層表面進行處理，賦予鈀等之電鍍觸媒後含浸 於無電解電鎪液來形成金屬膜。可列舉出銅、鎳、金、鈀 等，當中較佳爲銅。金屬膜層的厚度，就可充分地被覆樹 脂表面以及成本效益之觀點來看，較佳爲0.1〜5.0 μηι，尤 佳爲0.2〜2·5μηι，更佳爲〇·2~1·5μηι。金屬膜層，亦可藉由 一種無電解電鍍之直接電鍍法來形成》 該（D)步驟後之絕緣層與金屬膜層之剝離強度的上 限値’就愈筒愈佳之觀點來看，較佳爲〇.8kgf/cm以下，尤 佳爲lkgf/cm以下，更佳爲3kgf/cm以下，又更佳爲5kgf/cm 以下，極佳爲10kgf/Cm以下。另一方面，絕緣層與金屬膜 層之剝離強度的下限値，就保持絕緣可靠度之觀點來看， 較佳爲0.45kgf/cm以上。 [(E )步驟] 本發明之方法中，可進一步進行（E)形成貫通孔之 &驟。（E )步驟只要可達目的者，則無特別限制，可藉 由一般所知的方法來形成貫通孔，可使用機械鑽頭，或是 碳酸氣體雷射、YAG雷射等之雷射。 (E) 形成貫通孔之步驟，就貫通孔形成時可保護絕 緣層表面之觀點來看，較佳是在（B)去除支撐體之步驟 前進行。此外，就防止絕緣層表面粗化之觀點來看，較佳 -28- 201230912 是在（D)藉由無電解電鍍於絕緣層表面上形成金屬膜層 之步驟後進行。當藉由雷射從支撐體上形成貫通孔時’爲 了提升雷射加工性，可於支撐體中含有雷射吸收性成分。 雷射吸收性成分，可列舉出金屬化合物粉、碳粉、金屬粉 、黑色染料等。雷射能量吸收性成分的調配量，在構成含 有該成分之層的全部成分中，較佳爲〇.〇5〜40質量％，尤佳 爲0 · 1〜2 0質量％，更佳爲1〜1 0質量％。碳粉可列舉出爐黑 、槽法碳黑、乙炔黑、熱黑、蒽黑等之碳黑粉末、石墨粉 末、或此等之混合物的粉末等。金屬化合物粉可列舉出氧 化鈦等之鈦石類、氧化鎂等之鎂石類、氧化鐵等之鐵氧化 物、氧化鎳等之鎳氧化物、二氧化錳、氧化鋅等之鋅氧化 物、二氧化矽、氧化鋁、稀土類氧化物、氧化鈷等之鈷氧 化物、氧化錫等之錫氧化物、氧化鎢等之鎢氧化物、碳化 砂、碳化鎢、氮化硼、氮化砂、氮化鈦、氮化銘、硫酸鋇 、稀土類硫氧化物、或此等之混合物的粉末等。金屬粉可 列舉出銀、銘、祕、銘、銅、鐵、鎂、猛、鉬、鎳、祀、 録、砂、錫、鈦、銳、鶴、鋅、或此等之合金或混合物的 粉末等。黑色染料可列舉出偶氮（單偶氮、雙偶氮）染料 、偶氮-次甲基染料、蒽醌染料、喹啉染料、酮亞胺染料 、營光酮染料、硝基染料、氧雜蔥染料、苊染料、喹淋黃 染料、胺基酮染料、次甲基染料、茈染料、香豆素染料、 芘酮染料、三苯基染料、三烯丙甲烷染料、酞菁染料、 inklophenol染料、二氮陸圜染料、或此等之混合物等。黑 色染料，爲了提升於水溶性樹脂中的分散性，較佳爲溶劑 -29- 201230912 可溶性的黑色染料。此等可使用1種或2種以上。雷射能量 吸收性成分，就雷射能量往熱能之轉換效率或泛用性等觀 點來看，較佳爲碳粉，特佳爲碳黑。 [(F )步驟] 本發明之方法中，可進一步進行（F)藉由電解電鎪 以形成導體層之步驟。較佳在（D )藉由無電解電鍍於絕 緣層表面上形成金屬膜層之步驟後，應用該金屬膜層來進 行（F)藉由電解電鍍以形成導體層之步驟。該導體層的 形成，可藉由半加成法等之一般所知的方法來進行。例如 ，形成電鍍抗蝕層，並以（D)步驟中所形成之金屬膜層 作爲電鎪遮蔽層，然後藉由電解電鍍來形成導體層。以電 解電鍍所形成之導體層，較佳爲銅。該厚度雖因期望之電 路基板的設計而有所不同，但較佳爲3〜35μηΊ，尤佳爲 5〜3 0 μ m。電解電鍍後，以鹼性水溶液等之電鍍抗蝕層剝離 液來去除電鍍抗蝕層，然後亦去除電鍍遮蔽層而形成配線 圖型。電鍍遮蔽層的去除方法，可使用蝕刻液，例如爲銅 時，可使用氯化鐵水溶液、過氧二硫酸鈉與硫酸之水溶液 等之酸性蝕刻液、Mec股份有限公司製的CF-6000、Meltex 股份有限公司製的E-Process-WL等之鹼性蝕刻液。爲鎳時 ，可使用以硝酸/硫酸爲主成分之蝕刻液，市售品可列舉 出Mec股份有限公司製的NH-1865、Meltex股份有限公司製 的Melstrip N-9 5 0等。導體層形成後，藉由進行150〜200 °C 、20〜90分鐘的退火處理，可進一步提升導體層的剝離強 201230912 度而達安定化。 (F)藉由電解電鍍以形成導體層之步驟，較佳是在 (E )形成貫通孔之步驟後進行，尤佳是在（E )形成貫通 孔之步驟、（C )對絕緣層表面進行粗化處理之步驟後進 行，更佳是在（E )形成貫通孔之步驟、（C )對絕緣層表 面進行粗化處理之步驟、（D)藉由無電解電鍍於絕緣層 表面上形成金屬膜層之步驟後進行。 當對厚度較小的預浸材進行（E)形成貫通孔之步驟 時，可在與（F)藉由電解電鍍以形成導體層之步驟的同 時，藉由電鍍來充塡貫通孔的內部。此係稱爲貫通孔充塡 電鍍，藉此可具有縮短電路基板的製程之優點。 [多層印刷配線基板] 接著說明使用本發明之層合板來製造本發明之多層印 刷配線基板的方法。較佳係採用下列方法，亦即將使硬化 性樹脂組成物以層形成在支撐體上之黏著膜的硬化性樹脂 組成物層’以直接接觸於層合板之方式疊合於層合板的單 面或雙面。然後藉由真空疊合法，在減壓下將黏著膜疊合 於層合板。疊合方法可爲分批式或輥連續式。此外，進行 疊合前，可因應必要預先加熱（預熱）黏著膜與層合板。 疊合條件’溫度較佳設爲70〜14(TC，壓力較佳設爲 l~llkgf/cm2 ( 9.8 X 1 〇4~ 1 07.9 X 1 04N/m2 )，空氣壓較佳設 爲2 0mmHg (26.7hPa)以下。真空疊合，可使用市售的真 空疊合機來進行。市售的真空疊合.機，例如可列舉出 -31 - 201230912Polymerization Co., Ltd., "P1700", "P3500", etc., can further enhance (d) hardening promotion from the viewpoint of efficiently curing the epoxy resin and the curing agent in the curable resin composition. Agent. Examples of the hardening accelerator include an imidazole compound, a pyridine compound, and an organic phosphine compound. Specific examples thereof include 2-methylimidazole, 4-dimethylimidazole, and triphenylphosphine. When one or two or more kinds of these can be used, when (d) a curing accelerator is used, it is preferably used in an amount of from 0.1 to 3.0% by mass based on the epoxy resin. The curable resin composition may further contain (e) an inorganic ruthenium material from the viewpoint of lowering the thermal expansion coefficient of the insulating layer. Examples of the inorganic cerium filling material include cerium oxide, aluminum oxide, mica, pure mica, ceric acid salt, barium sulfate, magnesium hydroxide, titanium oxide, etc., preferably cerium oxide or aluminum oxide, and particularly preferred A cerium oxide such as cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide or the like is formed. The cerium oxide is preferably spherical, and one type or two or more types can be used. From the viewpoint of lowering the dielectric constant, the dielectric tangent, and the coefficient of thermal expansion, it is preferred to use hollow cerium oxide. The hollow ceria is composed of a shell portion and a hollow portion, and the average void ratio is preferably from 30 to 80% by volume. The upper limit of the average particle diameter of the inorganic cerium filler is preferably 5 μm or less, more preferably 4 μηι or less, more preferably 3 μπι or less, and still more preferably 2 μηα or less, and is preferably 1 in terms of improving the reliability of the insulation. 5 μιη or less, particularly preferably 1 μη1 or less, and most preferably 〇.5 μπι or less. On the other hand, the lower limit of the average particle diameter of the inorganic ceramium filler material is preferably 〇.〇1 μπι to -14-201230912, and more preferably 0.05 μιη or more, more preferably 0.1μιη or more. The average particle size of the inorganic cerium can be determined by laser diffraction scattering according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic cerium material can be produced on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle diameter. The sample is measured and suitably used to superimpose the inorganic cerium filling material in water. For the laser diffraction type particle size distribution measuring device, LA-5 00 manufactured by Horiba, Ltd., etc. can be used. The upper limit of the content of the inorganic ceramium in the curable resin composition is a curable resin composition from the viewpoint of preventing the mechanical strength of the cured product from being lowered, improving the workability, and improving the adhesion of the plating. The non-volatile content is 100 mass ° /. The amount is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, and still more preferably 65% by mass or less. On the other hand, in the case where the lower limit of the content of the inorganic cerium material in the curable resin composition is 値, the thermal expansion coefficient is lowered, and the rigidity is imparted to the prepreg, the non-volatile matter in the curable resin composition is used. When the amount is 1% by mass, it is preferably 40% by mass or more. Inorganic cerium filling materials, in order to improve moisture resistance, dispersibility, etc., are preferably treated by the following surface treating agents, namely, amine propyl methoxy decane, amine propyl triethoxy decane, urea propyl triethoxy Amine decane coupling agent such as decane, N-phenylaminopropyltrimethoxy decane, N-2 (aminoethyl)amine propyl trimethoxy decane; glycidoxypropyltrimethoxy decane, propylene oxide Propyltriethoxy decane, glycidoxypropylmethyldiethoxy decane, glycidyl butyl trimethoxy decane, (3,4-epoxycyclohexyl)ethyltrimethoxy decane, etc. -15- Epoxy decane coupling agent of 201230912; mercapto decane coupling agent such as propyl propyl trimethoxane or propyl propyl triethoxy decane; methyl trimethoxy decane, octadecyl trimethoxy decane, phenyl trimethoxy a decane coupling agent such as decane, methacryloxypropyltrimethoxy decane, imidazolium or triazine decane; hexamethyldiazepine, hexaphenyldioxane, dimethylaminotrimethoxy decane Organic germanium nitrogen such as triazane, cyclotriazane, 1,1,3,3,5,5-hexamethylcyclotriazane An alkane compound; a butyl titanate dimer, a octyl titanate, a bis(triethanolamine) diisopropylate titanate, a dihydroxy ester of dilactate titanate, a di(urmonium lactate) titanate, Bis(dioctylpyrophosphate)vinyl titanate, bis(dioctylpyrophosphate) titanate oxyacetate, tri-n-butoxide monostearate, tetra-n-butyl titanate, titanic acid Tetrakis(2-hexylhexyl) ester, bis(dioctylphosphinic acid) tetraisopropyl titanate, bis(di(dodecyl)phosphinic acid) tetraoctyl titanate, bis (two (13) Alkyl)) phosphinate titanate tetrakis(2,2·diallyloxymethyl-1-butyl) ester, isopropyl trioctyl phthalate, isopropyl triisopropyl benzoate Phenyl phenyl ester, isopropyl triisostearyl phthalate, isopropyl isostearyl phthalate diacrylate, isostearyl isopropyl dimethacrylate, isopropyl titanate Tris(dioctylphosphinic acid) ester, isopropyl tris(dodecyl)benzenesulfonate titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl trititanate Titrate coupling of N-nonylamine ethyl/amine ethyl) ester Wait. These may be used alone or in combination of two or more. In the curable resin composition, a bismaleimide-triazine resin, an acrylic resin, a maleimide compound, or a bisallylylene may be blended in a range in which the effects of the present invention are exerted as necessary. A thermosetting resin other than the epoxy resin of the fluorene imine compound, the vinyl benzyl resin, the vinyl benzyl ether resin, the blocked isocyanate compound, etc., -16, 2012,309. These may be used in one type or two or more types. Examples of the maleimide include BMI1000, BMI2000, BMI3000, BMI40 00, BMI5 000 (made by Daiwa Kasei Kogyo Co., Ltd.), BMI, BMI-70, BMI-80 (made by KI Chemical Co., Ltd.), ANILIX- MI (Misui Fine Chemicals Co., Ltd.), bisallyl naphthyl imine compound, BANI-M, BANI-X (made by Jiu-Sen Petrochemical Co., Ltd.) V5000 (made by Showa Polymer Co., Ltd.), and vinyl benzyl ether resin, V1000X, V1100X (made by Showa Polymer Co., Ltd.), etc. are mentioned. In the curable resin composition, a flame retardant may be contained in a range in which the effects of the present invention are exerted as necessary. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyoxyalkylene-based flame retardant, and a metal hydroxide. Examples of the organic phosphorus-based flame retardant include phosphine compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd.; and phosphorus-containing benzoxazines such as HFB_2〇〇6M manufactured by Showa Polymer Co., Ltd. Compound; REOFOS 30, 50, 65, 90, 1 1 0, TPP, RPD, BAPP, CPD 'TCP ' TXP, TBP, TOP, KP140, TIBP, manufactured by Ajinomoto Fine Techno Co., Ltd. ppQ, OP9 30 from Clariant Co., Ltd., phosphate ester compound such as PX200 manufactured by Daeba Chemical Co., Ltd.; phosphorus-containing epoxy compound such as FX2 89 and FX3 10 manufactured by Dongdu Chemical Co., Ltd.; Phosphorus-containing phenoxy resin such as ERF00 1 manufactured by Huacheng Co., Ltd. Examples of the nitrogen-containing phosphorus compound of the organic system include phosphate phthalamide compounds such as SP670 and SP703 manufactured by Kokusai Kasei Co., Ltd., and phosphorus and nitrogen such as SPB100 and SPE1 manufactured by Otsuka Chemical Co., Ltd. An ene compound or the like. Examples of the metal hydroxy compound include magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Ube Materials Co., Ltd., and B.30, B_325, B_315, B.308, B-303, and UFH-20 manufactured by Ba Industrial Co., Ltd. Such as aluminum hydroxide and the like. These may be used alone or in combination of two or more. In the curable resin composition, it is possible to contain solid rubber particles for the purpose of improving the mechanical strength of the cured product and the stress relieving effect within the range in which the effects of the present invention are exerted. The solid rubber particles are preferably organic solvents which are not dissolved in the preparation of the resin composition, and are not compatible with the components in the resin composition such as epoxy resin, and are dispersed in the varnish of the resin composition. Exist. The rubber particles are generally prepared by increasing the molecular weight of the rubber component to such an extent that it does not dissolve in an organic solvent or resin. Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and examples thereof include a two-layer structure in which a shell layer of an outer layer is a glassy polymer, and a core layer of an inner layer is a rubbery polymer. The outer layer is composed of a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glassy polymer is composed of, for example, a polymer of methyl methacrylate or the like, and the rubbery polymer is composed of, for example, a butyl methacrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Stafiloid AC3 832, AC3 8 1 6N (product name of -18-201230912 of Ganz Chemical Co., Ltd.), and Metablen KW-4426 (trade name of Mitsubishi Rayon Co., Ltd.). Specific examples of the acrylonitrile butadiene rubber (NBR) particles include specific examples of styrene butadiene rubber (SBR) particles such as XER-91 (average particle diameter of 0.5 μm) and JSR Co., Ltd. XSK-500 (average particle diameter 〇.5μιη, manufactured by JSR Co., Ltd.) can be mentioned. Specific examples of the acrylic rubber particles include Metablen W300A (average particle diameter Ο.ίμιη), W4 50A (average particle diameter 0·5 μιη) (manufactured by Mitsubishi Rayon Co., Ltd.), and the like. In the curable resin composition, other components may be blended as necessary. Examples of the other components include a fluorene agent such as a polysiloxane powder, a nylon powder, and a fluoro powder; a tackifier such as an organic bentonite or bentonite; and a defoaming agent of a polyoxyalkylene-based, fluorine-based or polymer-based system. A tackifier for a coating agent, a flattening agent, an imidazole-based, a thiazole-based, a triazole-based or a decane-based coupling agent; a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow or carbon black; Wait. The sheet-like fibrous base material to be used for the prepreg can be one or more selected from the group consisting of glass fibers, organic fibers, glass nonwoven fabrics, and organic nonwoven fabrics. Among them, a sheet-like fibrous base material such as a glass woven fabric, a guanamine non-woven fabric, a liquid crystal polymer nonwoven fabric or the like can be preferably used, and a glass woven fabric is particularly preferable. The thickness of the sheet-like fibrous substrate is preferably from 1 to 200 μm, particularly preferably from 5 to 175 μm, more preferably from 10 to 150 μm, still more preferably from 20 to 125 μm, and most preferably from 30 to 100 μm. Specific examples of the sheet-like fibrous base material include Style 1 027MS manufactured by Asahi Schwebel Co., Ltd. (linear warp density 75 pieces/25 mm, weft density 75 pieces/25 mm, cloth weight 20 g/m2, thickness 19 μη〇, Style 1 03 7MS by Asahi Schwebel Co., Ltd. (warp density 70 -19-201230912 /25mm, weft density 73/25mm, cloth weight 24g/m2, thickness 28μιη), 10 manufactured by Tosawa Co., Ltd. 7 8 (the warp density is 54/25mm, the weft density is 54/25mm, the cloth weight is 48g/m2, the thickness is 43μιη), and the 2 1 16 (manufactured by Yoshizawa Seisakusho Co., Ltd.) (the warp density is 50/25mm, the weft density) 58 pieces/25 mm, cloth weight: 103.8 g/m2, thickness: 9 4 μm), etc. Further, the liquid crystal polymer is not woven, and Vecls of a non-woven fabric manufactured by a polyarylate-based liquid crystal polymer manufactured by Kuraray Co., Ltd. is mentioned. (a basis weight of 6 to 15 g/m2) or a non-woven fabric of a fiber material made of Kuraray Co., Ltd., which is a fiber raw material. The method for producing the prepreg used in the present invention is not particularly limited, and is preferably the following. method The prepreg can be produced by a commonly known hot melt method, a solvent method, etc. The hot melt method does not require the resin composition to be dissolved in an organic solvent, and is first applied to a release mold which is excellent in peelability from the resin composition. A method of producing a prepreg by superimposing it on a paper or by directly applying it to a sheet-like fibrous substrate or the like by press molding. Further, the solvent method is based on a sheet-like fibrous substrate. It is immersed in a resin composition varnish in which a resin composition is dissolved in an organic solvent, and the resin composition varnish is impregnated into a sheet-like fibrous base material' and then dried. Further, it may be hardened by lamination on a support. The adhesive film formed of the resin composition is prepared by continuously thermally laminating from both sides of the flaky reinforcing substrate under heat and pressure. The organic solvent in the preparation of the varnish is, for example, acetone. Ketones such as methyl ethyl ketone and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc. - 201230912 agent, butyl card Such as carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. One or two of these may be used. The drying conditions of the varnish are not particularly limited, and in the molding step, the curable resin composition must have fluidity and adhesion. On the other hand, when a large amount of organic solvent remains in the prepreg, it becomes The content of the organic solvent in the curable resin composition is preferably 5% by mass or less, and particularly preferably 2% by mass or less. The specific drying conditions vary depending on the curability of the curable resin composition or the amount of the organic solvent in the varnish, but in the varnish containing 30 to 60% by mass of the organic solvent, it is preferably 80 to 180 °. Drying was carried out for 3 to 13 minutes under C. The preferred drying conditions can be appropriately set by a simple experiment. The thickness of the prepreg is preferably in the range of 20 to 250 μm, particularly preferably in the range of 40 to 180 μm, more preferably 60, from the viewpoint of the cost of the sheet-like fibrous substrate and the desired rigidity of the prepreg. ~150μιη range. The thickness of the prepreg can be controlled by adjusting the impregnation amount of the curable resin composition. Further, since the prepreg must have a fluidity which can be laminated without being formed under the molding, the curable resin composition in the prepreg is preferably in the range of 200 to 30,000 Åise. Inside 'Ultra is in the range of 1 000~20000 poise. <Support> In the method of the present invention, since the support is used in place of the metal foil and the prepreg is hardened, the excess step of removing the metal foil is not required, and the productivity of the laminate - 21 - 201230912 is excellent. The advantages of the waste liquid can also be reduced in terms of the environmental aspect, and further have the advantage of being low cost and easy to remove compared with the metal foil. The support used in the present invention is a self-supporting film, and a plastic film can be suitably used. The plastic film may, for example, be polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamidimide, polyamine, polytetrafluoroethylene, polycarbonate, etc., preferably The polyethylene terephthalate film or the polyethylene naphthalate film is particularly preferably a polyethylene terephthalate film from the viewpoint of being inexpensive. In addition, for the purpose of improving the releasability after hardening, the plastic film is preferably a release plastic film subjected to surface treatment such as rough treatment or corona treatment, or a polyoxyalkylene resin is present on the surface of the support. A release plastic film of another release layer such as an alkyd resin or a fluororesin. In addition, the surface of the support may be subjected to a surface treatment. The arithmetic mean roughness (Ra値) is preferably 50 nm or less, and particularly preferably 40 nm, from the viewpoint of smoothly maintaining the surface of the prepreg when it comes into contact with the prepreg in contact with the prepreg. Hereinafter, it is more preferably 35 nm or less, still more preferably 30 nm or less, and most preferably 25 nm or less. The lower limit of the arithmetic mean roughness (Ra値) is not particularly limited, and is preferably 0.1 nm or more, and particularly preferably 〇 5 n m or more, from the viewpoint of practicality of the support. The measurement of the arithmetic mean roughness (R a 値 ) can be carried out by a generally known method, for example, by using a non-contact type surface roughness meter (for example, WYKO NT3300 manufactured by Veeco Instruments Co., Ltd.). Commercially available products can be used as the support, and examples thereof include T60 (manufactured by Toray Co., Ltd., polyethylene terephthalate film), and A4100 (manufactured by Toyobo Co., Ltd., polyethylene terephthalate film). ), Q83 (made by Teijin DuPont Co., Ltd., polyethylene naphthalate-22-201230912 ethylene glycol film), poly terephthalic acid with alkyd type release agent (AL-5) manufactured by Lintec Co., Ltd. An ethylenediester film, Diafoil B 1 000 (a polyethylene terephthalate film manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.), or the like. The thickness of the support is preferably from 1 〇 to 70 μm, and particularly preferably from 15 to 70 μm. When the thickness is too small, the handleability tends to deteriorate or the peelability of the support layer tends to decrease. In addition, when the thickness is too large, the cost-effectiveness tends to deteriorate. <Embedding the prepreg to form an insulating layer> In the step (Α), one or more prepregs are placed between the supports, and the prepreg is heated and pressurized under reduced pressure. Hardened to form an insulating layer. When two or more prepregs are used, the same prepreg or different prepregs can be used. When a different prepreg is used, one or all of the composition of the curable resin composition, the material of the sheet-like fibrous base material, and the thickness of the sheet-like fibrous base material may be different from each other. The insulating layer of the present invention can be directly used in the production of a laminate without providing an adhesive layer. Further, from the viewpoint of workability, a prepreg with a support attached to the surface of the support to which the prepreg is applied may be used. The bonding of the support to the prepreg can be carried out by heating and pressing by means of a molding, a batch type laminator, a roll laminator or the like. The heating temperature is preferably from 60 to 140 ° C, particularly preferably from 70 to 130 ° C, from the viewpoint of adhesion between the support and the prepreg. The pressing pressure is preferably in the range of 1 to 1 lkgf/cm 2 ( 9.8×10 4 to 107.9×10 4 N/m 2 ), particularly preferably 2 to 7 kgf/cm 2 ( 19.6×10 4 to 68.6×10 4 N). Within the range of /m2). The pressing time is preferably in the range of -23-201230912 5 seconds to 3 minutes. When a roll laminator is used, the line pressure is preferably in the range of l to 15 kgf/cm, and more preferably in the range of l~l〇kgf/cm. When the pressure is too small, the fluidity of the resin composition is insufficient, and the adhesion to the support tends to be lowered. When the pressure is too large, it tends to be difficult to maintain the film thickness due to the bleeding of the resin. For the vacuum laminating machine, a commercially available vacuum laminating machine can be used. For example, a batch type vacuum press laminating machine MVLP-500 manufactured by Nippon Seisakusho Co., Ltd., Nichigo Morton Co., Ltd. A vacuum wet film coater manufactured by the company, a roll dry coater manufactured by Hitachi Industries Co., Ltd., a vacuum laminator manufactured by Hitachi AIC Co., Ltd., or the like. When the prepreg with the support is used, the layers of the prepreg are overlapped relative to each other, or the other one or more prepregs are placed between the two prepreg layers of the prepreg with the support and overlap. Thereafter, heating and pressurization are performed under reduced pressure to harden the prepreg to form an insulating layer. As described above, the inserted prepreg ' can be the same as or different from the prepreg used as the prepreg layer of the prepreg to which the support is attached. The step of forming the insulating layer by hardening and pre-pressing the prepreg under reduced pressure can be carried out using a vacuum hot press. For example, it can be carried out by molding from a metal plate such as a heated S U S plate on both sides of the support body. The molding conditions are preferably carried out under reduced pressure of 1 x 1 〇·2 MPa or less. Heating and pressurization can be carried out in one stage. From the viewpoint of controlling the bleeding of the resin, it is preferable to carry out the conditions by dividing the conditions into two or more stages. The first stage of the molding ' is preferably at a temperature of 70. (:~150. (:, the range of pressure 1~15 kgf/cm2 -24-201230912, the time is in the range of 15~45 minutes. The second stage of molding, preferably at the temperature of 15〇C~250 °C, pressure 1~140kgf/cm2, time is 60~150 minutes, especially in the range of 160 °C ~ 240 °C, pressure 1~40kgf/Cm2, time is 75 It is carried out in the range of ～130 minutes. For example, MNPC-V-750-5-200 (Made Machine Co., Ltd.) and VH1-1603 (made by Kitagawa Seiki Co., Ltd.) ). The lower limit of the glass transition temperature of the insulating layer prevents cracking at the end of the through hole, improves the adhesion reliability between the resin composition and the conductor layer, and reduces warpage at high temperatures to enhance the wafer structure. From the viewpoint of the nature, it is preferably 150 ° C or higher, and more preferably 15 5 ° C or higher. In addition, the upper limit of the glass transition temperature of the insulating layer is preferably higher and better. 1 75 ° C or less, preferably 180 ° C or less, more preferably 190 ° C or less, and even more preferably 200 ° C or less, excellent 2 3 0 ° C or less, especially preferably 2,500 Ω or less, and most preferably 270 ° C or less. 'The tensile modulus of the insulating layer ensures the rigidity of the electronic component when it is assembled' and the low tilt From the viewpoint of the impact resistance of the curved product and the embossed product, it is preferably 10 OGPa or more, and more preferably 15 GPa or more. Further, the tensile elastic modulus of the insulating layer is preferably as high as 25 GPa or less. More preferably, it is 30 GPa or less, and more preferably 35 GPa or less. [(B) Step] (B) The step of removing the support is generally performed by mechanically peeling off by manual or automatic peeling -25-201230912. Preferably, the prepreg is cured to form an insulating layer and then peeled off. When the step of forming a through hole (E) is described later, (E) may be formed before or after the step of (B) removing the support. The step of the through hole is preferably a step of forming a through hole by (.E) before the step of removing the support (B) in the viewpoint of protecting the insulating layer when the through hole is formed. [(C) Step] ( The step C) may be a dry method using plasma or the like, or an oxygen based on an alkaline permanganic acid solution or the like. A generally known method such as a wet method performed by a treatment agent, in particular, it is preferable from the viewpoint of roughening the surface of the insulating layer and increasing the adhesion strength of the plating layer based on the degreasing performed by the oxidizing agent. When the step (C) is carried out by an oxidizing agent, it is preferred to carry out the swelling treatment according to the swelling liquid, the roughening treatment according to the oxidizing agent, and the neutralization treatment according to the neutralizing agent in this order. The swelling liquid is not particularly limited. An alkali solution, a surfactant solution, and the like are exemplified, and an alkali solution is preferred. The alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. For example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by Atotech Japan Co., Ltd., may be mentioned. The swelling treatment of the swelling liquid is not particularly limited. Specifically, the swelling liquid at 30 to 90 ° C may be allowed to adhere for 1 minute to 15 minutes. In view of workability and the fact that the resin is not excessively swollen, it is preferred to immerse the swelling liquid at 40 to 80 ° C for 5 seconds to 10 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution. The roughening treatment by an oxidizing agent such as a base-26-201230912 permanganic acid solution or the like is preferably carried out by heating to 60 to 8 (the oxidizing agent solution of TC is immersed for 10 minutes to 30 minutes. Further, alkaline permanganic acid is used. The concentration of the solution-neutral permanganate is preferably from 5 to 10% by mass. Examples of the commercially available oxidizing agent include an alkalinity such as Concentrate Compact CP and Dosing Solution Securiganth P manufactured by Atotech Japan Co., Ltd. Further, the neutralizing agent is preferably an acidic aqueous solution, and a commercially available product is a reduction solution Securiganth P (neutralizing solution) manufactured by Atotech Japan Co., Ltd. According to the neutralization treatment of the neutralizing agent, it can be used. The method of adhering the neutralizing solution at 30 to 80 ° C to the treated surface after the roughening treatment according to the oxidizing agent solution is carried out for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferred to carry out the coarsening according to the oxidizing agent solution. The object after the treatment is immersed in a neutralizing solution at 40 to 70 ° C for 5 minutes to 20 minutes. In the step (C), the wall residue generated by the step of forming the through hole by (E) can be removed, and Can be carried out From the viewpoint of the roughening treatment of the wall surface, it is preferably carried out after the step of forming the through hole (E). The upper limit 算术 of the arithmetic mean roughness (Ra値) of the insulating layer after the step (C) can be From the viewpoint of forming finer wiring under high smoothness, it is preferably 600 nm or less, more preferably 570 nm or less, more preferably 540 nm or less, still more preferably 510 nm or less, and most preferably 480 nm or less, and particularly preferably 45 〇. On the other hand, the lower limit of the arithmetic mean roughness (Ra値) of the insulating layer is preferably Ο-lnm or more, and more preferably 〇.5 nm or more, from the viewpoint of obtaining high peel strength. Preferably, it is 1 nm or more, more preferably 10 nm or more, and most preferably 50 nm or more, particularly preferably 100 nm or more. 201230912 [(D) Step] (D) Step of forming a metal film layer on the surface of the insulating layer by electroless plating It can be carried out by a generally known method, for example, by treating the surface of the insulating layer with a surfactant or the like, and then impregnating the electroless electrolytic solution with a plating catalyst such as palladium to form a metal film. Nickel, gold, palladium, etc., among which copper is preferred. The thickness is preferably from 0.1 to 5.0 μηι, particularly preferably from 0.2 to 2·5 μηι, more preferably from 2 to 1.5 μm, from the viewpoint of sufficiently covering the surface of the resin and cost-effectiveness. It can also be formed by a direct electroplating method of electroless plating. The upper limit of the peeling strength of the insulating layer and the metal film layer after the step (D) is preferably 〇.8kgf. The thickness of /cm or less is particularly preferably lkgf/cm or less, more preferably 3 kgf/cm or less, still more preferably 5 kgf/cm or less, and most preferably 10 kgf/cm or less. On the other hand, the lower limit of the peel strength of the insulating layer and the metal film layer is preferably 0.45 kgf/cm or more from the viewpoint of maintaining insulation reliability. [(E) Step] In the method of the present invention, (E) a step of forming a through hole can be further performed. The step (E) is not particularly limited as long as it can reach the intended purpose, and a through hole can be formed by a generally known method, and a mechanical drill or a laser such as a carbon dioxide gas laser or a YAG laser can be used. (E) The step of forming the through hole is preferably performed before the step of (B) removing the support, from the viewpoint of protecting the surface of the insulating layer when the through hole is formed. Further, from the viewpoint of preventing the surface of the insulating layer from being roughened, it is preferred that -28 to 201230912 be carried out after (D) a step of forming a metal film layer on the surface of the insulating layer by electroless plating. When the through hole is formed from the support by the laser, the laser absorbing property can be contained in the support in order to improve the laser workability. Examples of the laser absorptive component include metal compound powder, carbon powder, metal powder, and black dye. The blending amount of the laser energy absorbing component is preferably from 5% to 40% by mass, particularly preferably from 0 to 1% by mass, more preferably 1%, of all the components constituting the layer containing the component. ~10% by mass. Examples of the carbon powder include carbon black powder such as furnace black, channel black, acetylene black, hot black, and black, graphite powder, or a mixture of such a powder. Examples of the metal compound powder include titanium oxide such as titanium oxide, magnesia such as magnesium oxide, iron oxide such as iron oxide, nickel oxide such as nickel oxide, zinc oxide such as manganese dioxide or zinc oxide, and the like. Cobalt oxide such as cerium oxide, aluminum oxide, rare earth oxide, cobalt oxide, tin oxide such as tin oxide, tungsten oxide such as tungsten oxide, carbonized sand, tungsten carbide, boron nitride, silicon nitride, Titanium nitride, nitriding, barium sulfate, rare earth oxysulfide, or a mixture of such a powder. The metal powder may be a powder of an alloy or a mixture of silver, Ming, Mi, Ming, copper, iron, magnesium, lanthanum, molybdenum, nickel, lanthanum, lanthanum, sand, tin, titanium, sharp, crane, zinc, or the like. Wait. Examples of the black dye include azo (monoazo, disazo) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketimine dyes, ketone dyes, nitro dyes, and oxa dyes. Scallion dye, anthraquinone dye, quinoxaline dye, aminoketone dye, methine dye, anthraquinone dye, coumarin dye, anthrone dye, triphenyl dye, triallyylene dye, phthalocyanine dye, inklophenol dye , diazonine dye, or a mixture of these, and the like. The black dye is preferably a solvent -29-201230912 soluble black dye in order to enhance the dispersibility in the water-soluble resin. These may be used alone or in combination of two or more. The laser energy absorbing component is preferably carbon powder, and particularly preferably carbon black, in terms of conversion efficiency or versatility of laser energy to heat energy. [(F) Step] In the method of the present invention, (F) a step of forming a conductor layer by electrolytic electricity can be further carried out. Preferably, after (D) a step of forming a metal film layer on the surface of the insulating layer by electroless plating, the metal film layer is applied to carry out (F) a step of forming a conductor layer by electrolytic plating. The formation of the conductor layer can be carried out by a generally known method such as a semi-additive method. For example, a plating resist is formed, and the metal film layer formed in the step (D) is used as an electric shielding layer, and then a conductor layer is formed by electrolytic plating. The conductor layer formed by electrolytic plating is preferably copper. Although the thickness varies depending on the design of the desired circuit substrate, it is preferably 3 to 35 μη, more preferably 5 to 30 μm. After the electrolytic plating, the plating resist is plated with an alkaline aqueous solution or the like to remove the plating resist, and then the plating mask is removed to form a wiring pattern. For the method of removing the plating mask layer, an etching solution can be used. For example, in the case of copper, an acidic etching solution such as an aqueous solution of ferric chloride, an aqueous solution of sodium peroxodisulfate and sulfuric acid, or a CF-6000 manufactured by Mec Co., Ltd., Meltex can be used. An alkaline etching solution such as E-Process-WL manufactured by the company. In the case of nickel, an etching solution containing nitric acid/sulfuric acid as a main component can be used, and commercially available products include NH-1865 manufactured by Mec Co., Ltd., and Melstrip N-9 50 manufactured by Meltex Co., Ltd., and the like. After the formation of the conductor layer, by annealing at 150 to 200 ° C for 20 to 90 minutes, the peeling strength of the conductor layer can be further increased to a stability of 201230912 degrees. (F) the step of forming a conductor layer by electrolytic plating, preferably after the step of forming a through hole (E), particularly preferably the step of forming a through hole in (E) and (C) the surface of the insulating layer After the step of roughening treatment, it is more preferably a step of forming a through hole in (E), (C) a step of roughening the surface of the insulating layer, and (D) forming a metal on the surface of the insulating layer by electroless plating. The step of the film layer is carried out. When the step of (E) forming the through hole is performed on the prepreg having a small thickness, the inside of the through hole can be filled by electroplating while (D) is subjected to electrolytic plating to form a conductor layer. This is called through-hole filling, whereby it has the advantage of shortening the process of the circuit substrate. [Multilayer printed wiring board] Next, a method of manufacturing the multilayer printed wiring board of the present invention using the laminate of the present invention will be described. Preferably, the curable resin composition layer of the adhesive film in which the curable resin composition is formed as a layer on the support is laminated on one side of the laminate or directly in contact with the laminate. Double sided. The adhesive film was then laminated to the laminate under reduced pressure by vacuum lamination. The lamination method can be batch or roll continuous. In addition, the adhesive film and laminate may be preheated (preheated) as necessary before the lamination. The superposition condition 'temperature is preferably set to 70 to 14 (TC, the pressure is preferably set to l~llkgf/cm2 (9.8 X 1 〇4~1 07.9 X 1 04N/m2), and the air pressure is preferably set to 20 mmHg ( 26.7 hPa) or less. Vacuum lamination can be carried out using a commercially available vacuum laminating machine. Commercially available vacuum laminating machines, for example, -31 - 201230912

Nichi go Morton股份有限公司製的真空濕膜塗佈機、名機 製作所股份有限公司製的真空加壓式疊合機、Hitachi Industries股份有限公司製的輕式乾式塗佈機、Hitachi AIC股份有限公司製的真空疊合機等。 如此將黏著膜疊合於層合板後，於剝離支撐膜時，係 進行剝離及熱硬化，藉此可將絕緣層形成於層合板。加熱 硬化的條件，可在150°C〜220 °C、20分鐘~180分鐘的範圍 內選擇，尤佳爲160 °C〜200 °C、30分鐘〜120分鐘。形成絕 緣層後，於硬化前未剝離支撐膜時，可在此剝離。接著對 絕緣層進行開孔來形成導通孔。開孔可藉由鑽頭、雷射、 電漿等一般所知的方法來進行。接著藉由與前述方法相同 之使用氧化劑的方法，進行絕緣層表面的粗化處理，在藉 由粗化處理形成有凹凸的定錨之絕緣層表面，藉由組合無 電解電鍍與電解電鏟之方法來形成導體層。對導體層進行 圖型加工來形成電路之方法，例如可使用該業者所熟知之 減成法、半加成法等。 [半導體裝置] 再者，可藉由使用本發明之多層印刷配線基板來製造 出本發明之半導體裝置。藉由將半導體元件接合於多層印 刷配線基板上的連接用電極部分，來製造出半導體裝置。 半導體元件的裝載方法並無特別限定，例如可列舉出導線 接合構裝、覆晶構裝、依據異向性導電膜（ACF )之構裝 、依據非導電性膜（NCF)之構裝等。 -32- 201230912 〔實施例〕 以下係顯示實施例來更具體說明本發明，但本發明並 不限定於以下實施例。以下的記載中之「份」係意味著「 質量份」。 首先說明本說明書中之物性評估的測定方法及評估方 法。 &lt;導體層之剝離強度（剝離強度）的測定&gt; 依據JIS C648 1來測定導體層的剝離強度。具體而言 ，將實施例及比較例中所得之電路基板切斷爲150mmx 3 0 mm的小片。以切割刀在小片的銅箔部分上切入寬i〇mrn 、長100mm的缺口，將銅箔的一端剝離並以夾持具夾住， 使用Instron萬用試驗機’在室溫下以50mm/分的速度往垂 直方向拉開35mm，並測定此時的荷重而作爲剝離強度。 導體層的厚度大約設爲30 μιη。 &lt;絕緣層之算術平均粗糙度（Ra値）的測定&gt; 以銅蝕刻液來去除電路基板上的無電解鍍銅層及電解 鍍銅層，使用非接觸型表面粗糙度儀（Veec〇 Instruments 公司製的WYKO NT3300 )，在VSI接觸模式下’藉由50倍 透鏡以測定範圍作爲121 μιηχ 92 μιη來測定絕緣層的表面， 以求取算術平均粗糙度（“値）° Ra値係隨機設定10點的 測定場所，並採用此等的平均値。 -33- 201230912 &lt;玻璃轉移溫度（Tg)的測定&gt; 將實施例及比較例中所製作之絕緣層切斷爲寬度約 5mm、長度約15mm的試驗片，使用Rigaku股份有限公司製 的熱機械分析裝置（Thermo Plus TMA8310)，以拉伸加 重法來進行熱機械分析。將試驗片裝著於前述裝置後，在 荷重1 g、升溫速度5 °C /分的測定條件下連續測定2次。並 從第2次的測定中之尺寸變化信號的斜率所產生變化之點 ，來算出玻璃轉移溫度（°C )。 &lt;拉伸彈性率的測定&gt; 依據日本工業規格（JIS K7127)，使用Tensilon萬用 試驗機（A and D股份有限公司製）對實施例及比較例中 所製作之絕緣層進行拉伸試驗，並測定拉伸彈性率。 &lt;有無金屬箔去除步驟之評估&gt; 在實施例及比較例中所製作之層合板中，以無金屬箔 去除步驟者爲「〇」，以有金屬箔去除步驟者爲「X」。 (實施例〇 &lt;預浸材的製作&gt; 將液狀雙酚A型環氧樹脂（環氧當量180、三菱化學股 份有限公司製「Epikote 828EL」）28份、萘型4官能環氧 樹脂（環氧當量163、DIC股份有限公司製「HP4700」） -34- 201230912 28份、苯氧樹脂（三菱化學股份有限公司製「 YX6954BH30」、固形份30質量％2MEK與環己酮1: 1的 溶液）20份，於MEK1 5份與環己酮15份的混合溶劑中一邊 攪拌一邊加熱溶解。然後將含有三嗪的酚-酚醛樹脂（羥 基當量125、DIC股份有限公司製「LA7054」、固形份60 質量％的MEK溶液）27份、萘酚系硬化劑（羥基當量215、 東都化成股份有限公司製「SN-485」）之固形份50%的 MEK溶液27份、硬化觸媒（四國化成股份有限公司製、「 2E4MZ」）0.1份、球形二氧化矽（平均粒徑0·5μπι、 Admatechs股份有限公司製「SOC2」）70份、聚乙烯丁醛 樹脂（積水化學工業股份有限公司製「KS-1」），溶解於 乙醇與甲苯的質量比爲1: 1之混合溶劑而製作出固形份 15%的溶液，將此溶液30份與上述加熱溶解後的溶液混合 ，藉由高速旋轉摻混機使其均一地分散，而製作出硬化性 樹脂組成物的清漆。將該清漆含浸於有澤製作所股份有限 公司製的2116玻璃織物（厚度94μιη)，於縱型乾燥爐中， 在140°C下乾燥5分鐘而製作出預浸材。預浸材的殘留溶劑 量，爲不含玻璃織物之硬化性樹脂組成物中的0.1〜1 wt %， 預浸材的厚度爲12〇μπι。 &lt;絕緣層的形成&gt; 藉由裁切機將上述製作出的預浸材分別裁切爲3 40mm x5 00mm的大小。然後將2片預浸材設置在2片四氟乙烯膜 (旭硝子股份有限公司製、「Aflex」50μιη )間，藉由名 -35- 201230912 機製作所股份有限公司製的真空模壓機（MNPC-V-75 0-5 -200 )，將減壓度設爲lxl〇'3MPa，在壓力10kgf/cm2、升溫 速度3 °C/分下，從室溫上升至130 °C並保持30分鐘後，將 壓力設爲30 kgf/cm2，以升溫速度3°C /分升溫至190°C並保 持90分鐘，藉此形成絕緣層。 &lt;電路基板的製作&gt; 將四氟乙烯膜剝離，將絕緣層表面藉由Atotech Japan 股份有限公司製的Swelling Dip Securiganth P’在60°C下 進行5分鐘的膨潤處理》水洗後，藉由Atotech Japan股份 有限公司製的Concentrate Compact CP (驗性過猛酸溶液 )，在80 °C下進行20分鐘的粗化處理。水洗後，藉由 Atotech Japan 股份有限公司製的 Reduction Solution Securiganth P(中和液），在40°C下進行5分鐘的中和處 理。然後進行無電解銅電鍍（使用下列所詳述之Atotech Japan股份有限公司製的藥液並採用無電解銅電鍍的製程 )來製作出層合板。無電解銅電鍍的膜厚爲km。然後進 行電解銅電鍍，形成合計30μηι厚的導體層而得電路基板。 〈使用Atotech Japan股份有限公司製的藥液之無電解銅電 鍍的製程&gt; 1.鹼洗淨（樹脂表面的洗淨及電荷調整） 商品名稱：Cleaning cleaner Securiganth 902 條件：60°C下5分鐘 -36- 201230912 2. 軟性蝕刻 硫酸酸性過氧二硫酸鈉水溶液 條件：3 0 °C下1分鐘 3. 預浸（以貞了在下—步驟中賦予以而調整表面電荷 者爲目的） 商品名稱：Pre. Dip Neoganth B 條件：室溫下1分鐘 4. 活化（將Pd賦予至樹脂表面） 商品名稱：Activator Neoganth 834 條件：35°C下5分鐘 5. 還原（使附著於樹脂之Pd還原）Vacuum wet film coater manufactured by Nichigo Morton Co., Ltd., vacuum pressurizing laminator manufactured by Nippon Seisakusho Co., Ltd., light dry coater manufactured by Hitachi Industries Co., Ltd., Hitachi AIC Co., Ltd. Vacuum laminating machine, etc. After the adhesive film is laminated on the laminate as described above, the support film is peeled off and thermally cured, whereby the insulating layer can be formed on the laminate. The conditions of heat hardening can be selected from 150 ° C to 220 ° C for 20 minutes to 180 minutes, preferably 160 ° C to 200 ° C for 30 minutes to 120 minutes. After the formation of the insulating layer, the support film may not be peeled off before the hardening. Next, the insulating layer is opened to form via holes. The opening can be carried out by a generally known method such as a drill, a laser, or a plasma. Then, the surface of the insulating layer is roughened by the same method as the above method using an oxidizing agent, and the surface of the insulating layer which is formed by the roughening treatment is formed by combining the electroless plating and the electrolytic shovel. Method to form a conductor layer. For the method of patterning the conductor layer to form a circuit, for example, a subtractive method, a semi-additive method, or the like which is well known to those skilled in the art can be used. [Semiconductor device] Further, the semiconductor device of the present invention can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device is manufactured by bonding a semiconductor element to a connection electrode portion on a multilayer printed wiring board. The method of loading the semiconductor element is not particularly limited, and examples thereof include a wire bonding structure, a flip chip mounting structure, an assembly according to an anisotropic conductive film (ACF), and a structure according to a non-conductive film (NCF). [32] The following is a more detailed description of the present invention, but the present invention is not limited to the following examples. The "parts" in the following description means "parts by mass". First, the measurement method and evaluation method of the physical property evaluation in the present specification will be described. &lt;Measurement of peel strength (peel strength) of conductor layer> The peel strength of the conductor layer was measured in accordance with JIS C648 1. Specifically, the circuit board obtained in the examples and the comparative examples was cut into small pieces of 150 mm x 30 mm. A slit having a width i〇mrn and a length of 100 mm was cut into a copper foil portion of the small piece by a cutter, and one end of the copper foil was peeled off and clamped by a holder, and an Instron universal testing machine was used at room temperature at 50 mm/min. The speed was pulled 35 mm in the vertical direction, and the load at this time was measured as the peel strength. The thickness of the conductor layer is set to approximately 30 μm. &lt;Measurement of Arithmetic Average Roughness (Ra値) of Insulating Layer&gt; The electroless copper plating layer and the electrolytic copper plating layer on the circuit board were removed by a copper etching solution, and a non-contact surface roughness meter (Veec〇Instruments) was used. WYKO NT3300, manufactured by the company, in the VSI contact mode, the surface of the insulating layer was measured by a 50-fold lens with a measurement range of 121 μm χ 92 μm to obtain an arithmetic mean roughness (“値)° Ra値 system random setting. The measurement site at 10 o'clock was used, and the average enthalpy was used. -33 - 201230912 &lt;Measurement of glass transition temperature (Tg)&gt; The insulating layers produced in the examples and the comparative examples were cut into a width of about 5 mm and a length. A test piece of about 15 mm was subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer (Thermo Plus TMA8310) manufactured by Rigaku Co., Ltd. After the test piece was placed in the above apparatus, the load was increased by 1 g. The measurement was carried out twice under the measurement conditions of a speed of 5 ° C /min. The glass transition temperature (°C) was calculated from the point where the change in the slope of the dimensional change signal in the second measurement was performed. Measurement of the rate of the property> The insulating layer produced in the examples and the comparative examples was subjected to a tensile test using a Tensilon universal testing machine (manufactured by A and D Co., Ltd.) according to the Japanese Industrial Standard (JIS K7127), and the tensile test was performed. Elastic modulus. <Evaluation of the presence or absence of the metal foil removing step> In the laminates produced in the examples and the comparative examples, the step of removing the metal foil is "〇", and the step of removing the metal foil is " X". (Example 〇 & <Preparation of Prepreg> 28 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "Epikote 828EL" by Mitsubishi Chemical Corporation), naphthalene type 4-functional epoxy resin (epoxy equivalent 163, "HP4700" manufactured by DIC Co., Ltd.) -34- 201230912 28 parts, phenoxy resin ("XX6954BH30" manufactured by Mitsubishi Chemical Corporation, solid content 30% by mass 2MEK and cyclohexanone 1:1) 20 parts of the solution, and the mixture was heated and dissolved in a mixed solvent of 5 parts of MEK1 and 15 parts of cyclohexanone while stirring. Then, a triazine-containing phenol-phenolic resin (hydroxyl equivalent 125, "LA7054" manufactured by DIC Co., Ltd., solid type) 27 parts by mass of MEK solution) 27 parts, a naphthol-based curing agent (hydroxyl equivalent 215, "SN-485" manufactured by Tohto Kasei Co., Ltd.), a solid solution of 50% of MEK solution, 27 parts, and a hardening catalyst (four countries) 0.1 parts of "2E4MZ" manufactured by Kasei Co., Ltd., 70 parts of spherical cerium oxide (average particle size: 0.5 μm, "SOC2" manufactured by Admatech Co., Ltd.), and polyvinyl butyral resin (made by Sekisui Chemical Co., Ltd.) "KS-1"), A solution having a mass ratio of ethanol to toluene of 1:1 was prepared to prepare a solution having a solid content of 15%, and 30 parts of the solution was mixed with the solution prepared by heating and dissolving, and uniformly mixed by a high-speed rotary blender. A varnish of a curable resin composition was prepared by dispersing the varnish, and the varnish was immersed in a 2116 glass fabric (thickness: 94 μm) manufactured by Azawa Seisakusho Co., Ltd., and dried in a vertical drying oven at 140 ° C for 5 minutes. The amount of the residual solvent of the prepreg is 0.1 to 1 wt% of the curable resin composition containing no glass fabric, and the thickness of the prepreg is 12 μm. &lt;Formation of insulating layer&gt; The prepreg prepared above was cut into a size of 3 40 mm x 5 00 mm by a cutting machine, and then two prepregs were placed on two tetrafluoroethylene films ("Aflex" 50 μm by Asahi Glass Co., Ltd. In the case of a vacuum molding machine (MNPC-V-75 0-5 -200 ) manufactured by the name -35-201230912 Machine Manufacturing Co., Ltd., the decompression degree is set to lxl〇'3MPa at a pressure of 10kgf/cm2. Temperature rise rate of 3 °C / min, from room temperature to 130 °C and After holding for 30 minutes, the pressure was set to 30 kgf/cm2, and the temperature was raised to 190 ° C at a temperature increase rate of 3 ° C /min for 90 minutes to form an insulating layer. <Preparation of Circuit Board> Tetrafluoroethylene The film was peeled off, and the surface of the insulating layer was swelled by Swelling Dip Securiganth P' manufactured by Atotech Japan Co., Ltd. at 60 ° C for 5 minutes. After washing, the Concentrate Compact CP manufactured by Atotech Japan Co., Ltd. was used. The excess acid solution) was subjected to a roughening treatment at 80 ° C for 20 minutes. After washing with water, the solution was neutralized at 40 ° C for 5 minutes by Reduction Solution Securiganth P (neutralization solution) manufactured by Atotech Japan Co., Ltd. Then, electroless copper plating (using a chemical solution manufactured by Atotech Japan Co., Ltd. as described in detail below and electroless copper plating) was used to produce a laminate. The film thickness of electroless copper plating is km. Then, electrolytic copper plating was carried out to form a conductor layer having a total thickness of 30 μm to obtain a circuit board. <Process for electroless copper plating using a chemical solution manufactured by Atotech Japan Co., Ltd.> 1. Alkali cleaning (resin cleaning and charge adjustment) Product name: Cleaning cleaner Securiganth 902 Condition: 5 minutes at 60 ° C -36- 201230912 2. Soft etching of acidic sodium peroxodisulfate solution: 1 minute at 30 °C 3. Pre-dip (for the purpose of adjusting the surface charge in the next step) Product Name: Pre. Dip Neoganth B Condition: 1 minute at room temperature 4. Activation (Pd is imparted to the surface of the resin) Trade name: Activator Neoganth 834 Condition: 5 minutes at 35 ° C 5. Reduction (reduction of Pd attached to the resin)

冏品名稱：Reducer Neoganth WA :Reducer Acceralator 810 mod.的混合液 6. 無電解銅電鍍（將Cu析出於樹脂表面（Pd表面））Product Name: Reducer Neoganth WA : Mixed Liquid of Reducer Acceralator 810 mod. 6. Electroless Copper Plating (Cu is deposited on the resin surface (Pd surface))

商品名稱：B a s i c S ο 1 u t i ο η P r i n t g an t h M S K · D K :Copper Solution Printganth MSK :Stabilizer Printganth MSK-DK :Reducer Cu的混合液 條件：35°C下2 0分鐘 (實施例2 ) &lt;預浸材的製作&gt; 將液狀雙酚A型環氧樹脂（環氧當量18〇、三菱化學股 份有限公司製「Epikote 828EL」）13份、萘型4官能環氧 -37- 201230912 樹脂（環氧當量163、DIC股份有限公司製「HP4700」）6 份、聯苯芳烷型環氧樹脂（環氧當量27 5、日本化藥股份 有限公司製「NC3000L」）18份、聯苯型環氧樹脂（環氧 當量180、三菱化學股份有限公司製「YX4000H」）10份 、苯氧樹脂（三菱化學股份有限公司製「YX6954BH3 0」 、固形份30質量％2MEK與環己酮1: 1的溶液）1〇份，於 Μ E K 1 5份與環己酮1 5份的混合溶劑中一邊攪拌一邊加熱溶 解。然後將含有三嗪的酚-酚醛樹脂（羥基當量125、DIC 股份有限公司製「LA705 4」、固形份60質量％的MEK溶液 )1 5份、萘酚系硬化劑（羥基當量2 1 5、東都化成股份有 限公司製「SN-4 85」）之固形份60%的MEK溶液1 5份、硬 化觸媒（四國化成股份有限公司製、「2E4MZ」）0.1份、 球形二氧化矽（平均粒徑〇·5μπι、Admatechs股份有限公司 製「SOC2」）135份、伸菲基型磷化合物（三光股份有限 公司製「HCA-HQ」、平均粒徑2μιη) 6份、聚乙烯丁醛樹 脂（積水化學工業股份有限公司製「KS-1」），溶解於乙 醇與甲苯的質量比爲1 : 1之混合溶劑而製作出固形份1 5 % 的溶液，將此溶液1 5份與上述加熱溶解後的溶液混合，藉 由高速旋轉摻混機使其均一地分散，而製作出硬化性樹脂 組成物的清漆。將該清漆含浸於有澤製作所股份有限公司 製的2116玻璃織物（厚度94μπι)，於縱型乾燥爐中，在 14(TC下乾燥5分鐘而製作出預浸材。預浸材的殘留溶劑量 ，爲不含玻璃織物之硬化性樹脂組成物中的0 · 1〜1 wt% ’預 浸材的厚度爲120μπι。 -38- 201230912 然後與實施例1相同，形成絕緣層並製作出電路基板 (比較例1 ) &lt;預浸材的製作&gt; 將甲酚酚醛型環氧樹脂（環氧當量215、DIC股份有限 公司製「N-680」）之固形份75%的MEK溶液30份、甲酚酚 醛樹脂（羥基當量1 1 9、DIC股份有限公司製「KA-1 1 65」 )之60%的MEK溶液16.5份、硬化觸媒（四國化成股份有 限公司製、「2E4MZ」）0.05份、氫氧化鋁（平均粒徑 3·0μιη、巴工業股份有限公司製「UFE-20」）30份、 ΜΕΚ4 0份混合，藉由高速旋轉摻混機使其均一地分散，而 製作出硬化性樹脂組成物的清漆。將該清漆含浸於有澤製 作所股份有限公司製的2116玻璃織物（厚度94 μχη)，於縱 型乾燥爐中，在140 °C下乾燥5分鐘而製作出預浸材。預浸 材的殘留溶劑量，爲不含玻璃織物之硬化性樹脂組成物中 的0.1〜lwt%，預浸材的厚度爲120μιη。 然後與實施例1相同，形成絕緣層並欲製作出電路基 板，但無法在絕緣層上形成鍍層，無法進行剝離強度的測 定。第1表中表示爲「X」。 (比較例2 ) 使用實施例1中所製作之預浸材，並使用2片電解銅箔 (Nikko Mate rials公司製「JTC箔」、18μιη )來取代實施 -39- 201230912 例1的2片四氟乙烯膜，除此之外，其他與實施例1相同來 形成絕緣層。然後浸漬於FeCl3水溶液30分鐘，去除銅箔 ，並與實施例1相同來形成電路基板。 測定結果如下表所示。 【第1表】Product name: B asic S ο 1 uti ο η P rintg an th MSK · DK : Copper Solution Printganth MSK : Stabilizer Printganth MSK-DK : Reducer Cu mixture condition: 20 minutes at 35 ° C (Example 2) &lt; [Preparation of prepreg material] 13 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 18 〇, "Epikote 828EL" manufactured by Mitsubishi Chemical Corporation), naphthalene type 4-functional epoxy-37-201230912 resin (Epoxy equivalent 163, "HP4700" manufactured by DIC Co., Ltd.) 6 parts, biphenyl aralkyl type epoxy resin (epoxy equivalent 27 5, "Nippon Chemical Co., Ltd." "NC3000L") 18 parts, biphenyl type Epoxy resin (epoxy equivalent weight 180, "YX4000H" manufactured by Mitsubishi Chemical Corporation) 10 parts, phenoxy resin ("XX6954BH3 0" manufactured by Mitsubishi Chemical Corporation, solid content 30% by mass 2MEK and cyclohexanone 1: 1 The solution was dissolved in 1 part by stirring in a mixed solvent of EK 1 5 parts and 15 parts of cyclohexanone while stirring. Then, a triazine-containing phenol-phenolic resin (hydroxyl equivalent of 125, DIC Co., Ltd. "LA705 4", solid content of 60% by mass of MEK solution) of 15 parts, and a naphthol-based curing agent (hydroxyl equivalent of 2 1 5, 15 parts of MEK solution of 60% solid content of "SN-4 85" manufactured by Dongdu Chemical Co., Ltd.), 0.1 part of hardening catalyst ("2E4MZ" manufactured by Shikoku Chemicals Co., Ltd.), spherical cerium oxide (average 135 parts of particle size 〇·5μπι, "SOC2" manufactured by Admatech Co., Ltd.), phenanthrene-based phosphorus compound ("HCA-HQ" manufactured by Sanko Co., Ltd., average particle size 2μιη) 6 parts, polyvinyl butyral resin ( "KS-1" manufactured by Sekisui Chemical Co., Ltd.), dissolved in a mixed solvent of ethanol and toluene in a mass ratio of 1:1 to prepare a solution of 15% solid solution, and dissolved 15 parts of the solution with the above heat. The latter solution was mixed and uniformly dispersed by a high-speed rotary blender to prepare a varnish of a curable resin composition. The varnish was impregnated with a 2116 glass fabric (thickness 94 μm) manufactured by Azawa Seisakusho Co., Ltd., and dried in a vertical drying oven at 14 (TC for 5 minutes to prepare a prepreg. The amount of residual solvent of the prepreg, 0 to 1 to 1 wt% of the curable resin composition containing no glass fabric. The thickness of the prepreg was 120 μm. -38 - 201230912 Then, in the same manner as in Example 1, an insulating layer was formed and a circuit board was produced (Comparative Example) 1) &lt;Preparation of prepreg&gt; 30 parts of MEK solution of 75% solid content of cresol novolac type epoxy resin (epoxy equivalent 215, "N-680" manufactured by DIC Corporation), cresol novolac 16.5 parts of a 60% MEK solution of a resin (hydroxyl equivalent: 119, "KA-1 1 65" manufactured by DIC Co., Ltd.), a curing catalyst (manufactured by Shikoku Chemicals Co., Ltd., "2E4MZ"), 0.05 parts, hydrogen 30 parts of alumina (average particle size 3·0μιη, "UFE-20" manufactured by Ba Industrial Co., Ltd.) and 40 parts of 混合 were mixed, and uniformly dispersed by a high-speed rotary blender to prepare a curable resin. Varnish of the material. Immerse the varnish in the Azawa Manufacturing Co., Ltd. 2116 glass fabric (94 μχ thickness) made by Co., Ltd. was dried in a vertical drying oven at 140 ° C for 5 minutes to prepare a prepreg. The residual solvent amount of the prepreg was glass-free. 0.1 to 1 wt% of the curable resin composition, and a thickness of the prepreg of 120 μm. Then, as in the case of Example 1, an insulating layer was formed and a circuit board was produced, but a plating layer could not be formed on the insulating layer, and peeling strength could not be obtained. In the first table, it is indicated as "X". (Comparative Example 2) The prepreg prepared in Example 1 was used, and two electrolytic copper foils ("JTC foil", 18 μιη, manufactured by Nikko Mate rials Co., Ltd.) were used. An insulating layer was formed in the same manner as in Example 1 except that the two sheets of the tetrafluoroethylene film of Example 1 of -39-201230912 were used, and then immersed in an aqueous solution of FeCl3 for 30 minutes to remove the copper foil, and Example 1 was The circuit board is formed in the same manner. The measurement results are shown in the following table. [Table 1]

實施例1 實施例2 比較例1 比較例2 剝離強度(kgf/cm) 0.5 0.45 X 0.9 算術平均粗糙度(nm) 450 350 700 1200 玻璃轉移溫度(。〇 155 155 180 155 拉伸彈性率(GPa) 16 21 17 16 有無金屬箔去除步驟 之評估 〇 〇 〇 X 從實施例1、2中可得知，根據本發明之方法，可在不 須透過去除金屬箔之多餘步驟，來製造出可一邊維持玻璃 轉移溫度與拉伸彈性率，且同時在平滑絕緣層表面上形成 剝離強度佳之導體層之層合板。比較例1中，可得知由於 未使用本發明之預浸材，所以完全無法得到剝離強度。此 外，比較例2並非使用本發明之方法，並且使用銅箔，所 以算術平均粗糙度的控制極爲困難，並且須進行去除金屬 箔之多餘步驟。實際上在使用銅箔時，會因銅箔凹凸的影 響而使層合板的算術平均粗糙度增大，難以形成細微配線 產業上之可利用性： -40- 201230912 根據本發明’可在不須透過去除金屬箱之多餘步驟， 來製造出可一邊維持玻璃轉移溫度與拉伸彈性率，且同時 在平滑絕緣層表面上形成剝離強度佳之導體層之層合板^ 該層合板，可在溫和條件下進行由蝕刻所進行之電鍍遮蔽 層的去除，而抑制配線圖型的溶解，故特別適合於要求細 微配線形成之電路基板的製造。再者，亦可提供裝載此等 層合板之多層印刷配線基板、半導體裝置、電腦、行動電 話、數位相機、電視等之電化製品，或是摩托車、汽車、 電車、船舶、飛機等之乘用機器。 -41 -Example 1 Example 2 Comparative Example 1 Comparative Example 2 Peel strength (kgf/cm) 0.5 0.45 X 0.9 Arithmetic average roughness (nm) 450 350 700 1200 Glass transition temperature (. 〇155 155 180 155 Tensile modulus (GPa) 16 21 17 16 Evaluation of the presence or absence of the metal foil removal step 〇〇〇X As can be seen from Examples 1 and 2, according to the method of the present invention, one side can be manufactured without unnecessary steps of removing the metal foil. A laminate of a conductor layer having a good peeling strength was formed on the surface of the smooth insulating layer while maintaining the glass transition temperature and the tensile modulus. In Comparative Example 1, it was found that the prepreg of the present invention was not used, so that it was completely impossible to obtain. In addition, Comparative Example 2 does not use the method of the present invention, and copper foil is used, so the control of arithmetic mean roughness is extremely difficult, and an unnecessary step of removing the metal foil is required. Actually, when copper foil is used, The influence of the unevenness of the copper foil increases the arithmetic mean roughness of the laminate, and it is difficult to form the fine wiring industry's availability: -40- 201230912 According to the present invention, By removing the excess steps of the metal box, a laminate which can maintain the glass transition temperature and the tensile modulus while maintaining a peeling strength of the conductor layer on the surface of the smooth insulating layer can be manufactured under mild conditions. Since the removal of the plating mask by etching is performed to suppress the dissolution of the wiring pattern, it is particularly suitable for the production of a circuit board in which fine wiring is required. Further, a multilayer printed wiring board on which such laminates are mounted may be provided. , electrochemical devices such as semiconductor devices, computers, mobile phones, digital cameras, televisions, etc., or passenger machines for motorcycles, automobiles, trams, ships, airplanes, etc. -41 -

Claims (1)

201230912 七、申請專利範圍： 1. 一種層合板的製造方法，其特徵係包含：（A)於 支撐體之間配置1片以上的預浸材，並藉由在減壓下進行 加熱及加壓使預浸材硬化而形成絕緣層之步驟， (B)去除支撐體之步驟， (C )對絕緣層表面進行粗化處理之步驟，以及 (D)藉由無電解電鍍於絕緣層表面上形成金屬膜層 之步驟；且 相對於前述預浸材中之硬化性樹脂組成物中的非揮發 份1〇〇質量％，含有無機塡充材40質量％以上80質量％以下 » 前述絕緣層的玻璃轉移溫度爲1 5 0 °C以上2 7 0。(：以下， 拉伸彈性率爲lOGPa以上35GPa以下； 在前述（C)對絕緣層表面進行粗化處理之步驟後之 絕緣層的算術平均粗糙度爲〇.lnm以上600nm以下； 在前述（D)藉由無電解電鍍於絕緣層表面上形成金 屬膜層之步驟後之絕緣層與金屬膜層的剝離強度爲 〇.45kgf/cm 以上 10kgf/cm 以下。 2. 如申請專利範圍第1項之層合板的製造方法，其中 支撐體爲脫模塑膠膜。 3_如申請專利範圍第1項之層合板的製造方法，其中 預浸材是由硬化性樹脂組成物與薄片狀纖維基材所構成。 4.如申請專利範圍第3項之層合板的製造方法，其中 預浸材中的薄片狀纖維基材’係含有選自玻璃纖維、有機 -42- 201230912 纖維、玻璃不織布、有機不織布之1種或2種以上。 5 .如申請專利範圍第3項之層合板的製造方法，其中 薄片狀纖維基材爲厚度1〜200 μιη的玻璃纖維。 6. 如申請專利範圍第1項之層合板的製造方法，其中 預浸材中的硬化性樹脂組成物含有環氧樹脂及硬化劑。 7. 如申請專利範圍第1項之層合板的製造方法，其中 預浸材中的硬化性樹脂組成物含有萘型環氧樹脂及萘酣系 硬化劑。 8. 如申請專利範圍第〗項之層合板的製造方法，其係 在150〜250 °C、60〜150分鐘的條件下硬化預浸材而形成絕 緣層。 9·如申請專利範圍第1項之層合板的製造方法，其中 進一步包含（E)形成貫通孔之步驟。 10.如申請專利範圍第9項之層合板的製造方法，其中 在（B)去除支撐體之步驟前，進行（E)形成貫通孔之步 驟。 Π .如申請專利範圍第丨項之層合板的製造方法，其中 進一步包含（F)藉由電解電鍍以形成導體層之步驟。 1 2. —種多層印刷配線基板，其係使用藉由如申請專 利範圍第1至Π項中任一項之製造方法所得之層合板。 1 3 ·—種半導體裝置，其係使用藉由如申請專利範圍 第1至1 1項中任一項之製造方法所得之層合板.。 -43 - 201230912 四 指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件符號簡單說明：無 201230912 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無201230912 VII. Patent Application Range: 1. A method for manufacturing a laminate, comprising: (A) arranging one or more prepregs between the supports, and heating and pressurizing under reduced pressure a step of hardening the prepreg to form an insulating layer, (B) a step of removing the support, (C) a step of roughening the surface of the insulating layer, and (D) forming an insulating layer on the surface of the insulating layer by electroless plating The step of forming a metal film layer; and containing not less than 1% by mass of the nonvolatile matter in the curable resin composition in the prepreg, 40% by mass or more and 80% by mass or less of the inorganic ceramium filler material » Glass of the foregoing insulating layer The transfer temperature is above 150 °C and 270 °. (The following, the tensile modulus is 10 GPa or more and 35 GPa or less; and the arithmetic mean roughness of the insulating layer after the step of roughening the surface of the insulating layer (C) is 〇.1 nm or more and 600 nm or less; The peeling strength of the insulating layer and the metal film layer after the step of forming the metal film layer on the surface of the insulating layer by electroless plating is 〇45 kgf/cm or more and 10 kgf/cm or less. 2. As in the first claim of the patent scope A method for producing a laminate, wherein the support is a release plastic film. The method for producing a laminate according to the first aspect of the invention, wherein the prepreg is composed of a curable resin composition and a sheet-like fibrous substrate. 4. The method for producing a laminate according to claim 3, wherein the flaky fibrous substrate in the prepreg contains a fiber selected from the group consisting of glass fiber, organic-42-201230912 fiber, glass nonwoven fabric, and organic nonwoven fabric. 5. The method for producing a laminate according to the third aspect of the invention, wherein the sheet-like fibrous substrate is a glass fiber having a thickness of from 1 to 200 μm. A method for producing a laminate, wherein the curable resin composition in the prepreg contains an epoxy resin and a hardener. 7. The method for producing a laminate according to the first aspect of the invention, wherein the curable resin in the prepreg The composition contains a naphthalene type epoxy resin and a naphthoquinone type hardener. 8. A method for producing a laminate according to the scope of the patent application, which is a hardened prepreg at 150 to 250 ° C for 60 to 150 minutes. The method of manufacturing a laminate according to the first aspect of the invention, further comprising (E) the step of forming a through hole. 10. The method for manufacturing a laminate according to claim 9 of the patent application, The step of forming a through hole by (E) before the step of removing the support (B). The method for manufacturing a laminate according to the above application, further comprising (F) forming by electrolytic plating. The step of the conductor layer. The layered board obtained by the manufacturing method according to any one of the first to third aspects of the invention, wherein a multilayer printed wiring board is used. A laminate obtained by the production method according to any one of claims 1 to 11 is used. -43 - 201230912 Four designated representative drawings: (1) The designated representative figure of the case is: none (2) A brief description of the symbol of the representative figure: No 201230912 If there is a chemical formula in the case of this case, please reveal the chemical formula that best shows the characteristics of the invention: none
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TWI804597B (en) * 2018-03-28 2023-06-11 日商積水化學工業股份有限公司 Resin materials and multilayer printed wiring boards

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TWI578871B (en) 2017-04-11

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