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TW201251534A - Prepreg, laminate, print circuit board and semiconductor device - Google Patents

Prepreg, laminate, print circuit board and semiconductor device Download PDF

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Publication number
TW201251534A
TW201251534A TW101102467A TW101102467A TW201251534A TW 201251534 A TW201251534 A TW 201251534A TW 101102467 A TW101102467 A TW 101102467A TW 101102467 A TW101102467 A TW 101102467A TW 201251534 A TW201251534 A TW 201251534A
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TW
Taiwan
Prior art keywords
prepreg
glass
resin
woven fabric
mass
Prior art date
Application number
TW101102467A
Other languages
Chinese (zh)
Other versions
TWI539869B (en
Inventor
Noriyuki Ohigashi
Original Assignee
Sumitomo Bakelite Co
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Publication of TW201251534A publication Critical patent/TW201251534A/en
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Publication of TWI539869B publication Critical patent/TWI539869B/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • 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
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0275—Fibers and reinforcement materials
    • H05K2201/029—Woven fibrous reinforcement or textile

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Textile Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The prepreg of the present invention is a prepreg (40) formed by impregnating a fibrous fabric composed of strands with a resin composition. In addition, in the prepreg of the present invention, silica particles exist in the strands. Thereby, it is possible to obtain a prepreg excellent in impregnating ability of the resin composition with respect to the fibrous fabric. In addition, a print circuit board and a semiconductor device can be manufactured by using the prepreg and/or a metal-clad laminate produced by using the prepreg.

Description

201251534 六、發明說明： 【發明所屬之技術領域】 本發明係關於預浸體、積層板、印刷佈線板及半導體裝置 【先前技術】 近年來，隨著電子機器之高機能化等要求，電子零件之高 密度集成化、進而高密度安裝化等正進展著。因此，此等所 使用之高密度安裝對應的印刷佈線板被要求電路佈線之細 微化，以及穿孔(through hole)與通孔(viah〇le)的縮小化。 穿孔及通孔係使用鑽頭、二氧化碳雷射等之雷射等而形 成彳在特別小徑的打孔時係使用雷射。由雷射所進行的打 孔力—口工中，成孔之絕緣層壁面的凹凸越大，則孔徑或形狀 越谷易偏差，而加工精度降低。 印刷佈線板之絕緣層可藉由對預浸體之—片或重疊了複 數片者進行加熱加壓而形成。預浸體—般係藉由將於溶劑中 含有以熱硬化性樹脂為主成分之樹脂組成物而成的清漆，含 反於玻璃布等之基材中，使其加熱乾燥*製作。在藉雷射 工而形成孔之_層壁面中’於基材部分與樹脂組成物部二 有因雷射所造_祕㈣。_，若基社 = 地跡，則有孔徑、形狀容易偏差的傾向。另-方面^由質 使用吳地細緻之高密度基材，則可提升絕緣層之由 行的打孔加工性(專利文獻卜2)。 進 另外，為了#應零件安裝於印刷佈線板上的高密度化，而 101102467 201251534 要求減小由印刷佈線板之熱膨脹所造成之曲輕以確保連接 可靠性。半導體裝置（半導體封袭）係將半導體元件搭载 刷佈線板’但半導體元件之熱膨脹率為3〜6ppm/<t，車六 之半導體封裝用樣、線板的熱膨脹率。二，在； 體封裝施加了熱衝擊時’有因半導體元件 體 刷佈線板之熱膨脹率差，而於半導體料發生曲躺情开/ 此時’在半導ϋ元件與半導體封裝用印刷佈線板之間、或半 導體封裝與所安裝之印刷佈線板之間有發生連接不良的情 藉由於絕緣層使用熱膨脹率較小之絕緣性材料，則可減小 印刷佈線板之熱膨脹所造成的曲翹。為了使成為絕緣性材料 之預浸體低線膨脹化，作為預浸體製造中所使用之樹脂組成 物，係使用使無機填充材經高填充化者（專利文獻3)。 專利文獻1 :日本專利特開2001-38836號公報 專利文獻2:曰本專利特開2000-22302號公報 專利文獻3:日本專利特開2009-138〇75號公報 【發明内容】 然而’若使用高密度之基材製作預浸體’則樹脂組成物對 基材的含浸性差劣’尤其是多量地含有填充材之樹脂組成 物，因填充材不會進入基材之纖維間，故樹脂組成物的含浸 困難。又，為了提升含浸性，而在例如進行了填充材之含量 減低等時，有難以維持預浸體所具有之其他各種特性的情 101102467 5 201251534 本發明係為了消除 於提供一種於維持預 樹脂組成私.... 除上迷問題點而完成者，本發明之目的在 預浸體所具有之各種特性之下，熱硬化性201251534 VI. Description of the Invention: [Technical Field] The present invention relates to a prepreg, a laminate, a printed wiring board, and a semiconductor device. [Prior Art] In recent years, with the demand for high functionality of electronic devices, electronic components The high-density integration and the high-density mounting are progressing. Therefore, the printed wiring boards corresponding to the high-density mounting used by these are required to be fine-tuned in circuit wiring, and to reduce the through holes and vias. The perforation and the through hole are formed by using a laser such as a drill, a carbon dioxide laser or the like to form a laser, and a laser is used for punching a particularly small diameter. Punching force by laser—In the case of mouth-to-mouth, the larger the unevenness of the wall surface of the insulating layer in which the hole is formed, the more the aperture or the shape is more likely to be deviated, and the machining accuracy is lowered. The insulating layer of the printed wiring board can be formed by heating and pressurizing the prepreg or the plurality of sheets. The prepreg is usually made of a varnish containing a resin composition containing a thermosetting resin as a main component in a solvent, and is prepared by heating and drying the substrate against a glass cloth or the like. In the wall surface of the hole formed by the laser shooter, the substrate portion and the resin composition portion are made of a laser (4). _, Joakie = lands, there is a tendency that the aperture and shape are easily deviated. In addition, the high-density substrate of the fineness of the ruthenium can improve the punching workability of the insulating layer (Patent Document 2). Further, in order to increase the density of parts to be mounted on a printed wiring board, 101102467 201251534 requires reduction of the lightness caused by thermal expansion of the printed wiring board to ensure connection reliability. In the semiconductor device (semiconductor encapsulation), the semiconductor element is mounted on the brush wiring board, but the thermal expansion coefficient of the semiconductor element is 3 to 6 ppm/<t, the semiconductor package for the vehicle and the thermal expansion coefficient of the wiring board. Second, when the thermal impact is applied to the body package, the thermal expansion coefficient of the semiconductor device body brush wiring board is poor, and the semiconductor material is bent and opened/at the time of the semi-conductive element and the semiconductor package printed wiring board. There is a connection failure between the semiconductor package and the printed wiring board to be mounted. Since the insulating layer uses an insulating material having a small coefficient of thermal expansion, the warpage caused by the thermal expansion of the printed wiring board can be reduced. In the resin composition used for the production of the prepreg, the inorganic filler is highly filled (Patent Document 3). Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-38836 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2000-22302 (Patent Document 3) Japanese Patent Laid-Open Publication No. 2009-138 No. A high-density substrate is used to produce a prepreg, and the resin composition has poor impregnation with the substrate. In particular, a resin composition containing a filler in a large amount, since the filler does not enter between the fibers of the substrate, the resin composition Difficulty in impregnation. Further, in order to improve the impregnation property, for example, when the content of the filler is reduced, it is difficult to maintain the other various characteristics of the prepreg. 101102467 5 201251534 The present invention is intended to eliminate the need to provide a pre-resin composition. Private.... In addition to the problem, the purpose of the present invention is to be thermosetting under the various characteristics of the prepreg.

根據本發明，係提供一 T的含浸性優越的預浸體。又，本發 了該預浸體的金屬箔積層板，進而提 佈線板及半導體裝置。 由線月又所構成之纖維織布中而成者，於上述線股中存在二氧 一種預浸體，係使樹脂組成物含浸於 化矽粒子。 根據本發明，可提供一種於維持預浸體所具有之各種特性 之下，熱硬化性樹脂組成物對纖維織布之含浸性優越的預浸 體。 另外，根據本發明’可使用上述預浸體及/或使用上述預 浸體而製造的金屬箔積層板’製造印刷佈線板及半導體裝 置。 【實施方式】 上述目的及其他目的、特徵與優點，係藉由以下所述之較 佳實施形態及隨附之圖式進一步闡明。 以下，針對本發明之預浸體、金屬箔積層板、印刷佈線板 及半導體裝置進行詳細說明。 1.預浸體 本發明之預浸體係使樹脂組成物含浸於由線股所構成之 101102467 6 201251534 纖維織布中而成的預浸體。又，構成纖維織布之線股中係存 在二氧化石夕粒子。又，線股係指構成纖維織布之纖維的束。 藉由將線股織成後述之織物構造，而形成纖維織布。 本發明者發現，在依於線股中存在二氧化矽粒子之方式形 成預浸體時，則可於維持預浸體所具有之各種特性之下，提 升樹脂組成物對纖維織布的含浸性。於此，所謂各種特性， 係指例如後述之印·線板之_可#性、預浸體之雷射加 工性、.或預浸體之低熱膨脹性等。 在樹脂組成物對纖_布之含浸性良好時，可抑制所得預 浸體中發生空隙。II此，在將該預浸體用於絕緣層而得之印 刷佈線板中可達到絕緣可靠性的提升。 另外即使在使用了高密度之纖維織布的情況，仍可得到 =雜。因此，使用高密度之纖維織布，可形成雷射加工 性優越的預浸體。 充材於纖維織布内:=二維織布的含浸性’可將 } π Ά目可相預浸體的低 y θ可抑制將該預浸體用於絕緣声 線板發生她。因+ mg ^而付之印刷 構成預浸體的樹月旨組成物，係至少含絲HZ 充材的熱—刚⑽ 物」）β π吋間稱為「樹脂組, 構成預浸體之—組成物 較佳係例如依填充材之1〜20 101102467 201251534 質量％之比例含有平均粒徑5〜w()nm之二氡切粒子。本 發明者發現’即使是將含有多量填充材之樹脂組成物含浸於 高密度之纖維織布中而得的預浸體，藉由依上述填充材之 1〜20質量％之比例含有平均粒徑5〜1〇〇nm之二氧化矽粒 子，則樹脂組成物之含浸性良好。此理由可認為，由於上述 平均粒徑5〜⑽run之二氧化帅子進4纖_布之纖維 間、亦即線股内並擴散至纖維間，故平岣粒徑5〜i〇〇nm之 二氧化麵子以外的填充材亦可進人至纖維織布中所致。如 此’藉由使用平均粒徑5〜1 〇〇nm之♦半p 不木尺寸的二氧化矽粒 子作為填充材，則可得到於線股中具有二氧化矽粒子的 * 另外，由於平均粒徑5〜lOOnm之二惫a 乳化矽粒子之表面電 位與其他之填充材之表面電位的差 而使平均粒徑 5〜lOOnm之二氧化矽粒子與上述填充纟 ^ T鳍由相互作用而拉 附。因此，平均粒獲5〜lOOnm之二惫儿 氣化矽粒子存在於上述 填充材之周圍，平均粒徑5〜lOOnm之~ — _ 〜氣化石夕粒子且有問 隔件般之作用。如此，平均粒徑5〜]ηΛ . η111之二氧化石夕粒子 存在於上述填充材之周圍，藉由發揮作 _ 上述填充材之凡得瓦力所造成的拉附力^ 作用，使 此，上述填充材成為更高分散狀態 低防止凝集。藉 上述平均粒徑5〜lGGnm之二氧化 動⑨的降低。 分散於有機溶媒巾的料而使用。II 較佳係作成事先 9 ，可提升填充材之分 101102467 8 201251534 ====__之她降低。其理 的粒子大多容易_’1°奈米尺寸之二氧切般之奈米尺寸 集體等，仲由:周配至樹脂組成物中時形成二次凝 精由使用聚料狀物，則可防止此錄 此可防止流動性的降低。又，本發=凝集，藉 於凝集防止及分耑& & 斤使用之填充材，由 岛故較佳鱗先施行表面處理。 之織入根數，胃高密度之纖輯布’係指不僅提高紗 由扁平化而減f地進行高_、藉 布係例如體積密户=處理3的纖維織布。高密度之纖維織 又為1.05g/cm以上。藉此， 組成物含餘—根根纖維之間，故可達尊充^可使_ 化。再者，㈣可充分確保纖維織布上 、=填充 在預浸體上積層_而作成銅紐層板時、維持 表面平滑化時的成形性。 …4積層板之 如此’本發明之預浸體由於樹脂組成物對纖維 性良好’故空_發生較少。又，由於 =^浸 真充材&為低熱膨脹性，使用本發 的印刷佈線板的曲翹較小。又 ^體而付 膨服性，《使預賴魏讀許的1；^浸體之熱 另外’本發明之預浸體係#由使填紐 熱性優越、高剛性。再者，本發明之構成預浸體=維: 的體積讀，較佳為⑽韻〆。藉由使用體積密度為 101102467 201251534 1’05〜1.30g/cm之高密度之纖維織布，則使用作為印刷佈線 板之絕緣層時，可藉由雷射加工，形成孔徑及形狀之精度良 好'且抑制了纖維突出的孔。 另外’一般而言’使用多量含有填充材之樹脂組成物而得 的預/又體纟於樹脂纟且成物對基材的含浸性惡化，故基材難 以依均勻厚度保持樹脂組成物，在將該預浸體用於絕緣層而 作成印刷佈線板時，上述絕緣層之表面平滑性或與導體層間 之密黏性差，有難以進行細微佈線加工的問題。此情況係在 使預浸體薄型化時，有更加惡化的傾向。另—方面，本發明 之預浸體由於樹脂組成物對纖維織布之含浸性良好，故纖維 、哉布可依均勻厚度保持樹脂組成物，表面平滑性或與導體 間之密黏性良好’進而亦獨應薄型化。又，本發明 =係藉^用多量地含有填充材之樹脂組成物，而成為‘ 熱性、南剛性。 首先，針對本發明所使用之纖維織布進行說明。 作為本發明所使用之纖維織布，並無特別限定，可舉例如 由玻璃纖維、芳醯胺、㈣、芳香族聚自旨、氟樹脂等之合^ 纖維、金屬纖維、碳麟、礦物纖料所構成的纖維織布。 其中，由於呈低熱膨脹性、高剛性、尺寸安定性優越，故較 佳為由玻璃纖維所構成的玻璃纖維織布。 上述玻璃纖維並無特別限定，較佳係依si〇2為刈質旦 % 100質1%、Al2〇3為〇質量％〜3〇質量％、⑽為〇質量 101102467 201251534 %〜30質量％的比例含有上述各者，特佳為使用從τ玻璃（有 時亦稱為「S玻璃」）、D玻璃、Ε玻璃、ΝΕ玻璃、石英玻 璃所組成群選出之至少1種玻璃而成；其中，更佳為Τ玻 璃（S玻璃）、石英玻璃、D玻璃，由低熱膨脹性優越、高強 度的觀點而言，再佳為Τ玻璃（S玻璃）、石英玻璃。 尚且，本發明中，Τ玻璃（S玻璃）係指依Si02為62質量 %〜65質量％、a1203為20質量％〜25質量％、CaO為0質量 %〜0.01質量％、MgO為10質量％〜15質量％、B2〇3為〇質 量％〜0.01質量％、Na20及K20合計為0質量％〜1質量％的 比例含有上述各者之組成的玻璃；D玻璃係指依Si02為72 質量％〜76質量％、Al2〇3為0質量％〜5質量％、CaO為〇質 量％〜1質量％、MgO為0質量％〜1質量％、B2〇3為20質量 %〜25質量％、Na20及K20合計為3質量％〜5質量％的比例 含有上述各者之組成的玻璃；Ε玻璃係指依Si02為52質量 %〜56質量％、Al2〇3為12質量。/〇〜16質量％、CaO為15質 量％〜25質量％、Mg0為〇質量％〜6質量％、b2〇3為5質量 %〜10質量％、Na2〇及K20合計為0質量％〜〇.8質量％的比 例含有上述各者之組成的玻璃；ΝΕ玻璃係指依Si02為52 質量％〜56質量。/。、a1203為10質量％〜15質量％、CaO為〇 質量％〜10質量％、Mg0為〇質量％〜5質量％、B2〇3為15 質量°/〇〜20質量％、Na20及K20合計為〇質量％〜1質量％、 Ti〇2為〇.〇5質量％〜5質量％的比例含有上述各者之組成的 101102467 201251534 玻璃；石英玻璃係指依99.0質量％〜ι〇〇質量％之比例含有 Si〇2之組成的玻璃。 上述玻璃纖維並無特別限定，較佳係作成板狀時之楊氏率 (Young s modulus)為50〜l〇〇GPa、作成板狀時之拉張強度為 25GPa以上、作成纖維織布時之長度方向之拉張強度為 30N/25mm以上，更佳係作成板狀時之楊氏率為 80 1 OOGPa、作成板狀時之拉強強度為35Gpa以上，作成纖 維織布時之長度方向之拉張強度為45N/25mm以上。藉此， 可得到尺寸安定性優越的預浸體。又，上述楊氏率係根據 JIS R1602’藉由一般所使用之公知的3點弯曲試驗機所測 定的值，上述拉張強度係根據JIS R3420，藉由一般所使用 之公知的定速伸長形拉張試驗機所測定之值，上述長度方向 之拉張強度係根據JIS r342〇，將玻璃纖維作成織布，藉由 與上述相同之定速伸長形拉張試驗機所測定的值。 尚且上述揚氏率之測定及上述拉張強度之測定中，所謂 「板狀」係指將與玻璃纖維為相同組成之玻璃組成物作成^ Wm之玻璃板的狀態。又，在上述長度方向之拉張強 度測疋巾所5月「長度方向」係指經線⑽線)方向。 上述玻璃纖維並無特別限定，根據jisr所測定之經 線方向讀膨脹係數較佳為1〇卯武以下，特佳為加就 以下、。藉此’可減小印刷佈線板之熱膨脹所造成的曲趣。 上述纖維織布之厚度並無特別限定，較佳為⑺〜一、 101102467 12 201251534 更佳10〜140μιη、再更佳2〇〜9〇μηι。藉此，樹脂組成物對纖 維織布的含浸性良好，亦可對應薄型化。 上述纖維織布之體積密度較佳為1.05〜1.30g/cm3、特佳 1,10〜啤“。若體積密度未滿上述，則絕緣層之 雷射加工性差，若超過上述上限值’則樹脂組成物對纖維織 布的含浸性惡化。又，纖維織布之體積密度的調整，係藉由 。周整經線與㈣之織人根數、與、_纖、扁平處理之纖維 度而進行。 上述纖維織布並無特別限定，通氣度較佳為 更佳3〜5Gee/em2/see。若職度未滿上 限值’則樹脂組成物對纖維織布的含浸性惡化，錢過 上限值，則絕緣層之雷射加工性差。 姓上述纖維織布並無特別限I基重較佳為UM6CW、 特佳15〜130g/m2。若基重未、篇 熱膨脹性差，若超過上，顧浸體之低 的含浸性惡化、或絕緣層之雷成物對物^ 較 使用之纖維的扁平率Α μ、… ^。藉由使纖維織布所 诚總 為'内’則由於樹脂組成物對上 緣可靠性、从㈣料可提料孔間之絕 謂扁平率，仙性。又，本發明中所 由線之厚度：線之寬度所表示的值。 101102467 13 201251534 另外，上述纖維織布之織物構造並無特別限定，可舉例如 平織、斜織、朱子織、斜紋織等之織物構造等，其中由雷射 加工!生、強度、通孔之層間絕緣可靠性優越的觀點而言，較 佳為平織構造。 接著，說明本發明所使用之熱硬化性樹脂組成物。 本發明所使用之熱硬化性樹脂組成物，係至少含有熱硬化 性樹脂及填域。上述填充材係依上频硬化⑽脂組成物 之固形份之50〜85質量％的比例含有。又，上述熱硬化性樹 月曰組成物係依上述填充材之^20質量％的比例含有平均粒 徑5〜l〇〇nm之二氧化矽粒子。進而，上述熱硬化性樹脂組 成物中進一步視需要亦可含有硬化劑、偶合劑等。 (填充材） 上述填充材係依上述填充材整體之idO質量％的比例含 有平均粒徑5〜lOOnm之二氧化矽粒子。 作為上述二氧化矽粒子，並無特別限定，可例如使用藉由 VMC(Vaporized Metal Combustion)法、PVS(Physical Vapor Synthesis) 法等之燃燒法、對破碎二氧化矽進行火焰熔融之熔融法、沉 降法、凝膠法等之方法所製造者。其中特佳為VMc法❶所 謂上述VMC法，係指於在含氧氣體中所形成之化學焰中投 入矽粉末，使其燃燒後，予以冷卻，藉此形成二氧化矽微粒 子的方法。上述VMC法中，藉由調整所投入之矽粉末的粒 徑、投入量、火焰溫度等，則可調整所得之二氣化矽微粒子 101102467 14 201251534 的粒徑。又’作為上述*一氧化梦粒子，亦可使用 NSS-5N(TOKUYAMA(股）製）、Sicastar43-〇〇-501(Microm〇d 公司製）等之市售物。 上述平均粒徑5〜100nm之二氧化矽粒子，由含浸性之觀 點而言’特佳係平均粒徑為10〜75nm。二氧化;ς夕粒子之平均 粒徑未滿5nm時，則無法於纖維織布之纖維間擴散，又， 大於lOOnm時，則有無法進入纖維間的情形。According to the present invention, a prepreg excellent in impregnation of T is provided. Further, the metal foil laminate of the prepreg was obtained, and the wiring board and the semiconductor device were further provided. In the fiber woven fabric composed of the wire and the moon, a pre-dip of dioxane is present in the strand, and the resin composition is impregnated with the ruthenium-free particles. According to the present invention, it is possible to provide a prepreg which is excellent in impregnation of a thermosetting resin composition with a fiber woven fabric while maintaining various characteristics of the prepreg. Further, according to the present invention, a printed wiring board and a semiconductor device can be manufactured using the above-described prepreg and/or a metal foil laminated board manufactured using the above prepreg. The above and other objects, features, and advantages of the invention will be apparent from the preferred embodiments described herein. Hereinafter, the prepreg, the metal foil laminate, the printed wiring board, and the semiconductor device of the present invention will be described in detail. 1. Prepreg The prepreg of the present invention is obtained by impregnating a resin composition into a prepreg of 101102467 6 201251534 fiber woven fabric composed of strands. Further, in the strands constituting the fiber woven fabric, there are silica dioxide particles. Further, a strand is a bundle of fibers constituting a fiber woven fabric. The fiber woven fabric is formed by weaving the strands into a fabric structure to be described later. The present inventors have found that when a prepreg is formed in such a manner that the ceria particles are present in the strands, the impregnation property of the resin composition to the fiber woven fabric can be improved while maintaining various characteristics of the prepreg. . Here, the various characteristics are, for example, the stencil of the printing plate described later, the laser processing property of the prepreg, or the low thermal expansion property of the prepreg. When the impregnation property of the resin composition to the fiber cloth is good, voids in the obtained prepreg can be suppressed. II. In this case, the insulation reliability can be improved in the printed wiring board obtained by using the prepreg for the insulating layer. In addition, even in the case of using a high-density fiber woven fabric, it is possible to obtain = miscellaneous. Therefore, a high-density fiber woven fabric can be used to form a prepreg excellent in laser workability. Filling in the fiber woven fabric: = impregnation of the two-dimensional woven fabric can reduce the low y θ of the π Ά 可 phase prepreg to suppress the use of the prepreg for the insulating sound ray plate. The composition of the tree-forming composition of the prepreg, which is composed of + mg ^, is a heat-gang (10) material containing at least a silk HZ filler.) β π 吋 is called a "resin group, which constitutes a prepreg. The composition preferably contains, for example, bismuth-cut particles having an average particle diameter of 5 to w (meter nm) in a ratio of 1 to 20,101,102,467,2012,515,34% by mass of the filler. The present inventors have found that even a resin containing a large amount of filler is formed. A prepreg obtained by impregnating a high-density fiber woven fabric with a cerium oxide particle having an average particle diameter of 5 to 1 〇〇 nm in a ratio of 1 to 20% by mass based on the filler, the resin composition The impregnation property is good. For this reason, it is considered that the above-mentioned average particle diameter of 5~(10)run of the oxidized handsome is in the fiber of the 4 fiber-cloth, that is, in the strand and diffused to the fiber, so the particle size of the flat 5 5~i〇 A filler other than the oxidized surface of 〇nm can also be introduced into the fiber woven fabric. Thus, by using yttria particles having an average particle diameter of 5 to 1 〇〇 nm Material, it can be obtained in the strands with cerium oxide particles * In addition, due to The difference between the surface potential of the bismuth emulsified cerium particles having an average particle diameter of 5 to 100 nm and the surface potential of the other filler material causes the cerium oxide particles having an average particle diameter of 5 to 100 nm to interact with the above-mentioned filling T^T fins. Therefore, the average particle obtained 5~100 nm of the bismuth gasification ruthenium particles exist around the above-mentioned filler, the average particle size of 5~100 nm ~ - _ ~ gasification stone eve particles and have the role of spacers Thus, the average particle diameter of 5~]ηΛ. η111 of the dioxide dioxide particles exist around the filler, by exerting the tensile force caused by the van der Waals of the filler, so that The filler is made to have a higher dispersion state and is less agglomerated, and is reduced by the above-mentioned average particle diameter of 5 to 1 GGnm. The dispersion is dispersed in the organic solvent towel. II is preferably made in advance 9 to improve the filling. The material is divided into 101102467 8 201251534 ====__ she is reduced. The particles of the rationale are mostly easy _'1 ° nanometer size of the dioxin-like nanometer size collective, etc., secondary: weekly to resin composition Secondary condensation is formed by the use of aggregates The object can prevent this from being reduced to prevent the fluidity from being lowered. In addition, the present invention is agglomerated, and the surface of the island is preferably first treated by the agglomeration prevention and the use of the filler for the use of the island. The number of woven fabrics, the high-density fiber cloth is a fiber woven fabric that not only increases the yarn by flattening, but also reduces the weight of the yarn, such as a volume of dense households = treatment 3. Further, it is 1.05 g/cm or more. Thereby, the composition contains the remainder - the root fiber, so that it can be replenished and can be _. Further, (4) can fully ensure the fiber woven fabric, = filled in the prepreg When the copper layer is formed on the body, the formability when the surface is smoothed is maintained. In the case of the 4 sheets of the prepreg of the present invention, since the resin composition is excellent in fiber properties, it is less likely to occur. Further, since the =^ immersion filler & is low in thermal expansion, the warp of the printed wiring board of the present invention is small. In addition, the body pays for the expansion, "to make the pre-review of Wei 1; ^ the heat of the body. In addition, the prepreg system of the present invention is superior in heat and high rigidity. Further, the volume reading of the prepreg = dimension: of the present invention is preferably (10) rhyme. By using a high-density fiber woven fabric having a bulk density of 101102467 201251534 1'05 to 1.30 g/cm, when using an insulating layer as a printed wiring board, it is possible to form a hole and a shape with high precision by laser processing. And the pores in which the fibers protrude are suppressed. Further, 'generally' is a resin which is obtained by using a large amount of a resin composition containing a filler, and the impregnation property of the product is deteriorated, so that it is difficult for the substrate to maintain the resin composition in a uniform thickness. When the prepreg is used for the insulating layer to form a printed wiring board, the surface smoothness of the insulating layer or the adhesion between the conductor layers is inferior, and there is a problem that it is difficult to perform fine wiring processing. In this case, there is a tendency to deteriorate when the prepreg is made thinner. On the other hand, in the prepreg of the present invention, since the impregnation property of the resin composition to the fiber woven fabric is good, the fiber and the crepe cloth can maintain the resin composition in a uniform thickness, and the surface smoothness or the adhesion to the conductor is good. In addition, it is also thinner. Further, the present invention = "heating, south rigidity" by using a resin composition containing a filler in a large amount. First, the fiber woven fabric used in the present invention will be described. The fiber woven fabric to be used in the present invention is not particularly limited, and examples thereof include glass fibers, linaloamine, (IV), aromatic polyfluorene, fluororesin, and the like, and metal fibers, carbon lin, mineral fibers. A fiber woven fabric composed of materials. Among them, a glass fiber woven fabric composed of glass fibers is preferred because of its low thermal expansion property, high rigidity, and excellent dimensional stability. The glass fiber is not particularly limited, and is preferably 〇 〇 刈 刈 100 100 100 100 100% 1%, Al 2 〇 3 is 〇 mass % 〜 3 〇 mass %, and (10) is 〇 mass 101102467 201251534 % 〜 30 mass % The ratio includes the above-mentioned ones, and it is particularly preferable to use at least one type of glass selected from the group consisting of τ glass (sometimes referred to as "S glass"), D glass, bismuth glass, bismuth glass, and quartz glass; More preferably, bismuth glass (S glass), quartz glass, and D glass are preferably bismuth glass (S glass) or quartz glass from the viewpoint of excellent low thermal expansion property and high strength. Further, in the present invention, bismuth glass (S glass) means 62% by mass to 655% by mass of SiO 2 , 20% by mass to 25% by mass of a1203, 0% by mass to 0.01% by mass of CaO, and 10% by mass of MgO. ～15% by mass, B2〇3 is 〇% by mass to 0.01% by mass, Na20 and K20 are in a total amount of 0% by mass to 1% by mass, and the glass containing the composition of each of the above is included; D glass means 72% by mass based on SiO 2 . ～76 mass%, Al2〇3 is 0% by mass to 5% by mass, CaO is 〇% by mass to 1% by mass, MgO is 0% by mass to 1% by mass, and B2〇3 is 20% by mass to 25% by mass, Na20 And K20 is a glass containing the composition of each of the above in a ratio of 3% by mass to 5% by mass; the bismuth glass is 52% by mass to 56% by mass based on SiO 2 and 12% by mass of Al 2 〇 3 . /〇~16% by mass, CaO is 15% by mass to 25% by mass, Mg0 is 〇% by mass to 6% by mass, b2〇3 is 5% by mass to 10% by mass, and Na2〇 and K20 are 0% by mass to 合. The ratio of .8 mass% includes glass of the composition of each of the above; and the bismuth glass means 52 mass% to 56 mass by mass of SiO 2 . /. A1203 is 10% by mass to 15% by mass, CaO is 〇% by mass to 10% by mass, Mg0 is 〇% by mass to 5% by mass, B2〇3 is 15% by mass/〇20% by mass, and Na20 and K20 are total 〇质量%%1% by mass, Ti〇2 is 〇.〇5质量% to 5% by mass of the composition 101102467 201251534 glass containing the composition of each of the above; quartz glass means 99.0% by mass to 〇〇 mass% The ratio contains glass of Si〇2 composition. The glass fiber is not particularly limited, and is preferably a Young s modulus of 50 to 100 GPa when formed into a plate shape, and a tensile strength of 25 GPa or more when formed into a plate shape, and when the fiber is woven. The tensile strength in the longitudinal direction is 30 N/25 mm or more, and the Young's ratio in the case of a plate shape is preferably 80 1 OO GPa, and the tensile strength when the plate is formed into a plate shape is 35 GPa or more, and the length direction of the fiber woven fabric is pulled. The tensile strength is 45N/25mm or more. Thereby, a prepreg excellent in dimensional stability can be obtained. Further, the Young's rate is a value measured by a well-known three-point bending tester generally used in accordance with JIS R1602', and the tensile strength is a known constant-speed elongated shape generally used according to JIS R3420. The value measured by the tensile tester, the tensile strength in the longitudinal direction is a value measured by a constant-speed elongation type tensile tester similar to the above, using glass fiber as a woven fabric according to JIS r342. In the measurement of the Young's ratio and the measurement of the tensile strength, the term "plate shape" refers to a state in which a glass composition having the same composition as that of glass fibers is formed into a glass plate of MW. Further, in the longitudinal direction tensile strength measuring towel, the "longitudinal direction" in May means the direction of the warp (10) line. The glass fiber is not particularly limited, and the coefficient of read expansion in the warp direction measured by jisr is preferably 1 or less, and particularly preferably as follows. Thereby, the curvature caused by the thermal expansion of the printed wiring board can be reduced. The thickness of the above-mentioned fiber woven fabric is not particularly limited, and is preferably (7) to 1, 101102467 12 201251534, more preferably 10 to 140 μm, still more preferably 2 to 9 〇 μη. Thereby, the impregnation property of the resin composition with the fiber woven fabric is good, and the thickness can be made thinner. The fiber woven fabric preferably has a bulk density of 1.05 to 1.30 g/cm3 and particularly preferably 1,10 to beer. If the bulk density is less than the above, the laser processing property of the insulating layer is poor, and if the upper limit is exceeded, The impregnation property of the resin composition to the fiber woven fabric is deteriorated. Moreover, the bulk density of the fiber woven fabric is adjusted by the number of weaves of the circumference warp and (4), the fiber length of the fiber, and the flatness. The fiber woven fabric is not particularly limited, and the air permeability is preferably 3 to 5 Gee/em 2 /see. If the duty is less than the upper limit, the impregnation property of the resin composition to the fiber woven fabric is deteriorated. The upper limit value is inferior to the laser processing property of the insulating layer. The above-mentioned fiber woven fabric is not particularly limited to I. The basis weight is preferably UM6CW, particularly preferably 15 to 130 g/m2. If the basis weight is not, the thermal expansion property is poor, if it exceeds the upper limit The impregnation of the low impregnation of the Gu dip, or the flatness of the insulating layer is compared with the flattening ratio of the fiber used Α μ, ... ^. By making the fiber woven fabric always "inside" due to the resin The reliability of the composition on the upper edge, the flatness ratio between the holes of the (four) material can be extracted, and the fairyness. The thickness of the line in the invention is a value represented by the width of the line. 101102467 13 201251534 The fabric structure of the above-mentioned fiber woven fabric is not particularly limited, and examples thereof include a fabric structure such as plain weave, twill weave, woven fabric, and twill weave. In the laser processing, the thermal insulation resin composition used in the present invention is preferably a flat-woven structure from the viewpoint of excellent interlayer insulation reliability of the raw material, the strength, and the through hole. Next, the thermosetting resin composition used in the present invention will be described. The thermosetting resin composition contains at least a thermosetting resin and a filler. The filler is contained in a proportion of 50 to 85% by mass based on the solid content of the upper curing (10) fat composition. The ruthenium sulphate composition contains cerium oxide particles having an average particle diameter of 5 to 1 〇〇 nm in a ratio of 20% by mass of the filler. Further, the thermosetting resin composition may further contain hardening if necessary. A filler, a coupling agent, etc. (Filler) The filler is a cerium oxide particle having an average particle diameter of 5 to 100 nm in a ratio of idO mass% of the entire filler. The cerium oxide particles are not particularly limited, and for example, a combustion method such as a VMC (Vaporized Metal Combustion) method or a PVS (Physical Vapor Synthesis) method, a melting method for melting a crushed cerium oxide, a sedimentation method, or a coagulation can be used. A method such as a gel method, etc., particularly preferably a VMc method, wherein the VMC method refers to a method in which a tantalum powder is introduced into a chemical flame formed in an oxygen-containing gas to be burned and then cooled. In the VMC method, the particle diameter of the obtained bismuth oxide particles 101102467 14 201251534 can be adjusted by adjusting the particle size, the input amount, the flame temperature, and the like of the ruthenium powder to be supplied. Further, as the above-mentioned * oxidized dream particles, commercially available products such as NSS-5N (manufactured by TOKUYAMA Co., Ltd.) and Sicastar 43-〇〇-501 (manufactured by Microm〇d Co., Ltd.) can be used. The above-mentioned cerium oxide particles having an average particle diameter of 5 to 100 nm have an average particle diameter of 10 to 75 nm from the viewpoint of impregnation. Dioxide; when the average particle size of the particles is less than 5 nm, it cannot diffuse between the fibers of the fiber woven fabric, and when it is larger than 100 nm, it may not enter between the fibers.

上述二氧化矽粒子之平均粒徑可藉由例如雷射繞射散射 法、以及動態光散射法等進行測定。在上述平均粒徑 5〜lOOnm之二氧化矽粒子的情況’係藉由超音波使粒子分散 於水中’利用動態光散射式粒度分佈測定裝置(HORIB A 製’ LB-550) ’依體積基準測定粒子之粒度分佈，以其中徑 〇350)作為平均粒徑。 另外，上述二氧化矽粒子並無特別限定，較佳為疏水性。 藉此可抑制二氧化粒子之凝集，可使二氧化矽粒子良好分散 於本發明之樹脂組成物中。又，由於熱硬化性樹脂與二氧化 矽粒子間之親和性提升，上述熱硬化性樹脂與上述二氧化矽 粒子間之表面密黏性提升，故可得到機械強度優越的絕緣 層。 作為使一氧化矽粒子成為疏水性的方法，可舉例如對二氧 化石夕粒子事先藉由含官能基之矽烷類及/或烷基矽氮烷類進 行表面處理的方法等。作為上述含官能基之石夕烧類可使用公 10Π02467 15 201251534 知物，可舉例如環氧基矽烷、胺基矽烷、乙烯基矽烷、丙烯 酸系矽烷、巯基矽烷、異氰酸酯矽烷、硫化矽烷、脲矽烷等。 作為上述烷基矽氮烷類，可舉例如六甲基二碎氮燒 (HMDS)、1，3-二乙烯基-1，1，3,3_四曱基二矽氮烷、八曱基三 矽氮烷、六甲基環三矽氮烷等。又，藉由對二氧化矽粒子進 行上述表面處理，則亦可發揮填充材之凝集防止、以及提高 分散性的效果。 對上述二氧化矽粒子事先進行表面處理之含有官能基之 矽烷類及/或烷基矽氮烷類的量並無特別限定，相對於上述 二氧化石夕粒子1()〇重量份，較佳為_重量份以上且$重 篁份以下。更佳為〇]重量份以上且3重量份以下。若含有 S此基之⑪烧類及/或：^基⑦氮㈣貞的含量超過上述上限 值，則印刷佈線板製料有_緣層發生裂痕的情形，未滿 上述下限值時，财樹脂成分與二氧切粒子間 低的愔形。 τ 氧化神子事先藉由含有官能基之魏類及/或 表面處理的方法，並無特別限定，較佳為 气\"^方}特佳為濕式方法。相較於乾式方法， 法可對上述二氧切粒子之表面進行均勻處理。 上迷平t絲面處理較佳係進行至比表_的以上。 量%的比例含有。==粒子係依填充材整體 右否置未滿上述下限值，則有 101102467 201251534 提升含浸性之效果不足的情形，若含量超過上述上限值，則 有含浸性反而惡化、或預浸體之成形性差之虞。又，上述平 均粒徑5〜100nm之二氧化矽粒子之含量更佳為填充材整體 的3〜15質量％。 本發明所使用之填充材中，除了上述平均粒徑5〜1〇〇nm 之二氧化矽粒子以外，並無特別限定，可含有例如滑石、燒 成黏土、未燒成黏土、雲母、玻璃等之矽酸鹽，氧化鈦、氧 化鋁、平均粒徑大於l00nm之二氧化矽粒子等之氧化物， 碳酸鈣、碳酸鎂、水滑石等之碳酸鹽，氫氧化鋁、水鋁土 (AIO(OH) ’通常稱為「類」水鋁土之水鋁土 (亦即， ai2o3 · XH20 ’於此’㈣至2)、氫氧化鎂、氫氧化鈣等之 氫氧化物’硫酸鋇、硫_、亞硫賴等之硫酸鹽或亞硫酸 鹽’砸义鋅、甲基侧酸鋇、石朋酸銘、爛酸辦、硼酸納等之硼 酸鹽，氮化銘、氮化哪、氮切、氮化碳等之氮化物，鈦酸 ，猶等之鈦酸鹽等之無機填充材。上述無機填充材可 早、/等中之一種’亦可併用2種以上。此等之卡，較 佳為氫氧化鎂、氫氧化 ...,,$ 鋁、水鋁土、平均粒徑大於100nm 之球狀一氧化矽粒子、 脹性、含浸性的觀點而▲ “石、⑽銘；由低熱膨 5，特佳為水鋁土、平均粒徑大於 lOOnm之球狀二氧 卞尺於 ^.,,, 夕柢子、球狀氧化鋁。 作為上述平均粒徑5 填充材（以下有時p nm之二氧切粒子以外的無機 其他之無機填充材」）並無特別限 101102467 17 201251534 定，可使用平均粒徑為單分散的無機填充材，亦可使用平均 粒徑為多分散的無機填充材。再者，可併用平均粒徑為單分 散及/或多分散之無機填充材的1種或2種以上。本發明中 所謂平均粒徑為單分散，係指粒徑之標準偏差為1〇%以下 者’所謂多分散係指粒徑之標準偏差為1〇%以上者。 上述其他之無機填充材之平均粒徑並無特別限定，較佳為 〇·1μηι〜5~m ’特佳〇.1μιη〜3.0μιη。若其他之無機填充材之 粒徑未滿上述下限值，則因樹脂組成物之黏度變高，故有對 預浸體製作時之作業性造成影響的情形。又，若超過上述上 限值，則有樹脂組成物中發生無機填充材之沉降等現象的情 形。又，平均粒徑可使用雷射繞射/散射式粒度分佈測定裝 置（島津製作所製，SALD-7000等之一般機器）進行測定。 再者，在進行小徑孔之加工、孔之狹間距加工、及細線加 工的情況，上述其他之無機填充材較佳係經粗粒分割。其中 較佳係經45μιη以上的粗粒分割、更佳為2〇μιη以上的粗粒 分割、特佳為1 〇 μπι以上的粗粒分割。又，所謂「粗粒分割」， 係指將其粒徑以上之大尺寸的粗粒排除。 另外，本發明所使用之填充材，較佳係除了上述無機填充 材以外亦含有橡膠粒子等之有機填充材等。作為本發明可使 用之橡膠粒子之較佳例，可舉例如核殼型橡膠粒子、交聯丙 稀腈丁二雜雜子、交聯苯乙射二烯橡膠粒子、丙稀酸 系橡膠缸子、聚矽氧粒子等。 101102467 201251534 核殼型橡膠㈣係具有核層與殼層的㈣粒子，可舉例 ^外層之殼層為由破璃狀聚合物所構成，内層之核層為由 :祕合物所構成的2層構造;或外層之殼層為由玻璃狀 K °物斤構成+間層為由橡膠狀聚合物所構成，核層為由 玻璃狀聚合物所構成的3層構造者等。玻璃狀聚合物層係例 如由甲基丙烯酸甲S旨之聚合物等所構成，橡膠狀聚合物層係 例如由丙_丁醋聚合物(丁基橡膠)等所構成。作為核殼塑 橡膠粒子之具體例’可舉例如Stafiloid AC3832、The average particle diameter of the above cerium oxide particles can be measured by, for example, a laser diffraction scattering method, a dynamic light scattering method, or the like. In the case of the above-described cerium oxide particles having an average particle diameter of 5 to 100 nm, the particles are dispersed in water by ultrasonic waves. The volume is determined by a dynamic light scattering type particle size distribution measuring apparatus (HORIB A 'LB-550'. The particle size distribution of the particles, in which the diameter 〇 350) is taken as the average particle diameter. Further, the above cerium oxide particles are not particularly limited, and are preferably hydrophobic. Thereby, aggregation of the dioxide particles can be suppressed, and the cerium oxide particles can be well dispersed in the resin composition of the present invention. In addition, since the affinity between the thermosetting resin and the cerium oxide particles is improved, the surface adhesion between the thermosetting resin and the cerium oxide particles is improved, so that an insulating layer having excellent mechanical strength can be obtained. As a method of making the ruthenium oxide particles hydrophobic, for example, a method in which a surface of the cerium oxide particles is subjected to surface treatment by a functional group-containing decane and/or a alkyl decazane is used. As the above-mentioned functional group-containing sinter, a known product can be used, and examples thereof include an epoxy decane, an amino decane, a vinyl decane, an acrylic decane, a decyl decane, an isocyanate decane, a decane sulfide, and a urea decane. Wait. Examples of the alkyl sulfonium alkane include hexamethyldiazepine (HMDS), 1,3-divinyl-1,1,3,3-tetradecyldioxane, and octadecyl. Trioxane, hexamethylcyclotriazane, and the like. Further, by performing the above surface treatment on the cerium oxide particles, the effect of preventing aggregation of the filler and improving the dispersibility can be exhibited. The amount of the functional group-containing decane and/or alkyl decazane to be surface-treated in advance with respect to the above-mentioned cerium oxide particles is not particularly limited, and is preferably 1 part by weight based on the weight fraction of the cerium oxide particles. It is _ parts by weight or more and more than 5% by weight. More preferably, it is more than 5% by weight and not more than 3 parts by weight. When the content of the 11-burning type and/or the base 7 nitrogen (tetra) fluorene of S is more than the above upper limit, the printed wiring board material may have a crack in the edge layer, and if the lower limit is not satisfied, The low resin shape between the resin component and the dioxate particles. The τ oxidized sage is not particularly limited by a method containing a functional group and/or a surface treatment, and it is preferably a gas method which is preferably a wet method. The surface of the above-mentioned dioxo particles can be uniformly treated compared to the dry method. The upper flat t-filament treatment is preferably carried out to the above table. The proportion of % is contained. ==The particle system is not full of the above lower limit depending on the overall right of the filler. If there is insufficient effect of improving the impregnation, if the content exceeds the above upper limit, the impregnation may deteriorate, or the prepreg The poor formability. Further, the content of the cerium oxide particles having an average particle diameter of 5 to 100 nm is more preferably 3 to 15% by mass based on the entire filler. The filler used in the present invention is not particularly limited as long as the above-mentioned cerium oxide particles having an average particle diameter of 5 to 1 〇〇 nm, and may contain, for example, talc, fired clay, unfired clay, mica, glass, or the like. Oxalate, titanium oxide, aluminum oxide, oxides such as cerium oxide particles having an average particle diameter of more than 100 nm, carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, aluminum hydroxide, bauxite (AIO (OH) ) 'Water bauxite commonly referred to as "class" bauxite (ie, ai2o3 · XH20 'here' (4) to 2), hydroxides of magnesium hydroxide, calcium hydroxide, etc. 'barium sulfate, sulfur_, Sulfate or sulfites such as sulfite or sulfites, such as zinc, methyl sulphate, saponin, sulphuric acid, borate, borate, nitriding, nitriding, nitrogen cutting, nitrogen An inorganic filler such as a nitride such as carbon, a titanic acid, or a titanate such as a titanate. The inorganic filler may be used in combination of two or more types, such as early, or the like. Magnesium hydroxide, hydroxide...,, aluminum, bauxite, spherical cerium oxide particles having an average particle diameter of more than 100 nm, swelling , impregnation point of view ▲ "Shi, (10) Ming; from low heat expansion 5, particularly good for bauxite, spherical dioxin with an average particle size greater than lOOnm in ^.,,, Xizizi, spherical oxidation Aluminium. The above-mentioned average particle size 5 filler (hereinafter, other inorganic inorganic fillers other than the oxidized particles of p nm) is not limited to 101102467 17 201251534, and an inorganic powder having an average particle diameter of monodisperse can be used. In addition, one or two or more types of inorganic fillers having an average particle diameter of monodisperse and/or polydisperse may be used in combination with the filler. In the present invention, the average is used. The particle size is monodisperse, which means that the standard deviation of the particle diameter is 1% or less. The so-called polydisperse means that the standard deviation of the particle diameter is 1% or more. The average particle diameter of the above other inorganic fillers is not particularly Preferably, it is preferably 〇·1μηι~5~m 'Special 〇.1μιη~3.0μιη. If the particle diameter of the other inorganic filler is less than the above lower limit, the viscosity of the resin composition becomes high, so A situation that affects the workability of the prepreg. When the above-mentioned upper limit is exceeded, a phenomenon such as sedimentation of the inorganic filler may occur in the resin composition. Further, the average particle diameter may be a laser diffraction/scattering particle size distribution measuring apparatus (SALD-manufactured by Shimadzu Corporation) The measurement is performed in a general machine such as 7000. Further, in the case of processing a small diameter hole, a narrow pitch processing of a hole, and a fine line processing, the other inorganic filler is preferably divided into coarse particles. It is divided into coarse particles of 45 μm or more, more preferably coarse particles of 2 μm or more, and fine particles of 1 μm or more. It is also referred to as "rough grain division". In addition, the filler used in the present invention preferably contains an organic filler such as rubber particles in addition to the inorganic filler. Preferred examples of the rubber particles usable in the present invention include core-shell type rubber particles, cross-linked acrylonitrile-butadiene-doped hetero-, cross-linked styrene-butadiene rubber particles, and acrylic acid-type rubber cylinders. Polyoxygenated particles, etc. 101102467 201251534 Core-shell rubber (4) is a (four) particle having a core layer and a shell layer. For example, the shell layer of the outer layer is composed of a glass-like polymer, and the core layer of the inner layer is composed of a layer composed of a secret compound. The structure or the outer shell layer is composed of a glassy K° material jin + the interlayer is composed of a rubber-like polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate or the like, and the rubbery polymer layer is composed of, for example, a propylene glycol polymer (butyl rubber). Specific examples of the core-shell rubber particles are exemplified by Stafiloid AC3822.

AC3816N(商品名 Ganz 化成（股）製），METABLEN KW_4426(商品名三菱嫘f (股）製）。作為交聯丙烯腈丁二稀 橡膠(臟)粒子的具體例’可舉例b XER-91(平均粒徑 〇.5μιη，JSR(股)製)等。 二 作為交聯苯乙烯丁二烯橡膠(SBR)粒子的具體例，可舉例 如XSK-500(平均粒徑〇 _，JSR(股）製）等。作為丙稀酸系 橡膠粒子之具體例，可舉例如METABLEN ws⑽A(平均粒 仅Ο.ίμηι)、W450A(平均粒徑〇.；2pm)(x菱嫘營(股)製）等。 上述聚矽氧粒子若為由有機聚矽氧烷所形成之橡膠彈性 微粒子’則無特別限定，可舉例如由聚矽氧橡膠（有機聚矽 氧烷交聯彈性體）本身所構成的微粒子，以及將由二維交聯 主體之聚矽氧所構成之核部藉三維交聯型主體之聚發氧所 被覆的核殼構造粒子等。作為上述聚矽氧粒子，可使用 KMP-605、ΚΜΡ-600、KMP-597、KMP-594(信越化學（股） 101102467 19 201251534 製）、TORAYFILE-500、TORAYFILE-600(東麗·道康寧(股) 製）等之市售物。 本發明所使用之填充材中，對於平均粒徑5〜i〇〇nm之二 氧化石夕粒子以外之填充材，亦為了防止凝集、提高分散性， 較佳亦事先施行表面處理。表面處理劑可使用公知之矽烷偶 合劑，可舉例如環氧基矽烷、胺基矽烷、乙烯基矽烷、丙烯 酸系矽烷、酼基矽烷等。又，表面處理較佳係進行比表面積 的50%以上。 本叙明所使用之樹脂組成物中之填充材的含量，較佳為樹 脂組成物整體之固形分基準的5〇〜85質量％、特佳&〜乃質 罝％。若填充材含量超過上述上限值，則樹脂級成物之流動 性極差，製造預浸體時之作業性劣化。若未滿上述下限值， 則熱膨脹係數較高，有絕緣層之強度不足的情形。 (熱硬化性樹脂） 作為熱硬化性樹脂並無特別限定，可使用環氧樹脂、衫 醋樹脂、雙順丁烯二醯亞胺樹脂、苯_脂、笨并十曰f 乙烯基f基_脂、苯并環丁_脂等，通常係 中適當組合其他之熱硬化性樹脂而使用。、、氧相 作為上述環氧樹脂並無特觀定，較佳係實質 子者。於此，所謂「實質上不含㈣子」，係 s虐 氧樹脂之合成過程中Ml ,、 、。來自名AC3816N (trade name Ganz Chemical Co., Ltd.), METABLEN KW_4426 (trade name Mitsubishi 嫘f (share) system). Specific examples of the crosslinked acrylonitrile butadiene rubber (dirty) particles are, for example, b XER-91 (average particle diameter 〇.5 μιη, manufactured by JSR Co., Ltd.). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include, for example, XSK-500 (average particle diameter 〇 _, manufactured by JSR Co., Ltd.). Specific examples of the acrylic rubber particles include, for example, METABLEN ws (10) A (average particle size only ί.ίμηι), W450A (average particle diameter 〇.; 2 pm) (manufactured by X.K.). The above-mentioned polyfluorene oxide particles are not particularly limited as long as the rubber elastic fine particles formed of the organopolysiloxane, and may be, for example, fine particles composed of a polyoxyxene rubber (organic polyoxyalkylene crosslinked elastomer). And a core-shell structure particle in which a core portion composed of a polyfluorinated oxygen of a two-dimensionally crosslinked body is coated with polyoxygenation of a three-dimensional crosslinked type body. As the above polysiloxane particles, KMP-605, ΚΜΡ-600, KMP-597, KMP-594 (Shin-Etsu Chemical Co., Ltd. 101102467 19 201251534), TORAYFILE-500, TORAYFILE-600 (Toray Dow Corning) can be used. ))). In the filler used in the present invention, it is preferable to carry out a surface treatment in advance in order to prevent aggregation and improve dispersibility for a filler other than the particles having an average particle diameter of 5 to i 〇〇 nm. As the surface treatment agent, a known decane coupling agent can be used, and examples thereof include epoxy decane, amino decane, vinyl decane, acrylic decane, and mercapto decane. Further, the surface treatment is preferably carried out at 50% or more of the specific surface area. The content of the filler in the resin composition used in the present invention is preferably 5 〇 to 85% by mass, particularly preferably & 〜% by mass based on the solid content of the entire resin composition. When the content of the filler exceeds the above upper limit, the fluidity of the resin grade is extremely poor, and the workability at the time of producing the prepreg deteriorates. If the lower limit is not exceeded, the coefficient of thermal expansion is high and the strength of the insulating layer is insufficient. (thermosetting resin) The thermosetting resin is not particularly limited, and an epoxy resin, a shirt vinegar resin, a bis-succinimide resin, a benzene-lipid, a stupid and a fluorene-based group can be used. A fat, a benzocyclobutyl-lipid or the like is usually used in combination with other thermosetting resins. The oxygen phase is not particularly limited as the above epoxy resin, and is preferably a substantial one. Here, the term "substantially free of (four) sub-" is a process in which Ml, , and are synthesized in the synthesis of an aerobic resin. From the name

太主 使用之南素系成分的齒素H 齒素去除步驟仍殘存於環氧樹脂^通常較佳係^2 101102467 20 201251534 中不含有超過30ppm的鹵原子。 型上不含^子的環氧樹脂，可舉例如雙紛A “氧奶日、雙型環氧樹脂、㈣E型 酚S型環氧樹脂、雙酚Z型環氧樹脂(4,4，、严:曰 環氧樹脂)、雙酴P型環氧樹脂(4,4，_(1，4)’_伸:—_雙_ 雙齡型環氧樹脂）、雙盼Μ型環氧樹脂(4‘二=丙基） :丙基)雙峨氧樹脂)等之環紛型環氧樹赌、 =崎旨侧議型環氧樹脂等之_清漆型： 氧樹月曰、聯苯型環氧樹脂、二曱笨型環 “- 型環氧樹脂、聯苯基芳咖環氧樹脂、聯心== ==:=甲㈣㈣漆型環氧樹m，2,2^ 乙烷之％虱丙基醚類、3官能或4官能 I:苯型環氧樹脂等之芳基伸‘氧樹：二 =1型:二萘改質甲_黍型環氧樹脂、甲氧基 —f基脂、萘·環氧樹 二葱型環氧樹脂、苯氧基型環氧樹脂、二環戊:= ^月曰降福烯型壤氧樹脂、金剛院型環氧樹脂、第型環氧樹 月曰將上述環氧樹脂經鹵化的難燃化環氧樹脂等。 =中’可單獨使用】種之環氧樹脂，:可併用 = 子量的2種以上之環氧樹月旨，或可併用】種或 以上之缞氧樹脂與環氧樹脂之預聚物。 此等環氧樹脂中，特佳為選自由聯苯基二亞甲基型環氧樹 101102467 21 201251534 難燃性 月曰酚搭/月型％氧料脂、萘改質甲紛紛酸清漆環氧樹 蒽型環氧龍所組鱗之至少1種。藉岐以等環^ 脂，可提升所得之制缺印刷板之料_耐熱性及 另外’此等環氧樹脂中，藉由使用萘醚型環氧樹脂，則可 提升所得之制板及印·線板的_性、低熱膨脹性及 熱收縮性。 - 蔡謎型環氧樹脂例如可由下述—般式⑴所表示。 [化1]The dentate H dentate removal step of the melanosome component used by the lord is still present in the epoxy resin. It is generally preferred that the system does not contain more than 30 ppm of halogen atoms. The type of epoxy resin does not contain a type of epoxy resin, for example, a double A "oxygen day, double type epoxy resin, (four) E type phenol S type epoxy resin, bisphenol Z type epoxy resin (4, 4, Strict: 曰 epoxy resin), double 酴 P type epoxy resin (4, 4, _ (1, 4) ' _ stretch: - _ double _ double age epoxy resin), double antimony type epoxy resin ( 4'di=propyl): propyl) bismuth oxy-resin), etc., epoch-type epoxy gambling, akiji-type epoxy resin, etc. varnish type: Oxygen tree, biphenyl ring Oxygen resin, two-pronged ring "-type epoxy resin, biphenyl aryl coffee epoxy resin, joint heart == ==:=A (four) (four) lacquer-type epoxy tree m, 2, 2 ^ % of 虱An aryl ether of a propyl ether, a trifunctional or a tetrafunctional I: benzene type epoxy resin, etc.: an oxygen tree: a two-type 1 type: a phthalocyanine-modified epoxy resin, a methoxy-f-based grease, Naphthalene·epoxy tree scallion type epoxy resin, phenoxy type epoxy resin, dicyclopentane:= ^yue 曰 pentene type oxy-resin, diamond-type epoxy resin, type epoxy tree A flame-retardant epoxy resin or the like obtained by halogenating the above epoxy resin. = "Metal" can be used alone. It can be used in combination with two or more kinds of epoxy resins, or a prepolymer of epoxy resin and epoxy resin. Among these epoxy resins, it is particularly preferred to be selected from the group consisting of biphenyl dimethylene type epoxy tree 101102467 21 201251534 flame retardant urecol phenol/month type % oxyester fat, naphthalene modified sulphur acid varnish epoxy At least one species of the tree-shaped epoxy dragon. By using 等 ^ , , , , , , _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ • _ properties, low thermal expansion and heat shrinkage of the wire. - The Charpy type epoxy resin can be expressed, for example, by the following general formula (1). [Chemical 1]

.上《氧樹脂之含量並無特靠定，較佳係以上述樹脂乡且 成物整體之_份基準計為5〜6G重量％。若含量未滿上述 下限則有樹脂組成物之硬化性降低、或使用該樹脂組成 物所付之預浸體或印刷佈線板的耐濕性降低的情形。又，若 超過上述上限值’財預浸體或印刷佈線板之熱膨服率變 大或耐熱性降低的情形。上述環氧樹脂之含量特佳係以樹 10Π02467 22 201251534 脂組成物整體之固形份基準計為1 〇〜5〇重量％。 上述環氧樹脂之重量平均分子量並無特別限定.，較佳為 Ι·0χΐ02〜2.0Χ104。苦重量平均分子量未滿上述下限值，則有 於預浸體之表面產生裂痕的情形，若超過上述上限值，則有 預浸體之焊錫耐熱性降低的情形。藉由將重量平均分子量設 為上述範圍内，則玎作成此等特性之平衡優越者。 本發明中，上述環氧樹脂之重量平均分子量係藉由例如凝 膠滲透層析法(GPC)所測定，作為聚苯乙烯換算之重量分子 量而特定。 上述樹脂組成物並無特別限疋，藉由含有氰酸酯樹脂，可 提升難燃性，減小熱膨脹係數，進而提升預浸體之電氣特性 (低介電係數、低介電損耗正切）等。 上述異氣酸樹脂並無特別限疋’例如可使鹵化氣化合物斑 酚類或萘酚類反應，視需要藉加熱等方法進行預聚合物化而 獲得。又，亦可使用如此調製之市售物。 作為上述氰酸酯樹脂之種類並無特別限定，可舉例如盼路 清漆型氰酸酯樹脂、雙酚Α型氰酸酯樹脂、雙酚Ε型氰酸 酯樹脂、四甲基雙酚F型氰酸酯樹脂等之雙酚型氰酸酯樹脂 等。 曰 上述氛暖龍樹脂較佳係於分子内具有2個以上氰酸g旨基 (•0-CN)。可舉例如2,2，_雙(4_氰氧基苯基)亞異丙基、1，】，_ 雙(4_氰氧基苯基）乙烷、雙(4-氰氧基-3,5-二甲基笨基）甲 101102467 23 201251534 烧、1，3·雙(4·氰氧基苯基·！♦曱基亞乙基))苯、二環戊二稀 型異氰酸酯、苯酚酚醛清漆型異氰酸酯、雙(4_氰氧基笨美) 硫喊、雙(4-氰氧基苯基)醚、Μ}參(4_氣氧基笨基）乙燒土' 參(4-氰氧基苯基)亞磷酸酯、雙(4_氰氧基苯基)砜、雙(4_ 氰氧基苯基）丙烷、1，3·、Μ_、1，6_、1，8_、2,6_或 27-二氰 氧基萘、1，3,6-三氰氧基萘、4,4_二氰氧基聯苯及苯酚酚醛清 漆型、曱酚酚醛清漆型之多元酚類與鹵化氰間之反應所得的 氰酸酯樹脂，由萘酚芳烷基型之多元萘酚類與鹵化氰間之反 應而得的氰酸酯樹脂等。 此等之中’苯酚酚醛清漆型氰酸酯樹脂係難燃性及低熱膨 脹性優越，2,2-雙(4-氰氧基苯基）亞異丙基及二環戊二締型 氰酸酯係交聯密度之控制及耐濕可靠性優越。由低熱膨服性 之觀點而言，特佳為苯酚酚醛清漆型氰酸酯樹脂。又，可進 一步併用1種或2種以上之其他氰酸酯樹脂，而無特別限定。 上述氰酸酯樹脂可單獨使用。又，亦可併用重量平均分子 量不同的2種以上之氰酸酯樹脂、或將上述氰酸酯樹脂與其 預聚物併用。 上述預聚物通常係將上述氰酸酯樹脂藉加熱反應等，予以 例如3聚化而獲得，為了調整樹脂組成物之成形性、流動性 而可適合使用。 上述預聚物並無特別限定’於例如使用3聚化率為2〇~5〇 重量％之預聚物時，可表現良好的成形性、流動性。 101102467 24 201251534 上述氰酸酯樹脂之含量並無特別限定，較佳係以樹脂組成 物整體之固形份基準計為5〜60重量。/。、更佳1〇〜5〇.重量％<> 右氰酸酯樹脂之含量為上述範圍内，則可更有效地提升預浸 體之耐熱性及難燃性。若氰酸酯樹脂之含量未滿上述下限 值，則有預浸體之熱膨脹性變大、耐熱性降低的情形，若超 過上述上限值，則有預浸體之強度降低的情形。 上述氰酸酯樹脂之重量分子量並無特別限定，較佳為 5’〇xl〇2〜4.5xl〇3、特佳6 〇xl02〜3.〇χ1〇3。若重量平均分子量 未滿上述下限值，則有於預浸體之表面產生裂痕、或機械強 度降低的情形。又，若重量平均分子量超過上述上限值，則 有樹脂組成物之硬化反應變快、與導體層間之密黏性惡化的 情形。 本發明中’上述氰酸醋樹月旨之重量平均分子量可藉由例如 凝勝滲透層析法(GPC)進行敎，作為聚苯乙_算之重量 分子量而特定。 ^述樹脂組成物並無特舰定，藉由含有雙順丁烯二酿亞 月女樹脂’可提升耐熱性。 作為上述雙順丁稀二醯亞胺樹脂並無特別限定，可舉例如 Ν，Ν，-(4,4，·二苯基甲烧)雙順丁婦二酿亞胺、雙(3-乙基_5·甲 基冰順丁烯二醯亞胺苯基）Wϋ雙卜(4_順丁稀二醯亞 胺苯氧娜細科之雙順谓二醯亞胺娜。上述雙順 丁稀二醯亞胺樹脂可進-步併用—種或2種以上之其他雙 101102467 25 201251534 順丁烯二醯亞胺樹脂，並無特別限定。又，上述雙順丁烯二 醯亞胺樹脂亦可單獨使用。又，亦可併用重量平均分子量不 同的雙順丁婦二酿亞胺樹脂，或併用上述雙順丁烯二醯亞胺 樹脂與其之預聚物。 上述雙順丁烯二醯亞胺樹脂之含量並無特別限定，較佳係 以樹脂組成物整體之固形份基準計為卜35重量％、特佳 5〜20重量％。 (硬化劑、硬化促進劑） 本發明所使用之樹脂組成物亦可併用硬化劑。作為硬化劑 並無特別限定，在例如使用環氧樹脂作為上述熱硬化性樹脂 時，可使用一般使用作為環氧樹脂之硬化劑的酚系硬化劑、 脂肪族胺、芳香族胺、二氰二醯胺、二羧酸二肼化合物、酸 酐等。 另外，本發明所使用之樹脂組成物中，視需要可添加硬化 促進劑。上述硬化促進劑並無特別限定，可舉例如有機金屬 鹽、3級胺類、咪唑類、有機酸、鑌鹽化合物等。作為硬化 促進劑，可單獨使用包括其等中之衍生物的1種，亦可併用 包括其等中之衍生物的2種以上。 (偶合劑） 上述樹脂組成物亦可進一步含有偶合劑。偶合劑係為了使 熱硬化性樹脂與填充材間之界面的濕潤性提升而予以調 配。藉此，可使樹脂及填充材對纖維織布均勻地定著，改良 Ϊ01102467 26 201251534 預浸體之耐熱性、尤其是吸濕後之焊锡耐熱性。 上述偶合劑並無特別限定，可舉例如環氧基魏偶合劑、 _子性外偶合劑、胺基魏偶合劑、鈦酸料偶合劑、 .聚魏油型偶合劑等。藉此，可提高與填充材之界面間的濕 潤性，藉此可更加提升預浸體的耐熱性。 ^述偶合劑之添加量並無特別限定，相對於填充材1〇〇 重量份，較佳為0.05〜3重量份、特佳〇卜2重量份。若含 量未滿上述下限值，_無法充分被覆填储，故有提升耐 熱性之效果降低的情形。又，若含量超過上述上限值，則尉 反應造成影響，而有彎曲強度等降低的情形。 (其他） β / 另外，上述樹脂組成物中，視需要亦可添加消泡劑、均平 劑、紫外線吸收劑、發泡劑、抗氧化劑、難燃劑、鱗系1 猜類等之難燃助劑、離子捕捉劑等之上述成分以外的添如 物。 、本發明之預浸體係將於溶财含有上述熱硬化性樹脂組 成物之清漆保持於纖維織布後，藉由去除上述溶劑而獲得。 •上述清漆之調製方法並無特別限定，較佳係例如調製使熱硬 ，化性樹脂及填充材分散於溶媒中的聚料，於該聚料中添加其 他之樹脂組錄之成分，再加人上述溶媒使其諸、混合的 方法。藉此，可提升填充材之分散性，使上述填充材中所含 之平均粒徑5〜100nm之二氧化石夕粒子容易進入纖維織布 101102467 27 201251534 中，可提升樹脂組成物對纖維織布的含浸性。 /尚且’本發明中所謂於溶射含有熱硬化性樹脂組成物， 係指上述熱硬化性樹缝成物所含之可溶性樹脂等溶解於 溶劑中，不溶性之填充材等分散於溶劑中。 作為上述溶媒並無特別限定，較佳係對上述樹脂組成物顯 示良好溶解性的溶媒，可舉例如丙酮、甲基乙基酮(mek)、 裱己酮(ANON)、曱基異丁基酮(ΜΙΒΚ)、環戊酮、二甲基曱 醯胺、二甲基乙醯胺、Ν-甲基鱗咬酮等。又，在不造成不 良影響的範圍内亦可使用不良溶媒(ρ·牆㈣。 上述清漆所含之樹脂組成物的固形份（由清漆去除了溶劑 的成分)並無特別限^，較佳為3G〜8G重量％、特佳4〇〜7〇 重量％。藉此，使樹脂組成物對纖維織布的含浸性提升。又， 可抑制塗敷時之表面平滑性、厚度偏差等。 使上述清漆含浸於上述纖維織布中的方法，可舉例如將纖 維織布浸潰於清漆中的方法、由各種塗佈器進行塗佈的方 法、由喷霧Is.進彳了切的方法、將清漆於基材上進行塗佈/ 乾燥而製作樹脂片並將該樹脂片依樹脂層與纖維織布相接 的方式配置而予以壓黏的方料。此等之中，較佳為將纖維 織布浸潰於清漆中的方法。藉此，可提升熱硬化性樹敝成 物對纖賴布的含浸性。又，麵藝織布浸漬於清漆中 時，可使用通常之含浸塗佈設備1，可將上述清漆之溶劑 於例如％〜18(TC進行乾燥卜10分鐘，藉此得到半硬化的預 101102467 28 201251534 浸體。 上述預次體係知錢維㈣所 該纖維織布層之兩面所形成 二，層、與在 層所構成。上述纖維織布層的厚p日、、，成物所構成之樹脂 1〇~200μΐη^„ 厚度（僅單面之-層份的厚度）並無特H述樹脂層之 〇.5〜2(^111、特佳2〜1〇 夢 …、’、疋，車父佳為 狀厚度為上缝_，則與導體層間 ^度及= 性更加良好。 在站性及表面平滑 上述預浸體之整體厚度 30〜220μιη、特佳 40〜165μιη。藉 且亦可對應薄型化。 並無特別限定，較佳為 此’則預浸體之操作性良好， 上述預浸體中 ^ 踝股中，於構成線股之 ，、維所，伸的方向上不存在具有以上長度的空隙。藉 ^可提升將觀_於絕緣層而得之印刷佈線板的絕緣可 罪性。再者，構成纖維織布之線財，較佳係於構成線股之 纖維所延伸的方向上^；存在具有2G_以上、尤其是 以上長度的空隙。 另外，上述預浸體中，構成纖維織布之線股中之直㈣ 5〇卿以上之空隙的數密度為5(W。此時，可提升將預浸 體用於絕緣層而得之印刷佈線板的絕緣可靠性。再者，構成 纖維織布之線股中之直徑5G_以上之空_數密度較佳為 101102467 29 201251534 20cm·1以下、特佳10cm·1以下。 尚且，上述線股中之空隙的長度或數密度，可藉由適當調 整存在於線股中之二氧化矽粒子之平均粒徑或纖維織布之 體積密度等而實現。 2.積層板 接著，說明積層板。 本發明之積層板的特徵在於使上述本發明之預浸體硬化 而獲得。又，本發明之積層板較佳係於上述本發明之預浸體 的至少一外側面上設置導體層而成。 上述預浸體可使用1片，亦可使用積層了 2片以上的積層 體。在設置導體層而成之積層板（以下有時稱為「金屬箔積 層板」）時，係於上述預浸體上積層金屬箔，予以加熱加壓 而獲得。在使用1片之預浸體時，係於其上下兩面或單面上 重疊金屬箔，在使用積層了 2片以上預浸體之積層體時，則 於該積層體之最外側的上下兩面或單面上重疊金屬箔。接 著，藉由對重疊了預浸體與金屬箔者進行加熱加壓成形，可 得到金屬箔積層板。 作為上述金屬箔，可舉例如銅、銅系合金、！呂、I呂系合金、 銀、銀系合金、金、金系合金、鋅、鋅系合金、鎳、鎳系合 金、錫、錫系合金、鐵、鐵系合金等之金屬箔。又，亦可藉 由鍍覆形成上述般之銅、銅系合金等之導體層。 在製造金屬箔積層板時，加熱溫度並無特別限定，較佳為 101102467 30 201251534 120〜220°C、特佳150〜200°C。加壓之壓力並無特別限定， 較佳為0.5〜5MPa、特佳1〜3MPa。又，視需要亦可於高溫槽 等在150〜300°C之溫度進行後硬化。 另外，作為製造本發明之金屬箔積層板的其他方法，可舉 例如使用圖1所示之具有樹脂層之金屬箔的金屬箔積層板 的製造方法。首先，準備於金屬箔11上藉塗佈器塗佈了均 勻之樹脂層12的具有樹脂層之金屬箔10。接著，於纖維織 布20之兩側上，將具有樹脂層之金屬箔10、10依樹脂層 12為内側進行配置（圖1(a))，於真空中依加熱60〜130°C、 加壓0.1〜5MPa使其層合含浸。藉此，得到具有金屬箔之預 浸體41(圖1(b))。接著，對具有金屬箔之預浸體41直接進 行加熱加壓成形，藉此可得到金屬箔積層板51(圖1(c))。 進而，作為製造本發明之金屬箔積層板的其他方法，亦可 舉例如圖2所示之使用了具有樹脂層之高分子薄膜片的金 屬箔積層板的製造方法。首先，準備於高分子薄膜片31上 藉塗佈器塗佈了均勻之樹脂層32的具有樹脂層之高分子薄 膜片30。接著，於纖維織布20之兩側上，將具有樹脂層之 高分子薄膜片30、30依樹脂層32為内側進行配置（圖2(a))， 於真空中依加熱60〜130°C、加壓0.1〜5MPa使其層合含浸。 藉此，得到具有高分子薄膜片之預浸體42(圖2(b))。接著， 將具有高分子薄膜片之預浸體42之至少單面的高分子薄膜 片31剝離後（圖2(c)中係剝離兩面），於剝離了高分子薄膜 101102467 31 201251534 片31之面上配置金屬g 11(圖2(d))，進行加熱如壓成形， 藉此可得到金屬箔積層板52(圖2(e))。進而，在剝離兩面之 高分子薄膜片時’係與上述預浸體同樣地亦可積層2片以 上。在積層2片以上之預浸體時，係在經積層之頓浸體之最 外側的上下雨面或單面上配置金屬落或高分子_片，藉由 進行加熱加魘成形而可得到金屬箱積層板。藉此耩製造方法 所得之金屬钿積層板係厚度精度高、厚度岣勻，進而表面平 滑性優越。又’由於可得到成形應變小的金屬箱積層板，故 使用藉該製造方法所得之金屬箔積層板而製成的印刷佈線 板及半導體裝置，係㈣較小、曲_差亦較γ進而可產 率佳地製造印刷佈線板及半導體裝置。 作為上述加熱加壓成形的條件，溫度並無特別隊定，較佳 為120〜250°C、特佳15〇〜22(rc。上述加壓之磨力並無特別 限疋，較佳為0.1〜5MPa、特佳0.5〜3MPa。進而祝需要可於 高溫槽等中在150〜3〇(TC之溫度進行後硬化。 圖1〜2等之金屬箔積層板並無特別限定，例如圩使用製造 具有樹脂層之金屬箔的裝置及製造金屬箔積層板之裝置進 行製造。 在製造上述具有樹脂層之金屬箔的裝置申，金屬箔係使用 例如將長尺之片材品作成捲物形態者等，藉此 < 連續地捲出 而進行供給。藉由樹脂之供給裝置，使樹脂清漆依既定量連 續地供給至金屬箔上。於此，作為樹脂清漆，係使用將本發 101102467 32 201251534 明之樹脂組成物溶解、分散於溶射而得之塗佈液。樹脂清 漆之塗佈量可藉由到刀親、與該刮刀輕之備用輥間之間隙所 控制。塗佈了既定量之樹脂清漆的金屬，係料至橫搬送 =風乾燥裝置之内部，將樹脂清漆中所含有之有機溶劑 貫質地乾燥去除，視需要可作成使硬化反應進行至途中的 “有樹^層之金屬_。具有樹脂層之金屬㈣藉由可直接進 ==的層合輥，在形成了樹脂層之侧上重疊保鹱薄膜，捲 ^ 了雜護_之具有樹脂層之金心，㈣_形態 的“有絕緣樹脂層之金屬箔。在使用圖丨〜2等之製乂方去 時，相較於習知之使清漆含浸的製造方法 _以方法 ” 3勻之樹脂量 、控制、以及面内厚度精度優越，故搭載 導體裳置的她偏差較小、產率提升。H件之半 另外，藉此種製造方法得到金屬箔積層板時，必啰 士 知組成物對纖賴布的含浸性。填充材㈣ i慮樹 5〜lOOnm之二氧化石夕粒子,而尤其可提升對纖維織布均=挺 ί"生，故在加熱加壓成形時，抑制金屬箔積層板内:=3夂 物的流動’抑制炫融樹脂之不均勻移動，故可防止曰、、且成 層板表面之條紋狀的不均，且可作成均勻厚度。金屬箔積 3·印刷佈線板 接著說明本發明之印刷佈線板。 本發明之印刷佈線板係將上述預浸體及/或上 於内層電路基板而成。 ’’層板用 10 U02467 33 201251534 卜本^月之印刷佈線板係將上述之預浸體用於内層電 路上之絕緣層而成。 尚且在將本發明之預浸體或本發明之積層板用於内層電 土板而得的印刷佈線板的情況，使内層電路基板之預浸體 硬化而成之層為絕緣層。 本發明中所謂印刷佈線板，係指在絕緣層上設置金屬馆等 之導體層而形成導體電路層者，可為單面印刷佈線板(單層 板）兩面印刷佈線板(二層板)及多層印刷佈線板（多層板) 之任種。所明多層印刷佈線板，係指藉由鍍穿孔法或增層 4重且了 3層以上的印刷佈線板，可藉由於内層電路基板 上重疊絕緣層並進行加熱加壓成形而獲得。作為上述内層電 路基板，可使用例如㈣了本發明之積層板及/或本發明之 員/又體而成者作為使用本發明之積層板而成的内層電路基 板’可適合使用例如於不具有金屬箔之本發明之積層板上藉 由半加成法專形成既定圖案的導體電路，對該導體電路部分 進行黑化處理者’或於本發明之金屬箔積層板之金屬箔上形 成既定圖案之導體電路，對該導體電路部分進行黑化處理 者。 另外，作為使用本發明之預浸體而成的内層電路基板，亦 可使用於由硬化樹脂等所構成之絕緣性的支撐體上搭載電 容器、電阻、晶片等之電氣/電子零件，於其上積層本發明 之預浸體’予以加熱加壓硬化而得到零件内藏基板，於該零 1〇1102467 34 201251534 牛内藏基板上藉半加祕等形成既定圖案 導體電路部分進行了黑化處理者。 之導體電路 對該 本奴明中’係在此種使用了本發明 本發明之預浸體而成的㈣電路基板、„知=層板及^ 板之導鱧電路上，進一步積層本發明之預浸體，;= ，硬化而作成㈣電路基板。作為上述内層 ^ 為上述内層21=2。又，於❹本發r預浸體作 用本發明之預浸體或積: ‘、、、本發明之印刷佈線板的代表例，針 =金屬 >自積層板作為内層電路基板、使用本發明 作為絕緣相情況的乡騎刷·板進行制。义體 *y\ |， 、内=電路基板係於上述金屬箱積層板之單面或兩面上形 = 導體電路，對該導體電路部分進行黑化處理而 ★ 〔導體電路之形成方法並滅靠^，可藉 法、加成法、半加成法等之公知方法進行。又，㈣電路基 板上’可藉由鑽頭加工、f射加工等形成穿孔，藉鍍覆等進 π兩面之電氣連接。由於上述内層電路基板為由本發明之金 屬箔積層板所構成，故尤其是藉由雷射加工，可形成孔徑、 形狀等之精度優越的穿孔。上述雷射可使用激元雷射、υν 雷射及二氧化碳雷射等。 其次’於該内層電路基板上重疊上述預浸體並進行加熱加 101102467 35 201251534 壓成形，再藉由加熱硬化而形成絕緣層。具體而言，係 述預浸體與上述内層電路基板重疊，使用真空加壓式層^ 置等進行真空加熱加壓成形，其後，藉熱風乾料置等= 緣層進行加熱硬化。於此，作為加熱加壓成雜件並另 限定，若列舉其—例，可依溫度…崎、壓力⑽^別 貫施。又’作為加熱硬化之條件並_舰定，若列舉其—a 例，可依溫度140〜240t;、時間3〇〜12〇分鐘實施。，、 接著，對經積層之絕緣層照射雷射，形成開孔部（通 上述雷射可使賴穿孔形成時所使用之雷_同者。由於上 述絕緣層為由本發明之預浸體所構成，故可藉“射加工， 形成孔徑、形狀等之精度優越的開孔部。 雷射照射後之樹脂殘糾亏跡）等，較佳係進行藉由過猛酸 鹽、重鉻酸鹽等之氧化齡h絲的處理、亦即去污處 理。若去污處理不足、未充分確保去污性，购使於開孔二 進行金屬鍍覆處理，仍有因污跡而無法充分確保上層導體電 路層與下層導體電路層間之通電性之虞。又，藉由進行去污 處理’由於可解社絕緣層表面同時進行粗化，故在藉金 屬鑛覆處雜絕緣層表面上形鱗體層時，絕緣層表面與導 體層間之密黏性優越。又，在藉f射照射進行開孔部形成之 前’亦可於絕緣層表面形成導體層。 接著，於開孔部及絕緣層表面進行金屬錢覆處理，形成導 體層。於上述絕緣層表面，係進—步藉由上述公知方法進行 101102467 201251534 導體電路形成。又，於開孔部進行金屬鍍覆處理，形成導體 層，藉此可達到上層導體電路層與下層導體電路層間的導 通。 亦可進而朗絕緣層，進行上述㈣的導體電路形成，但 在多層印刷佈線板巾’係於導體€路形錢，於最外層形成 抗焊膜。抗痒膜之形成方法並無特別限定，例如可藉由積層 (層合)乾_型之抗焊劑，藉由曝光及顯影而予以形成的方 法，或對印刷了液狀抗㈣者藉由曝光及顯影㈣以形成的 = 佈線板用於半導體裂置的情況， 設置連制電極部。連接用電極部 :金、_及焊錫㈣等之金屬 4.半導體裝置 斤反復 接著說明本發明之半導體裝置。 元佈線板上安^有焊錫凸塊的半導體 於印刷佈線板與半導^成:上述印刷佈線板的連接。然後， 裝置。焊锡凸塊_7L之間填充密封樹脂，形成半導體 合金所構1佳係由以錫、敍、銀、銅、祕等所構成之 半導體元件與印刷佈線板 合器等，進行印刷佈線板上 係㈣心晶片接 焊錫凸塊的位置對用電極部與半導體元件之 他加熱敦置將焊錫凸j使用1汉迴焊裝置、熱板、其 锡凸塊加熱至炫點以上，藉由使印刷佈線板 101102467 37 201251534 與焊錫凸塊進行熔融接合而Μ連接。又，為了使連接可靠 f生良好亦可事先於印刷佈線板上之連接用電極部形成焊锡 膏等溶點較低的金屬層。於此接合步驟前，亦可藉由於焊锡 凸塊及/或印刷佈線板上之連接用電極部的表層上塗佈助焊 劑’以提升連接可靠性。 (實施例） 以下根據實施例及比較例詳細說明本發明，但本發明並不 限定於此。 貫施例及比較例所使用之纖維織布，係將JIS R3413所規 疋之玻璃纖維進行平織而成的織布，為以下玻璃纖維織布 A〜L。 A . T玻璃，使用E11〇 1/()之玻璃纖維紗，經線與橫線之 每25mm的織入根數為44 5根、42根，經開纖、扁平處理 的厚度為13〇μηι，基重155g/m2 B . E玻璃，使用DE15〇 1/〇之玻璃纖維紗，經線與橫線 之每25mm的織入根數為46 5根、44根，經開纖、扁平處 理的厚度為95μηι，基重I21g/m2 c . τ玻璃，使用E225 1/〇之玻璃纖維紗，經線與橫線之 每25mm的織入根數為65根、64根，經開纖、扁平處理的 厚度為95μιη，基重121g/m2 D . D玻璃，使用£225 1/0之玻璃纖維紗，經線與橫線之 每25mm的織入根數為65根、64根，經開纖、扁平處理的 101102467 38 201251534 厚度為95μηι，基重121g/m2 E : T玻璃，使用D450 1/0之玻璃纖維紗，經線與橫線之 每25mm的織入根數為59根、59根，經開纖、扁平處理的 厚度為46μιη，基重53g/m2 F : T玻璃，使用BC1500 1/0之玻璃纖維紗，經線與橫線 之每25mm的織入根數為90根、90根，經開纖、扁平處理 的厚度為20μιη，基重24g/m2 G : T玻璃，使用C1200 1/0之玻璃纖維紗，經線與橫線 之每25mm的織入根數為74根、77根，經開纖、扁平處理 的厚度為25μιη，基重31g/m2 H : T玻璃，使用E110 1/0之玻璃纖維紗，經線與橫線之 每25mm的織入根數為44.5根、42根，經開纖、扁平處理 的厚度為115μιη，基重155g/m2 I : T玻璃，使用El 10 1/0之玻璃纖維紗，經線與橫線之 每25mm的織入根數為43根、40根，經開纖、扁平處理的 厚度為145μηι，基重150g/m2 J : T玻璃，使用E225 1/0之玻璃纖維紗，經線與橫線之 每25mm的織入根數為59根、54根，經開纖、扁平處理的 厚度為97μηι，基重100g/m2 K : T玻璃，使用D450 1/0之玻璃纖維紗，經線與橫線之 每25mm的織入根數為60根、47根，經開纖、扁平處理的 厚度為50μπι，基重48g/m2 101102467 39 201251534 L : T玻璃，使用Ci2〇〇 1/0之玻璃纖維紗，經線與朽線 之每25mm的織入根數為68根、72根，經開纖、扁平声理 的厚度為27μιη，基重25g/m2 實施例及比較例所使用之清漆，係藉由以下清漆製造例 1〜7 ’將樹脂組成物含有、混合於溶劑中而製造者。 (清漆製造例1) 將環氧樹脂(DIC公司製HP-5000)6重量份、笨酶紛酸主 漆型氰酸酯樹脂(R0nza公司製PT30)12重量份、紛系硬/ 劑（明和化成公司製MEH-7851-4L)6重量份、二氧化石夕板 (TOKUYAMA公司製NSS-5N，平均粒徑7〇nm)l〇重旦， 里里份、 球狀二氧化石夕（Admatechs公司製SO-31R，平岣津〜 1.0μπι)65重量份、環氧基矽烷（信越化學工業公司1 ΚΒΜ-403Ε)1.0重量份，於曱基乙基酮中含有、 δ製 〇西’使^用 高速㈣裝置進行攪拌，得到環氧基樹脂組成物以固形份其 準計為7G重！：％的清漆^又，若將清漆中所含有、現入二 樹脂組成物中所含有的填充材整體設為1〇〇質量％，則 充材中所含之二氧化雜子為13質量％，球狀二氧化2 87質量％。 馬 (清漆製造例2) 將作為環氧樹脂之聯苯基芳院基型環氧樹脂（日本化藥公 司製NC-3_9重量份、雙順丁烯二醱亞胺樹脂(κι化成工 業公司製丽·?〇)η重量份、4，m苯基甲烧3重量 101102467 201251534The content of the oxygen resin is not particularly determined, and is preferably 5 to 6 g% by weight based on the total of the above-mentioned resin. When the content is less than the above lower limit, the curability of the resin composition is lowered, or the moisture resistance of the prepreg or the printed wiring board to which the resin composition is applied is lowered. Further, when the above-mentioned upper limit value is exceeded, the thermal expansion ratio of the prepreg or the printed wiring board is increased or the heat resistance is lowered. The content of the above epoxy resin is particularly preferably 1 〇 to 5 〇 by weight based on the solid content of the whole of the resin composition 10 Π 02467 22 201251534. The weight average molecular weight of the above epoxy resin is not particularly limited. It is preferably Ι·0χΐ02 to 2.0Χ104. When the average molecular weight of the bitter weight is less than the above lower limit, cracks may occur on the surface of the prepreg. If the upper limit is exceeded, the solder heat resistance of the prepreg may be lowered. By setting the weight average molecular weight within the above range, the balance of these characteristics is superior. In the present invention, the weight average molecular weight of the epoxy resin is determined by, for example, gel permeation chromatography (GPC), and is specified as a molecular weight in terms of polystyrene. The resin composition is not particularly limited, and by containing a cyanate resin, the flame retardancy can be improved, the coefficient of thermal expansion can be reduced, and the electrical characteristics (low dielectric constant, low dielectric loss tangent) of the prepreg can be improved. . The above-mentioned hetero-acid resin is not particularly limited. For example, a halogenated gas compound phenol or naphthol can be reacted, and if necessary, prepolymerization can be carried out by a method such as heating. Further, a commercially available product thus prepared can also be used. The type of the cyanate resin is not particularly limited, and examples thereof include a clarified varnish type cyanate resin, a bisphenol fluorene type cyanate resin, a bisphenol hydrazine type cyanate resin, and a tetramethyl bisphenol F type. A bisphenol type cyanate resin such as a cyanate resin.曰 The above-mentioned entangled dragon resin preferably has two or more cyanate groups (•0-CN) in the molecule. For example, 2,2,-bis(4-cyanophenyl)isopropylidene, 1,,, bis(4-cyanophenyl)ethane, bis(4-cyanooxy-3) ,5-dimethylphenyl)methene 101102467 23 201251534 calcined,1,3·bis(4·cyanooxyphenyl·!♦decylethylene))benzene, dicyclopentadienyl isocyanate, phenol novolac Varnish-type isocyanate, bis(4-cyanooxy stupid) sulphur, bis(4-cyanooxyphenyl) ether, Μ} ginseng (4_oxyl stupid) Oxyphenyl) phosphite, bis(4-cyanophenyl)sulfone, bis(4-cyanophenyl)propane, 1,3·, Μ_, 1,6_, 1,8_, 2,6 _ or 27-dicyanoyloxynaphthalene, 1,3,6-tricyanooxynaphthalene, 4,4-dicyanooxybiphenyl and phenol novolac type, nonylphenol phenolic varnish type polyphenols and cyanogen halide The cyanate resin obtained by the reaction between the two is a cyanate resin obtained by a reaction between a naphthol aralkyl type polynaphthol and a halogenated cyanide. Among these, 'phenol novolac type cyanate resin is excellent in flame retardancy and low thermal expansion, 2,2-bis(4-cyanooxyphenyl) isopropylidene and dicyclopentadienyl cyanide The ester crosslink density is controlled and the moisture resistance reliability is superior. From the viewpoint of low heat spreadability, a phenol novolac type cyanate resin is particularly preferred. Further, one or two or more kinds of other cyanate resins may be used in combination, and are not particularly limited. The above cyanate resin can be used alone. Further, two or more kinds of cyanate resins having different weight average molecular weights or a combination of the above cyanate resins and prepolymers may be used in combination. The above-mentioned prepolymer is usually obtained by, for example, 3-polymerization of the cyanate resin by a heating reaction or the like, and can be suitably used in order to adjust the moldability and fluidity of the resin composition. The prepolymer is not particularly limited. For example, when a prepolymer having a polymerization ratio of 2 Å to 5 Å is used, good formability and fluidity can be exhibited. 101102467 24 201251534 The content of the cyanate resin is not particularly limited, but is preferably 5 to 60% by weight based on the total solid content of the resin composition. /. More preferably, it is 1 〇 to 5 〇.% by weight <> When the content of the dextran cyanate resin is within the above range, the heat resistance and flame retardancy of the prepreg can be more effectively improved. When the content of the cyanate resin is less than the above lower limit value, the thermal expansion property of the prepreg is increased and the heat resistance is lowered. When the content exceeds the above upper limit, the strength of the prepreg may be lowered. The weight molecular weight of the cyanate resin is not particularly limited, and is preferably 5'〇xl〇2 to 4.5xl〇3, particularly preferably 6 〇xl02~3.〇χ1〇3. When the weight average molecular weight is less than the above lower limit, cracks may occur on the surface of the prepreg or the mechanical strength may be lowered. In addition, when the weight average molecular weight exceeds the above upper limit, the curing reaction of the resin composition becomes fast, and the adhesion to the conductor layer is deteriorated. In the present invention, the weight average molecular weight of the above-mentioned cyanate vinegar can be determined by, for example, condensing osmosis chromatography (GPC), and is specified as the weight molecular weight of polystyrene. The resin composition is not specified, and the heat resistance can be improved by containing a bi-n-butylene-yellow resin. The above-mentioned bis-butadiene diimide imide resin is not particularly limited, and examples thereof include hydrazine, hydrazine, -(4,4,·diphenylmethyl) bis-butane di-imine, and bis(3-B). Base _5·Methyl ice cis-butenylene diimide phenyl) W ϋ 卜 ( (4_ cis-butyl bis-imide imiline phenoxynaphthalene bis- bis bis bis phthalate). The bis-imine resin may be further used in combination with two or more kinds of other double 101102467 25 201251534 maleimide resin, and is not particularly limited. Further, the above-mentioned bis-butenylene diimide resin may be used. Alternatively, it may be used in combination with a dicis-butanthrene diamine resin having a different weight average molecular weight, or a combination of the above-mentioned bis-butenylene diimide resin and a prepolymer thereof. The content of the resin is not particularly limited, but is preferably 35% by weight, particularly preferably 5 to 20% by weight based on the total solid content of the resin composition. (Resistant, hardening accelerator) Resin composition used in the present invention A hardener may be used in combination. The curing agent is not particularly limited, and for example, an epoxy resin is used as the above thermosetting resin. In the case of using a phenolic curing agent, an aliphatic amine, an aromatic amine, dicyandiamide, a dicarboxylic acid diterpene compound, an acid anhydride or the like which is generally used as a curing agent for an epoxy resin, the present invention can be used. In the resin composition, a curing accelerator may be added as needed. The curing accelerator is not particularly limited, and examples thereof include an organic metal salt, a tertiary amine, an imidazole, an organic acid, and an onium salt compound. One type of the derivative may be used alone or in combination of two or more kinds of derivatives including the same. (Coupling agent) The resin composition may further contain a coupling agent. The coupling agent is for heat generation. The wettability of the interface between the curable resin and the filler is improved, thereby allowing the resin and the filler to be uniformly fixed to the fiber woven fabric, thereby improving the heat resistance of the Ϊ01102467 26 201251534 prepreg, especially moisture absorption. Solder heat resistance after the above. The coupling agent is not particularly limited, and examples thereof include an epoxy-based coupling agent, an external coupling agent, an amine-based coupling agent, a titanate coupling agent, and polywei oil. By using a coupling agent or the like, the wettability between the interface with the filler can be improved, and the heat resistance of the prepreg can be further improved. The amount of the coupling agent added is not particularly limited, and the filler is used. The weight part is preferably 0.05 to 3 parts by weight, particularly preferably 2 parts by weight. If the content is less than the above lower limit, _ cannot be sufficiently filled and stored, so that the effect of improving heat resistance is lowered. When the content exceeds the above upper limit, the enthalpy reaction may be affected, and the bending strength may be lowered. (Others) β / Further, in the above resin composition, an antifoaming agent, a leveling agent, or an ultraviolet ray may be added as needed. Additives other than the above-mentioned components such as an absorbent, a foaming agent, an antioxidant, a flame retardant, a flame retardant auxiliary such as a scale 1 guess, and an ion trapping agent. The prepreg system of the present invention will be dissolved. The varnish containing the thermosetting resin composition described above is held in a fiber woven fabric and then obtained by removing the solvent. The method for preparing the varnish is not particularly limited, and is preferably, for example, a polymer obtained by dispersing a thermosetting resin, a filler, and a filler in a solvent, and adding other components of the resin to the polymer, and adding A method in which the above-mentioned solvents are mixed and mixed. Thereby, the dispersibility of the filler can be improved, and the silica dioxide particles having an average particle diameter of 5 to 100 nm contained in the filler can easily enter the fiber woven fabric 101102467 27 201251534, and the resin composition can be improved to the fiber woven fabric. Impregnation. In the present invention, the composition containing the thermosetting resin in the molten metal is dissolved in a solvent, and the insoluble filler or the like is dispersed in the solvent. The solvent is not particularly limited, and is preferably a solvent which exhibits good solubility to the above resin composition, and examples thereof include acetone, methyl ethyl ketone (mek), hexanone (ANON), and decyl isobutyl ketone. (ΜΙΒΚ), cyclopentanone, dimethyl decylamine, dimethyl acetamide, hydrazine-methyl butyl ketone, and the like. Further, a poor solvent (ρ·wall (4) may be used in a range that does not cause adverse effects. The solid content of the resin composition contained in the varnish (the component from which the solvent is removed by the varnish) is not particularly limited, and is preferably 3G to 8G% by weight, particularly preferably 4% to 7% by weight, thereby improving the impregnation property of the resin composition to the fiber woven fabric, and suppressing surface smoothness, thickness variation, and the like at the time of coating. The method in which the varnish is impregnated into the above-mentioned fiber woven fabric may, for example, be a method of impregnating a fiber woven fabric into a varnish, a method of coating with various applicators, a method of cutting by a spray Is, and a method of cutting The varnish is coated/dried on a substrate to prepare a resin sheet, and the resin sheet is placed so as to be adhered to the fiber woven fabric. The fiber woven is preferably woven. The method of immersing the cloth in the varnish, thereby improving the impregnation property of the thermosetting tree stalk to the ray cloth. Further, when the woven fabric is immersed in the varnish, the usual impregnation coating apparatus 1 can be used. The solvent of the above varnish can be dried, for example, at %~18 (TC) Drying for 10 minutes, thereby obtaining a semi-hardened pre-101102467 28 201251534 dip. The above-mentioned pre-system is known as Qian Wei (4). The two sides of the fiber woven fabric layer are formed by two layers, and the layers are formed. The thickness of the layer is p, and the resin consisting of the composition is 1〇~200μΐη^„ Thickness (only one side to the thickness of the layer). There is no specific resin layer. 5~2(^111, special Good 2~1 nightmare..., ', 疋, the car is good for the upper seam _, then the conductor layer is better and the degree is better. The standing and surface smoothing the overall thickness of the prepreg 30~ 220 μιηη, particularly preferably 40 to 165 μιη, and may also be thinned. It is not particularly limited, and it is preferred that the 'prepreg is excellent in handleability, and the above-mentioned prepreg is formed in the strands. There is no gap with the above length in the direction of the extension, and the insulation sin of the printed wiring board obtained by the insulation layer can be improved by the ^. Preferably, it is in the direction in which the fibers constituting the strands extend; there is 2G_ or more, especially In the above prepreg, the number density of the gaps of the straight line of the fiber woven fabric is 5 (W). In this case, the prepreg can be used for insulation. Insulation reliability of the printed wiring board obtained by the layer. Further, the _number density of the diameter of 5G_ or more in the strands constituting the fiber woven fabric is preferably 101102467 29 201251534 20cm·1 or less, and particularly preferably 10cm·1 or less. Further, the length or the number density of the voids in the strands can be achieved by appropriately adjusting the average particle diameter of the cerium oxide particles present in the strands or the bulk density of the fiber woven fabric, etc. 2. The laminated board of the present invention is characterized in that the prepreg of the present invention described above is cured. Further, the laminated board of the present invention is preferably formed by providing a conductor layer on at least one outer side surface of the prepreg of the present invention. One sheet may be used as the prepreg, or two or more laminates may be used. In the case of a laminate provided with a conductor layer (hereinafter sometimes referred to as a "metal foil laminate"), a metal foil is laminated on the prepreg and heated and pressurized. When one prepreg is used, the metal foil is superposed on the upper and lower surfaces or on one side, and when the laminated body in which two or more prepregs are laminated, the upper and lower sides of the outermost layer of the laminated body or The metal foil is overlapped on one side. Then, by laminating the prepreg and the metal foil by heating and press forming, a metal foil laminated board can be obtained. Examples of the metal foil include copper and a copper alloy. Metal foils such as Lv, Ilu alloy, silver, silver alloy, gold, gold alloy, zinc, zinc alloy, nickel, nickel alloy, tin, tin alloy, iron, iron alloy. Further, a conductor layer such as the above-described copper or copper alloy may be formed by plating. In the production of the metal foil laminate, the heating temperature is not particularly limited, and is preferably 101102467 30 201251534 120 to 220 ° C, particularly preferably 150 to 200 ° C. The pressure of the pressurization is not particularly limited, and is preferably 0.5 to 5 MPa, particularly preferably 1 to 3 MPa. Further, post-hardening may be carried out at a temperature of 150 to 300 ° C in a high temperature bath or the like as needed. Further, as another method of producing the metal foil laminate of the present invention, for example, a method of producing a metal foil laminate having a metal foil having a resin layer as shown in Fig. 1 can be used. First, a metal foil 10 having a resin layer coated with a uniform resin layer 12 by an applicator is prepared on the metal foil 11. Next, on both sides of the fiber woven fabric 20, the metal foils 10 and 10 having the resin layer are disposed inside the resin layer 12 (Fig. 1 (a)), and heated in a vacuum at 60 to 130 ° C, plus The laminate was impregnated with a pressure of 0.1 to 5 MPa. Thereby, a prepreg 41 having a metal foil was obtained (Fig. 1 (b)). Next, the prepreg 41 having the metal foil is directly subjected to heat and pressure molding, whereby the metal foil laminate 51 can be obtained (Fig. 1 (c)). Further, as another method of producing the metal foil laminate of the present invention, a method of producing a metal foil laminate using a polymer film sheet having a resin layer as shown in Fig. 2 can be exemplified. First, a polymer film sheet 30 having a resin layer in which a uniform resin layer 32 is applied to a polymer film sheet 31 by an applicator is prepared. Next, on both sides of the fiber woven fabric 20, the polymer film sheets 30 and 30 having the resin layer are disposed inside the resin layer 32 (Fig. 2(a)), and heated in a vacuum at 60 to 130 °C. The mixture was impregnated with a pressure of 0.1 to 5 MPa. Thereby, the prepreg 42 having the polymer film sheet was obtained (Fig. 2(b)). Next, the polymer film sheet 31 having at least one side of the prepreg 42 having the polymer film sheet is peeled off (two sides are peeled off in FIG. 2(c)), and the surface of the polymer film 101102467 31 201251534 is peeled off. The metal g 11 (Fig. 2(d)) is placed thereon, and heating, such as press forming, is performed, whereby the metal foil laminate 52 is obtained (Fig. 2(e)). Further, in the case of peeling off the polymer film sheets on both sides, it is possible to laminate two or more sheets in the same manner as the above-mentioned prepreg. When two or more prepregs are laminated, a metal falling or a polymer sheet is placed on the outermost rain surface or one side of the outermost layer of the laminated body, and the metal is obtained by heating and twist forming. Box laminate. The metal entangled layer obtained by the 耩 manufacturing method has high thickness precision, uniform thickness, and superior surface smoothness. In addition, since a metal case laminated board having a small forming strain can be obtained, a printed wiring board and a semiconductor device which are produced by using the metal foil laminated board obtained by the manufacturing method are small (4), and the difference is γ. A printed wiring board and a semiconductor device are manufactured with good yield. The temperature is not particularly limited as a condition of the above-described heat and pressure molding, and is preferably 120 to 250 ° C and particularly preferably 15 to 22 (rc. The pressing force of the above pressing is not particularly limited, and is preferably 0.1. 〜5 MPa, particularly preferably 0.5 to 3 MPa. Further, it is required to be post-hardened at a temperature of 150 to 3 Torr in a high temperature bath or the like. The metal foil laminate of Figs. 1 to 2 and the like is not particularly limited. An apparatus having a metal foil of a resin layer and an apparatus for producing a metal foil laminated board are manufactured. The apparatus for producing the metal foil having the resin layer is used as a metal foil, for example, a long-length sheet material is used as a roll form. In this way, the resin varnish is continuously supplied to the metal foil in a predetermined amount by the resin supply device. Here, as the resin varnish, the method of using the present invention is disclosed in Japanese Patent Application No. 10110246732 201251534 The resin composition is dissolved and dispersed in a coating liquid obtained by spraying. The coating amount of the resin varnish can be controlled by the gap between the knife holder and the spare roller which is light to the blade. A predetermined amount of resin varnish is applied. Metal, material In the inside of the air drying device, the organic solvent contained in the resin varnish is dried and removed, and if necessary, the metal having the resin layer can be formed in the middle of the hardening reaction. The laminated film is directly laminated on the side of the resin layer, and the protective film is laminated on the side on which the resin layer is formed, and the metal core having the resin layer is wound, and the metal foil having the insulating resin layer is formed in the form of (4) When using the 丨 2 2 2 2 , , , , 丨 丨 丨 丨 丨 丨 丨 丨 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 清 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀 匀Her deviation is small and the yield is improved. In addition to the half of the H piece, when the metal foil laminate is obtained by this manufacturing method, it is necessary to know the impregnation property of the composition to the fiber cloth. Filling material (4) i think tree 5~ lOOnm of dioxite ray particles, and especially can improve the fiber woven fabric = ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ Uneven movement, so it can prevent sputum, and The stripe surface of the laminate is unevenly formed and can be formed into a uniform thickness. Metal foil product 3·printed wiring board Next, the printed wiring board of the present invention will be described. The printed wiring board of the present invention has the above prepreg and/or The inner layer circuit board is formed. ''Laminar plate 10 U02467 33 201251534 The printed circuit board of the present invention is formed by using the above prepreg for the insulating layer on the inner layer circuit. The prepreg of the present invention is still used. Or, in the case of the printed wiring board obtained by using the laminated board of the present invention for the inner layer electric earth plate, the layer obtained by hardening the prepreg of the inner layer circuit board is an insulating layer. The so-called printed wiring board in the present invention means insulation. In the case where a conductor layer such as a metal hall is provided on the layer to form a conductor circuit layer, any one of a printed wiring board (two-layer board) and a multilayer printed wiring board (multilayer board) on both sides of a single-sided printed wiring board (single-layer board) can be used. The multilayer printed wiring board described above is a printed wiring board having three or more layers by means of a plating or by plating method, and can be obtained by superposing an insulating layer on an inner layer circuit board and performing heat and pressure forming. As the inner layer circuit board, for example, (4) the laminated board of the present invention and/or the member of the present invention can be used as the inner layer circuit board using the laminated board of the present invention. A metal foil on a laminate board of the present invention which is formed by a semi-additive method to form a predetermined pattern, and a blackening treatment is performed on the conductor circuit portion or a predetermined pattern is formed on the metal foil of the metal foil laminate of the present invention. The conductor circuit is blackened to the conductor circuit portion. In addition, as an inner layer circuit board using the prepreg of the present invention, an electric/electronic component such as a capacitor, a resistor, or a wafer may be mounted on an insulating support made of a cured resin or the like. The prepreg of the present invention is subjected to heat and pressure hardening to obtain a built-in substrate of the part, and the blackened person is formed by forming a predetermined pattern of the conductor circuit on the inner substrate of the zero-in-1102467 34 201251534. . The conductor circuit further superimposes the present invention on the circuit board of the (four) circuit board, the known circuit board, and the circuit board of the present invention using the prepreg of the present invention. The prepreg, ; = , hardened to form a (four) circuit substrate. The inner layer is the inner layer 21 = 2. Further, the prepreg or the product of the present invention is applied to the prepreg of the present invention: ',,, and A representative example of the printed wiring board of the invention, needle=metal> self-laminated board is used as an inner layer circuit board, and the present invention is used as a state-of-the-art brush board for the case of an insulating phase. Prosthetic body *y\ |, inner = circuit board Attached to the single-sided or two-sided shape of the above-mentioned metal box laminated plate = conductor circuit, the conductor circuit portion is blackened ★ [The formation method of the conductor circuit and extinguished ^, can be borrowed, added, half added Further, a method known in the art is carried out, and (4) on the circuit board, a through hole can be formed by a bit processing, a f-beam process, or the like, and electrical connection between the two sides can be performed by plating or the like. Since the inner layer circuit substrate is a metal foil of the present invention. Laminated boards, so especially borrowed Laser processing can form perforations with superior precision such as aperture, shape, etc. The laser can use excimer laser, υν laser and carbon dioxide laser, etc. Secondly, the prepreg is superimposed on the inner circuit board and performed. Heating, adding 101102467 35 201251534, press forming, and forming an insulating layer by heat hardening. Specifically, the prepreg is superposed on the inner layer circuit board, and vacuum heating and press forming is performed using a vacuum pressure type layer or the like. Then, it is heat-hardened by the hot air dry material, etc., and the edge layer is heat-hardened. Here, it is limited by heating and pressurization, and if it is listed as an example, it can be applied according to the temperature, the temperature, and the pressure (10). 'As a condition for heat hardening, if it is listed as a case, it can be carried out according to the temperature of 140 to 240 t; and the time is 3 〇 to 12 〇 minutes. Then, the laminated layer is irradiated with a laser to form a laser. The opening portion (the same as that used when the above-mentioned laser can be formed by the above-mentioned laser.) Since the insulating layer is composed of the prepreg of the present invention, it is possible to "shoot" to form an aperture, a shape, etc. superior Openings The resin residue after the laser irradiation correct track loss) and the like, the preferred system for processing by excessive acid salt, dichromate oxidation of h old yarn, i.e. the decontamination process. If the decontamination treatment is insufficient and the decontamination property is not sufficiently ensured, the metal plating treatment is performed on the opening 2, and the electrical conductivity between the upper conductor circuit layer and the lower conductor circuit layer cannot be sufficiently ensured due to the stain. Further, since the surface of the insulating layer is simultaneously roughened by the decontamination treatment, when the scale layer is formed on the surface of the insulating layer by the metal ore, the adhesion between the surface of the insulating layer and the conductor layer is excellent. Further, the conductor layer may be formed on the surface of the insulating layer before the formation of the opening portion by f-irradiation. Next, metal etching treatment was performed on the surface of the opening portion and the insulating layer to form a conductor layer. On the surface of the insulating layer, the conductor circuit is formed by the above-mentioned known method 101102467 201251534. Further, metal plating treatment is performed on the opening portion to form a conductor layer, whereby conduction between the upper conductor circuit layer and the lower conductor circuit layer can be achieved. Further, the insulating layer can be formed by the above-mentioned (4) conductor circuit, but the multilayer printed wiring board is formed on the conductor to form a solder resist film on the outermost layer. The method for forming the anti-itch film is not particularly limited, and for example, it can be formed by laminating (laminating) a dry-type solder resist, by exposure and development, or by exposure to a liquid-resistant (four) And development (4) to form a wiring board for semiconductor cracking, and to provide a connection electrode portion. Electrode for connection: metal such as gold, _, and solder (four) 4. Semiconductor device Repetition Next, the semiconductor device of the present invention will be described. A semiconductor wafer having a solder bump is mounted on the wiring board and connected to the semiconductor wiring board. Then, the device. The solder bumps are filled with a sealing resin between the _7L to form a semiconductor alloy. The semiconductor element is made of a semiconductor element such as tin, silver, copper, or copper, and a printed wiring board. (4) The position of the soldering bump of the core wafer is heated by the electrode portion and the semiconductor element, and the solder bump j is heated to a bright point or more by using a solder reflow device, a hot plate, and a tin bump thereof, by making the printed wiring Plate 101102467 37 201251534 is fused to the solder bumps and joined. Further, in order to make the connection reliable, it is possible to form a metal layer having a low melting point such as solder paste in advance on the electrode portion for connection on the printed wiring board. Before the bonding step, the soldering agent may be applied on the surface of the solder bump and/or the connection electrode portion on the printed wiring board to improve the connection reliability. (Examples) Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited thereto. The fiber woven fabric used in the examples and the comparative examples is a woven fabric obtained by flat woven the glass fibers defined in JIS R3413, and is the following glass fiber woven fabrics A to L. A. T glass, using E11〇1/() glass fiber yarn, the number of woven threads per 25mm of the warp and the horizontal line is 44 5, 42 pieces, and the thickness of the open fiber and flat processing is 13〇μηι , base weight 155g/m2 B. E glass, using DE15〇1/〇 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 46 5, 44, after being opened and flattened The thickness is 95μηι, the basis weight is I21g/m2 c. τ glass, using E225 1/〇 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 65, 64, through the fiber opening, flat processing The thickness is 95μηη, the basis weight is 121g/m2 D. D glass, using the glass fiber yarn of £225 1/0, the number of woven roots per 25mm of the warp and the horizontal line is 65, 64, through the fiber, Flat processed 101102467 38 201251534 Thickness is 95μηι, basis weight 121g/m2 E : T glass, using D450 1/0 glass fiber yarn, the number of weaving roots per 25mm of warp and transverse lines is 59, 59, The fiber-opened, flat-treated thickness is 46 μm, the basis weight is 53 g/m 2 F : T glass, and the BC1500 1/0 glass fiber yarn is used. The number of woven roots per 25 mm of the warp and the horizontal line is 90, 9 0, the thickness of the open fiber, flat treatment is 20μιηη, basis weight 24g/m2 G : T glass, using C1200 1/0 glass fiber yarn, the number of weaving roots per 25mm of warp and cross lines is 74 77, the thickness of the open fiber, flat treatment is 25μιη, the basis weight is 31g/m2 H : T glass, the glass fiber yarn of E110 1/0 is used, the number of weaving per 25mm of the warp and the horizontal line is 44.5 Root, 42 pieces, open-fiber, flat-processed thickness 115μιηη, basis weight 155g/m2 I : T glass, using El 10 1/0 glass fiber yarn, the number of weaving per 25mm of warp and cross lines 43 and 40, the thickness of the open fiber, flat treatment is 145μηι, the basis weight is 150g/m2 J : T glass, the fiberglass yarn of E225 1/0 is used, the weaving root of each 25mm of the warp and the horizontal line The number is 59, 54, the thickness of the open fiber is 97μηι, the basis weight is 100g/m2 K : T glass, the fiberglass yarn of D450 1/0 is used, the weaving of each warp and the horizontal line is 25mm. The number of roots is 60 and 47. The thickness of the open fiber is 50μπι, and the basis weight is 48g/m2. 101102467 39 201251534 L : T glass, using Ci2〇〇1/0 glass fiber. The number of woven roots per 25mm of the warp and the dead line is 68, 72, and the thickness of the open fiber and the flat sound is 27 μm, and the basis weight is 25 g/m2. The varnish used in the examples and the comparative examples is The following varnish production examples 1 to 7 'produced by containing and mixing a resin composition in a solvent. (Varnish Manufacture Example 1) 6 parts by weight of an epoxy resin (HP-5000 manufactured by DIC Corporation) and 12 parts by weight of a succinic acid-based lacquer-based cyanate resin (PT30 manufactured by R0nza Co., Ltd.) and various hardeners (Minghe) Chemical Co., Ltd. MEH-7851-4L) 6 parts by weight, dioxide stone plate (NSS-5N, manufactured by TOKUYAMA Co., Ltd., average particle size 7〇nm) l〇重旦, 里里份, spherical SiO2 (Admatechs Company made SO-31R, 岣 岣 〜 ~ 1.0μπι) 65 parts by weight, epoxy decane (Shin-Etsu Chemical Co., Ltd. 1 ΚΒΜ-403 Ε) 1.0 parts by weight, contained in decyl ethyl ketone, δ system '西' ^ Stirring with a high-speed (four) device, to obtain an epoxy resin composition with a solid content of 7G weight! When the amount of the filler contained in the varnish and the resin composition contained in the varnish is 1% by mass as a whole, the amount of the oxidized impurities contained in the filler is 13% by mass. , spherical oxidized 2 87% by mass. Horse (varnish manufacturing example 2) Biphenyl phenyl-based epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3_9 parts by weight, bis-cis-butadiene imide resin (manufactured by κι Chemical Co., Ltd.) ·?〇) η parts by weight, 4, m phenyl ketone 3 weight 101102467 201251534

份、一氧化石夕教子(T0KUYAMA公司製Nss_5N 70nm)10重量伧, 卞叼拉徑 、水鋁土〇可合石灰公司製BMB， 0.5μιη)60重卞巧拉役 々、壤氧基石夕炫（信越化學工掌公 ΚΒΜ-403Ε)1 〇 皆〜、 J ^ ^ 」.重1伤，於二甲基甲醯胺中含有、混合。接 者使用同速搜拌襄置進行授拌將不揮發份調整為70重量 %、聰成如旨凊漆^又，若將清漆中所含有、混合之樹脂 組成2中所含有的填充材整體設為⑽質量％，則該填充材 中所含之二氧切粒子為14質量％，水土為86質量％。 (清漆製造例3) 將聯苯基芳烷基型環氧樹脂（日本化藥公司製 NC-3000FH)20重量份、萘型環氧樹脂（mc(股）公司製 HP4〇32D)5重量份、氰酸賴脂（東都化成(股）製SN485之 衍生物’萘酴型）17重量份、雙順丁烯二醯亞胺樹脂(Κι化 成工業公司製BMI-70)7.5重量份、二氧化矽粒子 (ΤΟΚϋΥΑΜΑ公司製NSS-5N，平均粒徑70nm)7重量份、 球狀二氧化矽（Admatechs公司製SO-31R，平均粒徑 1·0μιη)35.5重量份、聚矽氧粒子（信越化學工業（股）製 ΚΜΡ600 ’平均粒徑5μιη)7.5重量份、辛酸鋅0.01重量份、 環氧基矽烷(信越化學工業公司製ΚΒΜ-403Ε)0.5重量份， 於曱基乙基酮中含有、混合。接著，使用高速攪拌裝置進行 攪拌將不揮發份調整為70重量％，調製成樹脂清漆。又， 若將清漆中所含有、混合之樹脂組成物中所含有的填充材整 101102467 41 201251534 體設為100質量％’則該填充材中所含之二氧化矽粒子為14 質量％，球狀一氣化石夕為71質量〇/〇，聚石夕氧粒子為15質量 %。 (清漆製造例4) 將作為環氧樹脂之聯笨基芳烷基型環氧樹脂（曰本化藥公 司製NC-3_)18.5重量份、雙順丁稀二醯亞胺樹脂(KI化 成工業公司製BMI_7G)34.9重量份、4,4，·二胺基二苯基曱烧 6.1重量份、二氧化矽粒子(τ〇κυγΑΜΑ公司製nss_5N， 平均粒徑70nm)5重量份、水铭土（河合石灰公司製bMB， 平均粒徑0.5μηι)35重量份、環氧基石夕烧(信越化學工業公司 製KBM-4G3E)G.5重量份，於二曱基曱酿胺中含有、混合。 接著，使用高速攪拌襄置進行㈣將不揮發份調整為7〇重 量％，調製成樹脂清漆。又，若將清漆中所含有、混合之樹 脂組成物巾料填崎整體設為_質量％，則該填充 材中所3之-氧化發粒子為12 5質量％，水紹土為π』質 量％。 (清漆製造例5) 將作為環氧樹脂之聯苯基芳烧基型環 司製 NC-3000)2.80 舌旦，、10 parts by weight, oxidized stone shihiko (Nss_5N 70nm made by T0KUYAMA Co., Ltd.), 卞叼 径, 水 水 水 〇 石灰 石灰 石灰 B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B B Shin-Etsu Chemical Co., Ltd. - 403 Ε) 1 〇 all ~, J ^ ^ ”. Heavy 1 injury, contained and mixed in dimethylformamide. The picker uses the same speed search and mixing device to adjust the non-volatile content to 70% by weight, and the other is the filler material contained in the resin composition 2 contained in the varnish. When it is (10)% by mass, the dioxobic particles contained in the filler are 14% by mass, and the water and soil is 86% by mass. (Varnish Manufacture Example 3) 20 parts by weight of a biphenyl aralkyl type epoxy resin (NC-3000FH manufactured by Nippon Kayaku Co., Ltd.) and 5 parts by weight of a naphthalene type epoxy resin (HP4 〇 32D manufactured by mc Co., Ltd.) , 7.5 parts by weight of cyanic acid lysine (derivative of SN485, 'naphthoquinone type, manufactured by Tosoh Chemical Co., Ltd.), bisammoniximine resin (BMI-70, manufactured by Κι Chemical Co., Ltd.), 7.5 parts by weight, dioxide 7 parts by weight of cerium particles (NSS-5N, manufactured by Nippon Steel Co., Ltd., average particle diameter: 70 nm), spherical cerium oxide (SO-31R, manufactured by Admatech Co., Ltd., average particle diameter: 1.0 μm), 35.5 parts by weight, polyfluorene oxide particles (Shin-Etsu Chemical Co., Ltd.) 7.5 parts by weight of an industrial (manufactured) ' 600 'average particle diameter of 5 μm η, 0.01 parts by weight of zinc octoate, and 0.5 parts by weight of epoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.), containing and mixing in decyl ethyl ketone . Next, the nonvolatile content was adjusted to 70% by weight by stirring using a high-speed stirring device to prepare a resin varnish. In addition, when the filler contained in the resin composition contained in the varnish is 101102467 41 201251534, the amount of the cerium oxide particles contained in the filler is 14% by mass, spherical One gas fossil was 71 mass 〇 / 〇, and the poly stone particles were 15% by mass. (Varnish Manufacture Example 4) 18.5 parts by weight of a bis-butyl aralkyl type epoxy resin (NC-3_ manufactured by Sakamoto Chemical Co., Ltd.) as an epoxy resin, and a bis-butylene diimide resin (KI Chemical Industry) Company made BMI_7G) 34.9 parts by weight, 6.1 parts by weight of 4,4, diaminodiphenyl sulfonium, 5 parts by weight of cerium oxide particles (nss_5N, τs υ υ ΑΜΑ company, average particle diameter 70 nm), water Ming Tu ( 35 parts by weight of bMB, an average particle diameter of 0.5 μm), and 5 parts by weight of an epoxy group (KBM-4G3E, manufactured by Shin-Etsu Chemical Co., Ltd.), and contained and mixed in a dimercaptoamine. Then, using a high-speed stirring apparatus, (4) the nonvolatile content was adjusted to 7 〇 by weight to prepare a resin varnish. In addition, when the total amount of the resin composition to be mixed and mixed in the varnish is _ mass%, the oxidized hair particles of the filler material are 125% by mass, and the water is π mass. %. (Varnish Manufacture Example 5) A biphenyl aryl group-based ring made of epoxy resin NC-3000) 2.80 tongue,

曰本化藥公 0.93重量份、二氧化矽粒 、雙順丁烯二醯亞胺樹脂(KI化 重量份、4,4’-二胺基二苯基甲烷 平均粒徑70nm)l〇重量份 子(TOKUYAMA 公司製 NSS-5N， 、水鋁土（河合石灰公司製BMB， 101102467 42 201251534 平均粒徑0.5μιη)80重量份、環氧基矽烷(信越化學卫 菜公司 製ΚΒΜ-403Ε)1.0重量份，於二曱基曱醯胺中含有、、 接著，使用高速攪拌裝置進行攪拌將不揮發份調整為 量％，調製成樹脂清漆。又，若將清漆中所含有、、、曰 4 介匕合之樹 脂組成物中所含有的填充材整體設為100質量％，則 ' 材中所含之二氧化矽粒子為11質量％，水鋁土為89 、 ^ 買量0/0。 (清漆製造例6) 將環氧樹脂(DIC公司製ΗΡ-5000)6重量份、笨齡 漆型氰酸酯樹脂(Ronza公司製ΡΤ30)12重量份、“够者 劑（明和化成公司製MEH-7851-4L)6重量份、-备 一虱化矽极 (TOKUYAMA公司製NSS-5N，平均粒徑7〇nm)3〇 t曰 、 ®量份、 球狀二氧化矽（Admatechs公司製SO-31R，伞 、 1 ·0μηι)45重罝份、環氧基矽烷（信越化學工業八_ & KBM-403E)1.0重量份，於曱基乙基酮中含有、混八司製0.93 parts by weight of bismuth sulphate, cerium oxide granules, bis-xenylene diimide resin (KI parts by weight, average particle size of 4,4'-diaminodiphenylmethane 70 nm) (NSS-5N, manufactured by TOKUYAMA Co., Ltd., 80 parts by weight of bauxite (BMB, 101102467 42 201251534 average particle size 0.5 μιη), and 1.0 part by weight of epoxy decane (ΚΒΜ-403Ε manufactured by Shin-Etsu Chemical Co., Ltd.) It is contained in dimethyl carbamide, and then stirred in a high-speed stirring device to adjust the non-volatile content to a resin amount to prepare a resin varnish. Further, if the varnish is contained, When the total amount of the filler contained in the resin composition is 100% by mass, the cerium oxide particles contained in the material are 11% by mass, the alumina bauxite is 89, and the yield is 0/0. 6) Epoxy resin (manufactured by DIC Co., Ltd. - 5000) 6 parts by weight, idling lacquer type cyanate resin (Ronza Co., Ltd. ΡΤ 30) 12 parts by weight, "sufficient agent (Ming-Chemical Co., Ltd. MEH-7851-4L 6 parts by weight, a preparation of a bismuth (NSK-5N, manufactured by TOKUYAMA Co., Ltd., average particle size 7 〇 nm) 3〇t曰® parts, spherical cerium oxide (SO-31R, Umbrella, 1·0μηι, manufactured by Admatech Co., Ltd.), 45 parts by weight, epoxy decane (Shin-Etsu Chemical Industry Co., Ltd. _ & KBM-403E), 1.0 part by weight, in 曱Containing in the ethyl ketone

高速攪拌裝置進行攪拌’得到環氧基樹脂組成物以使用 準计為70重量％的清漆。又，若將清漆中所含有、卞- 樹脂組成物中所含有的填充材整體設為1〇〇質量％， 充材中所含之二氧化矽粒子為4〇質量％，球狀 則讀填 6〇質量°/〇。 氧化矽為 (清漆製造例7) —將壤氧樹脂（日本化藥公司製NC_3_)6重量份 紛 路清漆型_旨樹脂(R〇職公司製ρτ3〇)12重量份、紛系 101102467 43 201251534 硬化劑（明和化成公司製MEH-7851-4L)6重量份、球狀二氧 化矽(Admatechs公司製SO-31R’平均粒徑i 〇gm)75重量 份、環氧基矽烷(信越化學工業公司製KBM-403E)1.0重量 份，於曱基乙基酮中含有、混合，使用高速攪拌裝置進行攪 拌，得到環氧基樹脂組成物以固形份基準計為7〇重量％的 ’月漆。又，若將清漆中所含有、混合之樹脂組成物中所含有 的填充材整體設為100質量％ ’則該填充材中所含之二氧化 矽粒子為〇質量％，球狀二氧化矽為1〇〇質量0/〇。 將清漆製造例1〜7中所使用之樹脂組成物的組成示於表 1。又’各成分之调配ϊ係以重量份表示。 [表1]The high-speed stirring apparatus was stirred to obtain an epoxy resin composition to use a varnish having a basis weight of 70% by weight. In addition, when the entire filler contained in the ruthenium-resin composition is 1% by mass, the cerium oxide particles contained in the filler are 4 〇 mass%, and the spherical shape is read and filled. 6 〇 mass ° / 〇.矽 矽 ( 清 清 清 清 清 清 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 6 parts by weight of spheroidal cerium oxide (SO-31R 'average particle size i 〇gm by Admatechs Co., Ltd.), 75 parts by weight of sclerosing agent (MEH-7851-4L, manufactured by Mingwa Kasei Co., Ltd.), Epoxy Chemical Co., Ltd. 1.0 part by weight of KBM-403E) was contained and mixed in mercaptoethyl ketone, and stirred using a high-speed stirring apparatus to obtain a monthly paint of 7 〇% by weight based on the solid content of the epoxy resin composition. In addition, when the entire filler contained in the resin composition contained in the varnish is 100% by mass, the cerium oxide particles contained in the filler are 〇% by mass, and the spherical cerium oxide is 1〇〇 quality 0/〇. The composition of the resin composition used in the varnish production examples 1 to 7 is shown in Table 1. Further, the formulation of each component is expressed in parts by weight. [Table 1]

使用上述玻璃纖維織布及上述清漆，製作預浸體、金屬唱 積層板、印刷佈、線板(内層電路紐）、多層印刷佈線板及^ 101102467 44 201251534 導體裝置。 <實施例ι> (1) 預浸體之製作 將製造例1所得之清漆流延塗佈於厚38μιη之聚對苯二甲 酸乙二酯基材（以下稱為PET基材）上，依溫度140°C、時間 10分鐘使溶劑揮發乾燥’使樹脂層厚度成為30μπι。將上述 具有樹脂層之基材，依於玻璃織布Α之兩面上使樹脂層接 觸玻璃織布的方式進行配置，以壓力〇5MPa、溫度14〇。(：、 1分鐘之條件藉真空加壓式層合器（名機製作所公司製 MLVP-500)進行加熱加壓，使樹脂組成物含浸。藉此，得到 於兩面具有PET基材的厚ΐ5〇μιη之預浸體(樹脂層（單面）： ΙΟμιη ’纖維織布層：ΐ3〇μηι)。 (2) 金屬箔積層板之製作 於上述預浸體之兩面上重疊具有載體之2μιη的銅箔（三井 金屬礦業公司製，MICROSIN ΜΤ18ΕΧ-2)，依壓力3MPa、 溫度220°C進行2小時加熱加壓成形。藉此，得到在使預浸 體硬化而成之厚150μπι之絕緣層的兩面上具有銅箔的金屬 - 箔積層板。 (3)多層印刷佈線板絕緣層用預浸體的製作 將上述製造例1所得之清漆含浸於玻璃織布（厚16μιη，Using the above-mentioned glass fiber woven fabric and the above varnish, a prepreg, a metal slab, a printing cloth, a wire board (inner layer circuit), a multilayer printed wiring board, and a conductor device of 101102467 44 201251534 were produced. <Example ι> (1) Preparation of prepreg The varnish obtained in Production Example 1 was cast-coated on a polyethylene terephthalate substrate (hereinafter referred to as a PET substrate) having a thickness of 38 μm. The solvent was evaporated and dried at a temperature of 140 ° C for 10 minutes to make the thickness of the resin layer 30 μm. The substrate having the resin layer was placed so as to contact the glass woven fabric on both sides of the glass woven fabric with a pressure of 5 MPa and a temperature of 14 Torr. (:, 1 minute condition was heated and pressurized by a vacuum pressure type laminator (MLVP-500 manufactured by Nihon Seisakusho Co., Ltd.) to impregnate the resin composition. Thereby, a thick crucible having a PET substrate on both sides was obtained. Prepreg of μιη (resin layer (single-sided): ΙΟμιη 'fiber woven fabric layer: ΐ3〇μηι). (2) Preparation of metal foil laminated board 2μιη copper foil with carrier on both sides of the above prepreg (MICROSIN ΜΤ18ΕΧ-2, manufactured by Mitsui Mining & Mining Co., Ltd.), heated and pressed at a pressure of 3 MPa and a temperature of 220 ° C for 2 hours, thereby obtaining two layers of a 150 μm thick insulating layer formed by hardening the prepreg. Metal-foil laminate with copper foil. (3) Preparation of prepreg for multilayer printed wiring board insulation layer The varnish obtained in the above Production Example 1 was impregnated into a glass woven fabric (thickness 16 μm,

Unichika公司製Ε玻璃織布，Ε02Ζ，基重i7.5g/m2)，於18〇t： 之加熱爐中乾燥2小時，得到預浸體中之樹脂組成物以固形 101102467 45 201251534 份基準計為約78重量％的預浸體(厚40μιη)。又，上述破螭 織布係體積密度1.09g/cm3、通氣度41cc/cm2/sec、扁平率 (厚：寬）1 : 16。又，上述玻璃織布係由作成板狀時之楊氏 率為93GPa、作為板狀時之拉張強度為48GPa、作成纖維織 布時之長度方向之拉張強度為9〇N/25mm的玻璃纖維所構 成者。 (4)印刷佈線板（内層電路基板)之製造 由上述金屬箔積層板剝離载體箔，使用二氧化碳雷射（三 菱電機公司製’ ML605GTX3-5100U2)，依孔徑φ l.4mm、 光束控約120μιη、能量7〜9mJ、射數6之條件，形成φ i〇〇_ 之貫通穿孔。接著，將該金屬箔積層板浸潰於70。(：之膨潤 液(ATOTECH JAPAN 公司製，Swelling Dip Securiganth P) 中5分鐘，再浸潰於80°C之過猛酸鉀水溶液(ATOTECH JAPAN 公司製 Concentrate Compact CP)中 1〇 分鐘後，予以 中和並進行粗化處理。接著，藉無電解鍍覆(上村工業公司 製THUR-CUP PEA製程)達到上下銅箔間的導通。 接著，於該無電解鍍覆的表面上，將厚25μιη之紫外線感 光性乾薄膜(旭化成公司製，SUNFORT UFG-255)藉加熱輥 層合器予以貼合。接著’對準描晝了最小線寬/線間為 20/20μηι之圖案的玻璃遮罩(Topic公司製）之位置。接著使 用該玻璃遮罩，藉曝光裝置（小野測器EV-0800)進行曝光 後，於碳酸鈉水溶液進行顯影，形成抗鍍遮罩。接著，以無 101102467 46 201251534 電解鍍覆層作為給電層電極，依3A/dm2、25分鐘進行電鍍 銅（奥野製藥公司製81-HL)。藉此，形成厚約2〇μιη的銅佈 線圖案。接著，使用剝離機，藉由單乙醇胺溶液(三菱氣體 化學公司製R-100)，將上述抗鍍遮罩剝離。然後，將屬於 給電層之圖案形狀以外之不需要的銅箔及無電解鍍覆層藉 快速餘刻（接原電產公司製SAC-702M與SAC-701R35之純 水溶液）予以去除，形成L/S=20/2(^m之圖案。 接著’進行導體電路之粗化處理（Mec公司製， MECetchBOND CZ-8100)。該粗化處理係藉由依液溫35。(：、 喷霧壓0.15MPa之條件進行噴霧器噴霧處理，對銅表面實 施粗度3μηι左右的粗面化而進行。接著，進行導體電路之 表面處理(Mec公司製，MECetchBOND CL-8300)。該表面 處理時，依溫度25°C、浸潰時間20秒之條件進行浸潰，對 銅表面進行防銹處理。如此製作印刷佈線板（内層電路基 板）。 (5)多層印刷佈線板之製造 接著以上述所得之印刷佈線板作為内層電路基板，於其 兩面上重蟹配置上述多層印刷佈線板絕緣層用預浸體與具 2帅銅、冶（三井金屬礦業公司製，Microsin MT18EX_2)，使用真空積層裝置進行積層，依溫度20CTC、 壓力 3MPa、時·ρη，、 ^ 、] 120分鐘進行加熱硬化’得到多層積層體。 接著/、上述(4)印刷佈線板（内層電路基板)之製造方法同樣 101102467 201251534 地進行外層電路形成，最後於電路表面形成抗焊層（太陽油 墨公司製，PSR4000/AUS308)，得到多層印刷佈線板。 上述多層印刷佈線板係對相當於半導體元件之焊錫凸塊 的連接用電極部實施ENEPIG處理。ENEPIG處理係藉由⑴ 清潔劑處理、[2]軟蝕刻處理、[3]酸洗處理、[4]預浸處理、 [5] 鈀觸媒賦予、[6]無電解鍍鎳處理、[7]無電解鍍鈀處理、 [8]無電解鍍金處理的步驟進行。 (6) 半導體裝置之製造 半導體裝置係在經ENEPIG處理之印刷佈線板上，藉由倒 裝aa片接5器裝置，將具有焊錫凸塊之半導體元件(丁晶 片，尺寸lOmmxlOmm，厚〇.lmm)藉加熱壓黏予以搭載， 接著，於IR迴焊爐將焊錫凸塊進行熔融接合後，填充液狀 密封樹脂(住友Bakelite公司製，CRP_4152S)，使液狀密封 樹脂硬化而獲得。又，液狀密封樹脂係依溫度15〇。〇、12〇 分鐘之條件進行硬化。又，上述半導體元件之焊錫凸塊係使 用由Sn/Pb組成之共晶所形成者。最後藉刻模機個片化為 14mmxl4mm之尺寸，得到半導體裝置。 &lt;實施例2〜3及比較例ι〜6&gt; 使用表4所示之纖維織布及由清漆之製造例所得的清 漆’與實施例1同樣地進行而得到預浸體、於厚15一之 絕緣層之兩面具有_的金㈣積層板、印刷佈線板（内層 電路基板）、乡騎㈣線缺半導體裝置。 101102467 201251534 〈實施例4〜6及比較例7&gt; 製作預浸體時，除了將具有樹脂層之基材的樹脂層厚度設 為如表5所示般以外，使用表5所示之纖維 製造例所得的清漆，與實施例1同樣地進行而得到預^體、 於厚ΙΟΟμιη之絕緣層之兩面具有銅箔的金屬帛積層=、印 刷佈線板（内層電路基板）、多層印刷佈線板及半導體裝置。 尚且，印刷佈線板之貫通穿孔形成’係使用二氧化碳雷射 (三菱電機公司製，ML605GTX3-5100U2)，依孔徑φ 1.1mm、 光束徑約ΙΙΟμιη、能量7〜9mJ、射數6之條件進行，形成直 徑ΙΟΟμιη之貫通穿孔。 &lt;實施例7、8及比較例8&gt; 實施例7及比較例8係於製作預浸體時，除了將具有樹脂 層之基材的樹脂層厚度設為如表6所示般以外，使用表6 所不之纖維織布及由清漆之製造例所得的清漆，與實施例j 同樣地進行而得到預浸體、於厚60μιη之絕緣層之兩面具有 銅箔的金屬箔積層板、印刷佈線板(内層電路基板）、多層印 刷佈線板及半導體裝置。 實施例8係於製作預浸體時，除了將具有樹脂層之基材的 樹脂層厚度設為如表6所示般以外，使用表6所示之纖維織 布及由清漆之製造例所得的清漆，與實施例丨同樣地進行而 得到預浸體（整體厚30μιη)、積層2片該3〇μηι之預浸體並硬 化而成之厚60μηι之絕緣層之兩面具有銅箔的金屬箔積層 101102467 49 201251534 板、内層電路基板、多層印刷佈線板及半導體裝置。 尚且，印刷佈線板之貫通穿孔形成，係使用二氧化碳雷射 (三菱電機公司製，ML605GTX3-5100U2)，依孔徑φ 1.1_、 光束控約ΙΙΟμιη、能量6〜8mJ、射數ό之條件進行，形成直 徑ΙΟΟμιη之貫通穿孔。 &lt;實施例9及比較例9&gt; 製作預浸體時’除了將具有樹脂層之基材的樹脂層厚度設 為如表7所示般以外，使用表7所示之纖維織布及由清漆之 製造例所得的清漆，與實施例1同樣地進行而得到預浸體、 於厚40μιη之絕緣層之兩面具有銅箔的金屬箔積層板、印刷 佈線板（内層電路基板）、多層印刷佈線板及半導體裝置。 尚且，印刷佈線板之貫通穿孔形成，係使用二氧化碳雷射 (三菱電機公司製，ML605GTX3-5100U2)，依孔徑、 光束徑約ΙΙΟμηι、能量6〜8mJ、射數6之條件進行， 徑ΙΟΟμιη之貫通穿孔。 針對實施例及比較例所得的預浸體、金屬猪積層板、印刷 佈線板(内層電路基板)及半導體裝置，進行以下評估。將評 估項目與内容-起表示^並將所得之評估結果示於表4〜7。 尚且，由則灸述之PKG曲紐之測定結果依存於金屬箱積 層板之絕緣層厚度’故將金制積層板之絕緣層之厚度為 15〇帅的實施例及比較例的評估結果示於表4，將金屬羯積 層板之絕緣層之厚度為100阿的實施例及比較例的評估結 10Π02467 50 201251534 果不於表5 ’將金屬箔積層板之絕緣層之厚度為6〇μΓη的實 施例及比較例的評估結果示於表6，將金屬箔積層板之絕緣 層之厚度為40μιη的實施例及比較例的評估結果示於表7。 另外，表4〜7中，樹脂組成物中之填充材量（質量％)係表 示將樹脂組成物整體設為1〇〇質量％時的填充材量者，填充 材之組成（質量)％係表示將填充材整體設為1〇〇質量％時之 各成分的比例。 &lt;評估方法&gt; (1) 樹脂組成物之含浸性 將上述實施例及比較例所得之預浸體依170t之溫度硬 化1】、時後，對剖面（寬度方向之剖面部300mm之範圍）藉 SEM(掃描型電子顯微鏡)進行觀察，評估於纖維内部有無空 隙。空隙係於影像上，以纖維剖面之白色粒狀的點之形式被 觀察到。 各符號係如下述。 〇.树脂組成物全部良好地含浸，於纖維内部無空隙 X.於纖維内部有空隙 (2) 成形性 對上述實施例及比較例所得之金屬落積層板之鋼馆進行 整面蝕刻後，對5〇〇mmx5〇〇mm之範圍藉sem(掃插型電= 顯微鏡)進行觀察，評估於絕緣層（位於纖維織布層之表面的 樹脂層）之表面有無空隙。空隙係於影像上，以白色粒狀= 101102467 51 201251534 點之形式被觀察到。 各符號係如下述。 〇：無空隙 X :有空隙 (3)吸濕焊錫财熱性 使用將上述實施例及比較例所得之金屬箱積層板切斷為 50mmx50mm見方的樣本，根據JIS c_648i，將上述樣本之 單面之-半以外_有_予以關去除，藉由壓力鍋試驗 機(ESPEC公司製)依121。(：、2氣壓處理2小時後於26〇t： 之焊錫槽中浸潰30秒’以目視觀察有無外觀變化的異常。 各符號係如下述。 〇：無異常 X:有膨脹、剝離 (4)線熱膨脹係數(CTE)(ppm/K) 線熱膨脹係數(CTE)係使用TMA(熱機械性分析)裝置(TA Instrument公司製’ Q400)，製作4mmx20mm的試驗片，依 溫度範圍30〜300°C、l〇°C/分鐘、負重5g之條件測定第2 循環之50〜100°C下的CTE。又’樣本係使用將各實施例及 比較例所得之金屬箔積層板的銅箔予以钱刻去除者。 (5)雷射加工性 使用上述實施例及比較例所得之印刷佈線板（内層電略茂 板）’測定碳酸雷射加工後之貫通穿孔的布料突出量、 子匕徨 101102467 52 201251534 之真圓度。布料突出量及真圓度的測定係使用彩色3D雷射 顯微鏡(Keyence公司製，裝置名VK-9710)，布料突出量的 測定係藉由由雷射入射側之孔的正上方進行觀察，測定由孔 .壁面之突出長度而進行；真圓度的測定係由雷射入射侧之孔 的正上方進行觀察，測定孔頂徑之長徑與短徑，藉由算出長 徑+短徑而進行。又，樣本係使用由上述實施例及比較例所 得之印刷佈線板（内層電路基板），依下述表2所示之二氧化 碳雷射條件’對直徑ΙΟΟμιη之孔加工即刻後的基板由正上 方進行觀察，作為貫通孔10個的平均值。 [表2] 金屬箔積層板之絕緣層厚度 (μηι) 孔徑 (min') 光束徑 能量 150 —、 V _ φ 1 4 _JL12〇^ 一(mj) 100 Φ ττ~ 7-9 6 _ . 60 Φ 1.1 11() 7-9 6 . 40 Φ μ 約1 ] 0 6-8 6 衣罝·二曼電機公司製，ML605GTX3-5100U2 6-8 6 脈衝長度：l〇pSec/lsh〇t+97psec/2〜6shot 各符號係如下述。 〇：布料突出量為ΙΟμιη以内，真圓度為〇 85以上 △:布料突出量為以上、或真圓度為未滿〇 85 X:布料突出量為ΙΟμιη以上，且真圓度為未滿〇 85 (6)貫通穿孔之絕緣可靠性 使用上述實施例及比較例所得之印刷佈線板（内層電路基 板）’評估貫通穿孔間之絕緣可靠性。 使用印刷佈線板之穿孔壁間〇.lmm部分，依施加電壓 101102467 53 201251534 10V、溫度130°c、濕度85%的條体 1午’以連續測定進行評估》 又’測定係使用高度加速壽命q n p式驗裴置（ESPEC公司製 EHS-211(M)，AMI離子遷移系蜞、、包^ 丁遊秒于、、死）進行，在絕緣電阻值成為 未滿108Ω的時點設為結束。 各符號係如下述。 ◎:超過200小時 〇：100小時以上且200小時以下 △ : 50小時以上且未滿1〇〇小時 X :未滿50小時 (7)PGK曲麵 將貫施例及比較例所得之半導體裝置（14mmx 14mm)，於 濕度可變雷射三維測定機（日立Technology and Service公司 製，形式LS220-MT100MT50)之樣本室内將半導體元件面朝 下設置，使用上述測定機，測定半導體裝置之室溫(25°C)及 260°C下的曲勉。曲翹之測定係測定高度方向的位移，以位 移差之最大值作為曲翹量。又，測定範圍係13mmxl3mm尺 寸。 各符號係如下述。又，PKG曲翹之測定由於依存於金屬 箔積層板之絕緣層厚度，故如表3所示般分別依金屬箔積層 板之絕緣層之厚度進行判定。 101102467 54 201251534 [表3] 金屬箱積層板之絕緣層厚度 (μιη) 25°C曲翹 260°C曲翹 150 〇 150μηι以下 〇：80μχη以下 X 超過150μιη X :超過 80μιη 100 〇 200μηι以下 〇：ΙΟΟμηα以下 X 超過200μιη )χ(:超過 ΙΟΟμηι 60 〇 250μηι以下 〇：120μπα以下 X 超過250μηι X :超過 120μιη 40 〇 320μηι以下 〇：150μηι以下 X 超過320μπι X :超過 150μηι 55 101102467 201251534 【寸&lt;】 比較例6 T玻璃 iTi 2 s p cc ?~H JQ S5 ΓΟ 8 »•4 in oi ο § X X X in in &lt;] 0 X 比較例5 X T玻璃 m un cn p 00 tn ro JO 00 m r*H 8 1 17.5 1 JO T—H ο jn X 〇 X Ο) &lt;] X 〇 比較例4 &lt; T玻璃 JO § 1—1.19 I QC g 卜 8 〇 T—η Ο 沄 ο in X X X VO X X X 比較例3 &lt; T玻璃 in m On 00 VO JQ S 穿 〇 r·^ ο 沄 ο iQ 1—Η X X X X X X 1比較例2 &lt; T玻璃| o ΓΛ | 1.19 — I 00 沄 a f«~H Ο ο 沄 Ο ι〇 X X X 卜 rn &lt; X X 比較例1 &lt; T玻璃 〇 m »—H Os 00 寸 ? 1 87.5 1 yr-i (N ο ο 沄 r&quot; Η Ο i〇 〇 〇 〇 m σ； 〇 ◎ X 實施例3 &lt; T玻璃 o 2 1 1.19 1 00 g m 8 ο 冢 V&quot;*H ο ΙΟ 〇 〇 〇 〇 ◎ 〇 丨實施例2 &lt; T玻璃 yn T—&lt; O cn 1 119 1 00 5! 卜 CN 〇 二 8 ο 沄 ο jn 泛 〇 〇 〇 Ο) 〇 ◎ 〇 實施例1 &lt; T玻璃 m O rn 1 1-19 1 00 g JO 00 ΓΛ f&quot;H 8 ο 沄 ο JO § 〇 〇 〇 (N rn 〇 ◎ ◎ 玻璃記號 玻璃繼 1 tlfhil ψ»Ί 1 12^ 1 I 1 m 時 ^r \a| ? % m 1 η ? ♦ 1 I € \iiji V 1 裒 τ〇Η Φ4 1 •6- 1)0 1 ρ 1·Η 磁 | I 1 1 f 5 1 1 u μ 1 1 磁 菊 | $ Ί ^ϊο&quot; I 1)01 s ? ΰ§α 1)01 &lt; 1 ii °4； xim 1 δ 费 癍 1 ψ 1 s 架 PP之含浸性 I 雷射加工性 il i&lt; fV ㈣ PKG曲翹 纖象織布 填充材之組成 (ft%) 預浸體 言啊古 9·°/.9301101 201251534 [表5]Unizhika company made glass woven fabric, Ε02Ζ, basis weight i7.5g/m2), dried in a heating oven of 18〇t: for 2 hours to obtain the resin composition in the prepreg as solid reference 101102467 45 201251534 About 78% by weight of the prepreg (thickness 40 μm). Further, the ruthenium-woven fabric had a bulk density of 1.09 g/cm3, a gas permeability of 41 cc/cm2/sec, and an aspect ratio (thickness: width) of 1:16. Further, the glass woven fabric has a Young's ratio of 93 GPa when formed into a plate shape, a tensile strength of 48 GPa when the plate is formed, and a tensile strength of 9 〇N/25 mm in the longitudinal direction when the fiber woven fabric is formed. The fabric of the fabric. (4) Manufacturing of printed wiring board (inner layer circuit board) The carrier foil was peeled off by the above-mentioned metal foil laminated board, and carbon dioxide laser (Mitsubishi Electric Corporation's ML605GTX3-5100U2) was used, and the aperture was φ l.4 mm, and the beam control was about 120 μm. The condition of energy 7~9mJ and number of shots 6 forms a through-perforation of φ i〇〇_. Next, the metal foil laminate was immersed in 70. (: The swelling liquid (Swelling Dip Securiganth P, manufactured by ATOTECH JAPAN Co., Ltd.) was immersed in an aqueous solution of potassium perchlorate (Concentrate Compact CP manufactured by ATOTECH JAPAN Co., Ltd.) at 80 ° C for 1 minute, and then And the roughening treatment is carried out. Then, the electroless plating (THUR-CUP PEA process manufactured by Uemura Industrial Co., Ltd.) is used to achieve the conduction between the upper and lower copper foils. Next, on the electrolessly plated surface, the ultraviolet rays are 25 μm thick. The photosensitive dry film (SUNFORT UFG-255, manufactured by Asahi Kasei Co., Ltd.) was attached by a heated roll laminator. Then, the glass mask with a minimum line width/line width of 20/20 μη was traced (Topic Corporation) Then, using the glass mask, exposure was performed by an exposure apparatus (Ono EV-0800), and then developed in an aqueous solution of sodium carbonate to form a plating resist. Then, electrolytic plating was performed without 101102467 46 201251534. The layer was used as an electrode layer electrode for electroplating copper (81-HL manufactured by Okuno Pharmaceutical Co., Ltd.) at 3 A/dm 2 and 25 minutes. Thereby, a copper wiring pattern having a thickness of about 2 μm was formed. Next, a stripper was used, and monoethanol was used. The solution (R-100, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used to peel off the above-mentioned anti-plating mask. Then, the copper foil and the electroless plating layer, which are not in the shape of the pattern of the power-feeding layer, were quickly replenished. The company's SAC-702M and SAC-701R35 pure aqueous solution were removed to form a pattern of L/S=20/2 (^m. Then, the conductor circuit was roughened (Mecetch BOND CZ-8100, manufactured by Mec Co., Ltd.). This roughening treatment is carried out by spraying the sprayer under the conditions of a liquid temperature of 35 (:, a spray pressure of 0.15 MPa, and roughening the surface of the copper to a thickness of about 3 μm. Then, the surface treatment of the conductor circuit is performed ( MEC Corporation, MECetchBOND CL-8300. In the surface treatment, it is impregnated under the conditions of a temperature of 25 ° C and an impregnation time of 20 seconds to rust the copper surface. Thus, a printed wiring board (inner circuit board) is produced. (5) Manufacturing of Multilayer Printed Wiring Board Next, the printed wiring board obtained as described above is used as an inner layer circuit board, and the prepreg for the above-mentioned multilayer printed wiring board insulating layer is disposed on both sides thereof and has a handsome copper and metallurgy (Mitsui gold Microsin MT18EX_2) manufactured by a mining company, laminated by a vacuum laminating apparatus, and heat-hardened by a temperature of 20 CTC, a pressure of 3 MPa, a time of ρη, , ^, and 120 minutes to obtain a multilayered laminate. Next, the above (4) printed wiring The manufacturing method of the board (inner layer circuit board) was similarly formed in the form of 101102467 201251534, and finally a solder resist layer (PSR4000/AUS308, manufactured by Sun Ink Co., Ltd.) was formed on the surface of the circuit to obtain a multilayer printed wiring board. The multilayer printed wiring board is subjected to an ENEPIG treatment on a connection electrode portion corresponding to a solder bump of a semiconductor element. ENEPIG treatment is performed by (1) detergent treatment, [2] soft etching treatment, [3] pickling treatment, [4] prepreg treatment, [5] palladium catalyst application, [6] electroless nickel plating treatment, [7] The steps of electroless palladium plating and [8] electroless gold plating are carried out. (6) Manufacturing of semiconductor device The semiconductor device is mounted on an ENEPIG-treated printed wiring board, and a semiconductor component having a solder bump (a wafer size of 10 mm x 10 mm, a thickness of .1 mm) is flip-chip mounted by a device. After the solder bumps were melt-bonded in an IR reflow furnace, the liquid sealing resin (CRP_4152S, manufactured by Sumitomo Bakelite Co., Ltd.) was filled and the liquid sealing resin was cured. Further, the liquid sealing resin is at a temperature of 15 Torr. It is hardened under conditions of 12 minutes. Further, the solder bump of the above semiconductor element is formed by using a eutectic composed of Sn/Pb. Finally, a semiconductor device was obtained by engraving a die to a size of 14 mm x 14 mm. &lt;Examples 2 to 3 and Comparative Examples ι to 6&gt; Using the fiber woven fabric shown in Table 4 and the varnish obtained by the production example of the varnish, the prepreg was obtained in the same manner as in Example 1, and the thickness was 15 The two sides of the insulating layer have a gold (four) laminate, a printed wiring board (inner circuit board), and a township (four) line missing semiconductor device. 101102467 201251534 <Examples 4 to 6 and Comparative Example 7> When the prepreg was produced, except that the thickness of the resin layer of the substrate having the resin layer was as shown in Table 5, the fiber production example shown in Table 5 was used. The obtained varnish was obtained in the same manner as in Example 1 to obtain a metal entangled layer having a copper foil on both sides of the insulating layer of the thick ΙΟΟ =, a printed wiring board (inner layer circuit board), a multilayer printed wiring board, and a semiconductor device. . In addition, the through-perforation of the printed wiring board is formed by using a carbon dioxide laser (ML605GTX3-5100U2, manufactured by Mitsubishi Electric Corporation), and is formed under the conditions of an aperture of φ 1.1 mm, a beam diameter of about ΙΙΟμιη, an energy of 7 to 9 mJ, and a number of shots. Perforation of the diameter ΙΟΟμιη. &lt;Examples 7 and 8 and Comparative Example 8&gt; In the case of producing a prepreg, the thickness of the resin layer of the base material having the resin layer was as shown in Table 6, and was used. In the same manner as in the example j, a fiber woven fabric and a varnish obtained in the production example of the varnish were obtained in the same manner as in the example j, and a metal foil laminate having copper foil on both sides of an insulating layer having a thickness of 60 μm and a printed wiring were obtained. Board (inner circuit board), multilayer printed wiring board, and semiconductor device. In the case of producing a prepreg, the thickness of the resin layer of the base material having the resin layer was as shown in Table 6, and the fiber woven fabric shown in Table 6 and the production example of the varnish were used. The varnish was obtained in the same manner as in Example 而 to obtain a prepreg (the overall thickness of 30 μm), a laminate of two sheets of the prepreg of 3 〇 μηι, and a metal foil layer having copper foil on both sides of the insulating layer having a thickness of 60 μm. 101102467 49 201251534 Board, inner layer circuit board, multilayer printed wiring board and semiconductor device. In addition, the through-holes of the printed wiring board are formed by using a carbon dioxide laser (ML605GTX3-5100U2, manufactured by Mitsubishi Electric Corporation), and are formed under the conditions of the aperture φ 1.1_, the beam control ΙΙΟμιη, the energy of 6 to 8 mJ, and the number of shots. Perforation of the diameter ΙΟΟμιη. &lt;Example 9 and Comparative Example 9&gt; When the prepreg was produced, the fiber woven fabric shown in Table 7 and the varnish were used except that the thickness of the resin layer of the substrate having the resin layer was as shown in Table 7. The varnish obtained in the production example was obtained in the same manner as in Example 1 to obtain a prepreg, a metal foil laminate having copper foil on both sides of an insulating layer having a thickness of 40 μm, a printed wiring board (inner circuit board), and a multilayer printed wiring board. And a semiconductor device. In addition, a through-hole is formed in the printed wiring board, and a carbon dioxide laser (ML605GTX3-5100U2, manufactured by Mitsubishi Electric Corporation) is used, and the diameter, the beam diameter is about ΙΙΟμηι, the energy is 6 to 8 mJ, and the number of shots is 6, and the diameter is 贯通μιη. perforation. The following evaluations were performed on the prepreg, the metal pig laminate, the printed wiring board (inner circuit board), and the semiconductor device obtained in the examples and the comparative examples. The evaluation items and contents are shown as ^ and the evaluation results obtained are shown in Tables 4 to 7. Furthermore, the results of the measurement of the PKG curve of the moxibustion are dependent on the thickness of the insulating layer of the metal laminated plate. Therefore, the evaluation results of the examples of the insulating layer of the gold laminated plate and the comparative example are shown in Table 4, evaluation of the thickness of the insulating layer of the metal delamination layer of 100 Å and the evaluation of the comparative example 10 Π 02467 50 201251534 The implementation of the thickness of the insulating layer of the metal foil laminated board is 6 〇 μ Γ The evaluation results of the examples and the comparative examples are shown in Table 6, and the evaluation results of the examples and comparative examples in which the thickness of the insulating layer of the metal foil laminate was 40 μm are shown in Table 7. In addition, in Tables 4 to 7, the amount of the filler (% by mass) in the resin composition is the amount of the filler when the entire resin composition is 1% by mass, and the composition (mass) % of the filler is The ratio of each component when the entire filler is 1% by mass is shown. &lt;Evaluation Method&gt; (1) Impregnation of Resin Composition The prepreg obtained in the above Examples and Comparative Examples was cured at a temperature of 170 t, and then the cross section (the range of the cross-sectional portion in the width direction of 300 mm) Observation was carried out by SEM (scanning electron microscope) to evaluate whether or not voids were present inside the fibers. The voids are attached to the image and are observed in the form of white granular spots of the fiber cross section. Each symbol is as follows.树脂. The resin composition is all well impregnated, and there is no void in the fiber. X. There are voids in the fiber. (2) Formability After the entire surface of the steel pavement of the metal-layered laminate obtained in the above examples and comparative examples is etched, The range of 5 〇〇 mm x 5 〇〇 mm was observed by sem (sweep type electric = microscope), and it was evaluated whether or not the surface of the insulating layer (the resin layer on the surface of the fiber woven layer) had a void. The voids were attached to the image and were observed in the form of white grain = 101102467 51 201251534 points. Each symbol is as follows. 〇: no voids X: voids (3) moisture-absorbing solders. The use of the metal box laminates obtained in the above examples and comparative examples was cut into 50 mm x 50 mm square samples, and according to JIS c_648i, one side of the above samples - Half of the other _ has _ removed, by the pressure cooker test machine (ESPEC company) according to 121. (:, 2 air pressure treatment for 2 hours, and then immersed in a solder bath of 26 〇t: for 30 seconds' to visually observe the presence or absence of an abnormal change in appearance. Each symbol is as follows. 〇: no abnormality X: expansion, peeling (4 ) Linear thermal expansion coefficient (CTE) (ppm/K) The linear thermal expansion coefficient (CTE) is a TMA (thermo-mechanical analysis) device (Q400) manufactured by TA Instrument Co., Ltd., and a test piece of 4 mm x 20 mm is produced, depending on the temperature range of 30 to 300°. The CTE at 50 to 100 ° C of the second cycle was measured under the conditions of C, l 〇 ° C / min, and a load of 5 g. Further, the sample was obtained by using the copper foil of the metal foil laminate obtained in each of the examples and the comparative examples. (5) Laser processing property Using the printed wiring board (inner layer) of the above-mentioned Examples and Comparative Examples', the amount of cloth protruding through the perforation after the carbonation laser processing was measured, and the amount of the cloth was measured. The roundness of 201251534. The measurement of the amount of protrusion and roundness of the fabric is measured by a color 3D laser microscope (manufactured by Keyence Corporation, device name VK-9710), and the amount of protrusion of the cloth is measured by the hole on the incident side of the laser. Observed directly above, measured by the hole. The measurement of the roundness is performed by directly above the hole on the incident side of the laser, and the long diameter and the short diameter of the top diameter of the hole are measured, and the long diameter + the short diameter are calculated. The printed wiring board (inner layer circuit board) obtained in the above-described examples and comparative examples was observed as a through hole 10 by directly observing the substrate immediately after the hole diameter of the diameter of the printed wiring board (the inner layer circuit board shown in Table 2 below). [Table 2] Thickness of insulating layer of metal foil laminate (μηι) Aperture (min') Beam diameter energy 150 —, V _ φ 1 4 _JL12〇^ One (mj) 100 Φ ττ~ 7-9 6 _ . 60 Φ 1.1 11() 7-9 6 . 40 Φ μ Approx. 1 ] 0 6-8 6 罝 罝 二 二 二 ML ML ML ML ML ML ML ML ML ML ML ML ML ML ML ML ML ML ML ML ML ML ML 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲 脉冲t+97psec/2~6shot Each symbol is as follows. 〇: The amount of cloth protrusion is within ΙΟμιη, and the roundness is 〇85 or more △: The amount of cloth protrusion is above, or the roundness is not full 〇85 X: Cloth highlight The amount is ΙΟμιη or more, and the roundness is less than 〇85 (6) The insulation reliability of the through-hole is the above The printed wiring board (inner layer circuit board) obtained in the examples and the comparative examples evaluated the insulation reliability between the through-holes. The portion of the perforated wall between the perforated walls of the printed wiring board was applied with a voltage of 101102467 53 201251534 10V and a temperature of 130 ° C. The bar with a humidity of 85% is evaluated by continuous measurement. The measurement system uses a highly accelerated life-time qnp-type test device (EHS-211 (M) manufactured by ESPEC, AMI ion migration system, ^ The travel is performed in the second or the second, and the end of the insulation resistance value is less than 108 Ω. Each symbol is as follows. ◎: more than 200 hours 〇: 100 hours or more and 200 hours or less △: 50 hours or more and less than 1 hour X: less than 50 hours (7) PGK curved surface will be obtained by the semiconductor device of the example and the comparative example ( 14mm x 14mm), the semiconductor element is placed face down in the sample chamber of the humidity variable laser three-dimensional measuring machine (form LS220-MT100MT50, manufactured by Hitachi, Technology and Service Co., Ltd.), and the room temperature of the semiconductor device is measured using the above measuring device (25 °C) and Qufu at 260 °C. The measurement of Quqiao is to measure the displacement in the height direction, and the maximum value of the displacement difference is used as the amount of warpage. Further, the measurement range was 13 mm x 13 mm. Each symbol is as follows. Further, since the measurement of the PKG curve was dependent on the thickness of the insulating layer of the metal foil laminate, the thickness of the insulating layer of the metal foil laminate was determined as shown in Table 3, respectively. 101102467 54 201251534 [Table 3] Thickness of insulating layer of metal box laminate (μιη) 25°C 翘260°C 翘150 150 〇150μηι or less 80: 80μχη below X exceeds 150μηη X : more than 80μιη 100 〇200μηι or less 〇:ΙΟΟμηα The following X exceeds 200μηη ) χ (: more than ΙΟΟμηι 60 〇 250μηι or less 120: 120μπα or less X exceeds 250μηι X: more than 120μιη 40 〇320μηι or less 150: 150μηι or less X exceeds 320μπι X : more than 150μηι 55 101102467 201251534 [inch &lt;] Comparative Example 6 T glass iTi 2 sp cc ?~H JQ S5 ΓΟ 8 »•4 in oi ο § XXX in in &lt;] 0 X Comparative Example 5 XT glass m un cn p 00 tn ro JO 00 mr*H 8 1 17.5 1 JO T—H ο jn X 〇X Ο) &lt;] X 〇Comparative Example 4 &lt;T-glass JO § 1—1.19 I QC g 卜8 〇T—η Ο 沄ο in XXX VO XXX Comparative Example 3 &lt; T Glass in m On 00 VO JQ S 〇r·^ ο 沄ο iQ 1—Η XXXXXX 1 Comparative Example 2 &lt;T glass | o ΓΛ | 1.19 — I 00 沄af«~H Ο ο 沄Ο ι〇XXX Rn &Lt; XX Comparative Example 1 &lt;T glass 〇m »-H Os 00 inch? 1 87.5 1 yr-i (N ο ο 沄r&quot; Η Ο i〇〇〇〇m σ; 〇 ◎ X Example 3 &lt; T glass o 2 1 1.19 1 00 gm 8 ο 冢V&quot;*H ο ΙΟ 〇〇〇〇◎ 〇丨Example 2 &lt;T glass yn T-&lt; O cn 1 119 1 00 5! 卜CN 〇 2 8 ο 沄ο jn 〇〇〇Ο 〇〇〇Ο 〇 〇 〇 Example 1 &lt; T glass m O rn 1 1-19 1 00 g JO 00 ΓΛ f&quot;H 8 ο 沄ο JO § 〇〇〇 (N rn 〇 ◎ ◎ Glass mark glass following 1 tlfhil ψ»Ί 1 12^ 1 I 1 m ^r \a| ? % m 1 η ? ♦ 1 I € \iiji V 1 裒τ〇Η Φ4 1 •6- 1)0 1 ρ 1·Η Magnetic | I 1 1 f 5 1 1 u μ 1 1 菊菊 | $ Ί ^ϊο&quot; I 1)01 s ? ΰ§α 1)01 &lt; 1 ii °4; xim 1 δ 费癍1 ψ 1 s frame impregnation of PP I Laser processing il i&lt; fV (4) Composition of PKG curved fiber woven fabric filler (ft%) Prepreg language ah ancient 9·°/.9301101 201251534 [Table 5]

實施例4 實施例5 實施例6 比較例7 纖維織布 玻瑀基材記號 B C D J 玻瑀種類 E玻璃 Τ玻璃 D玻瑀 τ玻璃 基重ω 121 114 114 100 厚度(wn) Ί 95 95 95 97 體積 fcia/cy) 1.27 1.20 1.20 1.03 通氣度(cc/cmz/s) 4.2 7.1 7.2 11.0 扁平準(厚： 1:6 1:8 1:8 1:10 玻璃之拉張強度(GPa) 46 32 25 46 玻瑀之楊氏準(GPa) 93 85 60 93 威布之矣度方向的拉張強度 (N/25mm) 395 350 390 730 清漆製造例 1 1 1 7 樹脂組成物中之填充材量(質量％) 75 75 75 75 填充材 之組戒 (質量％) 球狀二氣化矽(平均3 l.Oum') 87 87 87 100 二氣化矽粒子(平均i 徑 70nm) 13 13 13 0 計 100 100 100 100 具有樹脂/ 1之基材的樹脂層厚度(μτη) 27 29 29 31 預浸體 樹脂層ί單面)厚度(umi 2.5 2.5 2.5 1.5 纖維，鐵布層厚度Oun) 95 95 95 97 整體厚皮_ 100 100 100 100 金M f自積} 1板之絕緣層屢度(um) 100 100 100 100 評估 PP之含浸性 Ο Ο Ο X 成形性 Ο C； O X 吸濕焊錫 Ο Ο X CJlJi(ppm/K) 5.6 5.9 4.9 4.7 雷射加工性 Ο Ο Ο Δ 貫通穿孔之絕緣可靠性 CQ) (ο) ο Δ PKG曲翹 Ο ϋ ο X 57 101102467 201251534 [表6]Example 4 Example 5 Example 6 Comparative Example 7 Fiber woven glass substrate mark BCDJ glass type E glass Τ glass D glass 瑀 glass basis weight ω 121 114 114 100 thickness (wn) Ί 95 95 95 97 volume Fcia/cy) 1.27 1.20 1.20 1.03 Air permeability (cc/cmz/s) 4.2 7.1 7.2 11.0 Flat gauge (thickness: 1:6 1:8 1:8 1:10 tensile strength of glass (GPa) 46 32 25 46瑀 杨 杨 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 395 75 75 75 75 Packing ring (% by mass) Spherical gasified bismuth (average 3 l.Oum') 87 87 87 100 Two gasified bismuth particles (average i diameter 70 nm) 13 13 13 0 100 100 100 100 resin layer thickness (μτη) with resin / 1 substrate 27 29 29 31 prepreg resin layer 单 single side) thickness (umi 2.5 2.5 2.5 1.5 fiber, iron layer thickness Oun) 95 95 95 97 overall thickness Leather _ 100 100 100 100 Gold M f self-product} 1 board insulation layer repeat (um) 100 100 100 100 Evaluation of PP impregnation Ο Ο Ο X Formability Ο C; OX absorbing solder Ο Ο X CJlJi(ppm/K) 5.6 5.9 4.9 4.7 Laser processability Ο Ο Ο Δ Insulation reliability of through-holes CQ) (ο) ο Δ PKG 翘 Ο ϋ ο X 57 101102467 201251534 [Table 6]

實施例7 實施例8 比較例8 纖維織布 玻璃基材記號 E F Κ 玻瑀種類 T玻璃 Τ玻璃 Τ玻瑀 基重/β) 54 24 48 M-mrni) 50 20 50 體積备卓Cs/crp3) 1.08 1.2 0.96 通氣度(cc/cm /s) 8.8 9.0 20.0 扁平準(厚： 1:17 1:15 1:20 玻瑀之&amp;張強#(GPa) 46 46 46 玻瑀之楊氏率fcPa) 93 93 93 織蒂之長度方向的拉張強度 (N/25mm) 320 140 120 清漆製造例 1 1 7 樹脂組成物中之填充材量(質量％) 75 75 75 總。f組成 球狀二氣化矽(平均/i 立徑l.Oum) 87 87 100 二k化矽粒子ί平均ί 5iL徑 70nm) 13 13 0 言- 100 100 100 具有樹脂層之基材的樹脂層厚度(μηι) 19.5 11 21 預浸體 樹脂單面)厚度(um) 5 5 5 纖維1¾布層厚度Oun) 50 20 50 整厚皮(wm) 60 30 60 金贗箔精層板之絕緣層厚度Oun)「層數1 60Π1 60Γ21 60Π1 評估 PP之含浸性 Λ () X 成形性 〇 〇 〇 吸濕焊錫 〇 () 〇 CTECppm/K) 4.5 4.9 6.5 雷射加工性 〇 C) Δ 貫通穿孔之絕緣可靠性 ◎ 〇 〇 PKG曲翹 〇 X 58 101102467 201251534 [表7]Example 7 Example 8 Comparative Example 8 Fiber woven glass substrate mark EF Κ Glass type T glass Τ glass Τ glass 瑀 basis weight / β) 54 24 48 M-mrni) 50 20 50 volume preparation Cs/crp3) 1.08 1.2 0.96 Air permeability (cc/cm / s) 8.8 9.0 20.0 Flat gauge (thickness: 1:17 1:15 1:20) Glassy &amp; Zhang Qiang#(GPa) 46 46 46 Young's rate of glassy ash fcPa) 93 93 93 Tensile strength in the length direction of the woven woven fabric (N/25mm) 320 140 120 Varnish manufacturing example 1 1 7 Filling material amount (% by mass) in the resin composition 75 75 75 Total. f consists of globular gasified bismuth (average / i vertical diameter l.Oum) 87 87 100 two k yttrium particles ί average ί 5iL diameter 70nm) 13 13 0 言 - 100 100 100 resin layer of substrate with resin layer Thickness (μηι) 19.5 11 21 Prepreg resin single side) Thickness (um) 5 5 5 Fiber 13⁄4 cloth thickness Oun) 50 20 50 Thick skin (wm) 60 30 60 Thickness of insulating layer of gold foil foil Oun) "Number of layers 1 60Π1 60Γ21 60Π1 Evaluation of PP impregnation Λ () X Formability 〇〇〇 Absorbance solder 〇 () 〇CTECppm/K) 4.5 4.9 6.5 Laser processing 〇C) Δ Through-hole perforated insulation is reliable Sex ◎ 〇〇 PKG 〇 〇 X 58 101102467 201251534 [Table 7]

纖維織布 厚度(μπι) 體積密度(g/cm^T 通氣度(cc/cm2/s) 27 1.15 27 0.93 扁平率(厚：寬） 玻璃之拉張強度(GPa) 14.0 1:29 70.0 1:25Fiber woven fabric thickness (μπι) Bulk density (g/cm^T Air permeability (cc/cm2/s) 27 1.15 27 0.93 Flatness (thickness: width) Tensile strength of glass (GPa) 14.0 1:29 70.0 1: 25

歡組成 球狀二氧化矽(平均粒徑l.Oum) 二氧化矽粒子(平均粒徑70nm) 計 13 0 盖有樹脂層之基材的樹脂層厚度(μιη) 預浸體 榭脂層（單面)厚度(um) 纖維織布層厚度(μιη) 整體厚度(μηι) _金屬箔精層板之絕緣層厚度(μιη) ΡΡ之含浸性 成形性 14 6.5 27 40 40 100 15 6.5 27 40 40欢 球 球 矽 矽 平均 平均 平均 平均 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 13 13 13 13 13 13 13 13 13 13 13 13 13 13 预 预 预 预 预 预 预 预 预 预 预 预 预Surface) Thickness (um) Fiber woven layer thickness (μιη) Overall thickness (μηι) _ Metal foil slab insulation layer thickness (μιη) ΡΡ Impregnation formability 14 6.5 27 40 40 100 15 6.5 27 40 40

X 評估 吸濕焊錫 CTE(ppm/K) 雷射加工性 貫通穿孔之絕緣可靠性 PKG曲翹 4.8 〇 © 〇 6.2 Δ ◎X Evaluation Moisture solder CTE (ppm/K) Laser processability Insulation reliability through through hole PKG curved 4.8 〇 © 〇 6.2 Δ ◎

X 作為上述（1)樹脂組成物之含浸性之觀察結果的代表例， 將實施例1所得之預浸體之刳面圖的照片示於圖3，將比較 例4所得之預浸體之剖面圖的照片示於圖4。 由圖4可知，比較例4中由於樹脂組成物之含浸性惡化， 故於纖維織布中觀察到空隙。另一方面’由圖3可知，由於 實施例1中，樹脂組成物之含浸性良好’故於纖維織布中無 空隙。 實施例1中，認為係因奈米尺寸之二氧化石夕粒子進入至線 股中，故提升樹脂組成物的含浸性。相對於此，比較例4 101102467 59 201251534 故無法達到 中，可知由料含有奈求尺寸之二氧化石夕粒子 樹脂組成物之含浸性提升。 作為上述(2)金屬落積層板之成形性觀察結果的代表例， 將對實施爿1所付之金翻積層板之㈣進行了整面钮刻 之表面的照片示於圖5’將對比較例6所得之金屬_層板 之鋼fi進行了整域刻之表面的照片示於圖6，進而將圖6 所觀察之空隙(影像中為白色粒狀的點）的放大圖的聰照 片示於圖7,將圖7所觀察之空隙之剖面的放大圖的觀 照片不於圖8。如圖6、7、8 % 土凡(. U 〇 /、8所不般，比較例ό中在對金屬 箱積層板進行了整祕刻的表面上觀察到空隙ϋ面， 如圖5所示般’在實施例i中，經整面㈣之表面上未有空 隙。 圖9〜12係表示實施例丨所得之預浸體之構成纖維織布的 線股一部分之剖面圖的SEM照片。圖9表示與線股之延伸 方向呈平行之剖面。圖1〇〜12表示與線股之延伸方向呈垂直 的剖面。 如圖9〜12所示般，可知於實施例丨所得之預浸體中，在 線股中存在二氧化矽粒子。 於表4〜7所示之實施例卜9中，得到良好之預浸體含浸 性。另外，關於其他各種特性，可知全部得到良好結果。其 理由可認為係在二氧化矽粒子進入至構成纖維織布之線股 中的條件下，進行預浸體之作成所致。 ^1102467 60 201251534 :作為控制—氧化$粒子進人線股中的因子，可舉例 :-士氧^粒子之平均粒徑、填充材令之二氧化石夕粒子含 里樹月日組成物中之填充材含量、纖維織布之體積密度等各 種者。 由表4 7可知’實施例1〜9中，清漆所含有之樹脂組成 物係含有該樹脂組成物整體之〜85質量％的填充材，該填 充材中，含有1〜2〇質量％之平均粒徑5〜刚細之二氧化石夕 粒子，且纖維織布之體積密度為1〇5〜13〇細3。此時，於 上述所有。f估項目中為優越的評估結果。亦即，本實施例之 預浸體係樹脂組成物對纖維織布之含浸性優越、低熱膨服 性，在使用料印刷佈線板之絕緣層時雷射加工性優越，藉 雷射所形成之孔係孔徑及形狀_度佳，且可形成抑制了纖 維突出的孔°再者，本實_之預频由於吸祕錫耐熱性 優越’故為高耐熱性，成形性優越，故表面平滑性亦優越， 進而與導體層間之密黏性優越。又，可知由於本發明之半導 體裝置中之PKG曲綠小’故本發明之職體為低熱膨脹 性且高剛性。 比較例1及6中’亦得到良好之預浸體含浸性。 然而’比較例1 t，在CTE及封裝曲翹方面未得到良好 結果。此可認為由於填充材之含量較低，故僅有樹脂組^物 之樹脂成分進入線股内’而抑制二氧化石夕粒子進入線於中所 致。藉此，無法使填充材高填充化’預浸體之CT£變古 101102467 201251534 發生封裝曲翘。 另外，比較例 ，禾得到良好結果。此可認為由於體稍 =較^可使充分量的樹脂組成物含浸，故亦抑制了樹脂 ，、且成物中所含之二氧化雜子進人錢中所致。又，由於纖 維織布之體積密度較小而成為較厚纖維織布，故預浸體表層 之樹脂層厚度M。因此，成形性、吸濕_耐熱性差， CTE雖然良好但發生pKG曲翹。 比較例4及7〜9中，關於預浸體之含浸性，未得到良好結 :。：較例4及7〜”，在構成預浸體之樹脂組成物中並不 3有奈米尺寸的二氧化雜子。因此可認為二氧化雜子未 進入線股纟達到樹脂組成物之含浸性提升。X，因此， 於CTE及封裝自翹等其他各種特財面亦未得到良好結 果0 - 比較例7中，由於纖維織布之體積密度較小，故雷射加工 性差、含浸性差，而貫通穿孔的絕緣可靠性劣化。又，由於 使用了較厚之纖維織布，故預浸體之樹脂層的厚度變薄，成 形性、吸濕焊锡耐熱性差，而發生pKG曲翹。 比較例8及9中，由於金屬箔積層板之絕緣層厚度較薄， 故成形性、吸濕焊錫耐熱性、貫通穿孔之絕緣可靠性優越。 然而’由於纖維織布之體積密度較小，故在雷射加工性方面 未得到良好結果。 比較例2、3及5中，關於預浸體之含浸性未得到良好結 101102467 62 201251534 果。又，關於其他各種特性亦未復 中’可認為由於填充材之含量過故良好結果。比較例2 之二氧切粒子的餘性，結果抑制，未得到樹脂組成物中 的進入。比較例3中’可認為由化雜子朝線股中 之含量高，故奈米尺寸之二氧切之二氧化雜子 化石夕粒子朝線股中的進人。比_凝集，結果抑制二氧 布中，可認為由於纖維織 &amp; ’故抑制了二氧切粒子朝線股中的進 入0 比=例5中’認為纖維織布之體積密度過大，故樹脂組成 έ叹f生差、吸濕焊錫耐熱性差，雷射加工性及貫通穿孔 之絕緣可靠性亦差劣。 比較例6中’由於纖維織布之體積密度較小，故雷射加工 性及貫通穿孔之絕緣可靠性差。再者，由於纖維織布之體積 密度較小而成為較厚的纖維基材，故預浸體之表層的樹脂層 厚度變薄。因此，成形性、吸濕焊錫耐熱性差，發生PKG 曲翘。 本申請案係主張以2011年1月24曰申請之曰本申請案特 願2011-〇12166號為基礎的優先權，將其所有揭示内容引用 於此。 【圖式簡單說明】 圖1為表示本發明之金屬箔積層板之製造方法之一例的 概略圖。 101102467 63 201251534 圖2為表示本發明之金屬箔積層板之製造方法之另一例 的概略圖。 圖3為實施例1所得之預浸體之剖面圖的照片。 圖4為比較例4所得之預浸體之剖面圖的照片。 圖5為對實施例1所得之金屬羯積層板之銅羯進行了整面 蝕刻之表面的照片。 圖6為對比較例6所得之金屬箔積層板之銅箔進行了整面 蝕刻之表面的照片。 圖7為圖6所觀察點之放大圖的SEM照片。 圖8為圖7所觀察點之剖面之放大圖的SEM照片。 圖9為表示構成實施例1所得之預浸體之纖維織布的線股 一部分的剖面圖的SEM照片。 圖10為表示構成實施例1所得之預浸體之纖維織布的線 股一部分的剖面圖的SEM照片。 圖11為表示構成實施例1所得之預浸體之纖維織布的線 股一部分的剖面圖的SEM照片。 圖12為表示構成實施例1所得之預浸體之纖維織布的線 股一部分的剖面圖的SEM照片。 【主要元件符號說明】 10 金屬箔 11 金屬箔 12 樹脂層 101102467 64 201251534 20 30 31 32 40 41 42 51 52 纖維織布 具有樹脂層之高分子薄膜片 高分子薄膜片 樹脂層 預浸體 預浸體 預浸體 金屬箔積層板 金屬箔積層板 101102467 65X is a representative example of the observation result of the impregnation property of the above (1) resin composition, and a photograph of the top view of the prepreg obtained in Example 1 is shown in Fig. 3, and the profile of the prepreg obtained in Comparative Example 4 is shown. A photograph of the figure is shown in Fig. 4. As is clear from Fig. 4, in Comparative Example 4, the impregnation property of the resin composition was deteriorated, so that voids were observed in the fiber woven fabric. On the other hand, as seen from Fig. 3, in Example 1, the impregnation property of the resin composition was good, so that there was no void in the fiber woven fabric. In the first embodiment, it is considered that the infiltrating property of the resin composition is improved because the intrinsic size of the cerium dioxide particles enters the strands. On the other hand, in Comparative Example 4, 101102467 59 201251534, it was found that the impregnation property of the composition of the dioxide-containing particle resin containing the size of the material was improved. As a representative example of the result of the formability observation of the above (2) metal-laid layer, a photograph of the surface of the (4) gold-clad laminate to be subjected to the entire surface of the layer is shown in Fig. 5'. The photograph of the surface of the metal-layered steel obtained in Example 6 which has been subjected to the entire domain is shown in Fig. 6, and the photograph of the enlarged view of the void observed in Fig. 6 (the point of white granularity in the image) is shown. In Fig. 7, a photograph of an enlarged view of a section of the void observed in Fig. 7 is not shown in Fig. 8. As shown in Fig. 6, 7 and 8% of the soil (. U 〇 /, 8 are not the same, in the comparative example, the surface of the metal box laminate was observed on the surface of the void, as shown in Figure 5. In the example i, there is no void on the surface of the entire surface (four). Figs. 9 to 12 are SEM photographs showing a cross-sectional view of a part of the strand of the fiber woven fabric of the prepreg obtained in Example 。. 9 is a cross section parallel to the direction in which the strands extend. Figs. 1 to 12 show cross sections perpendicular to the direction in which the strands extend. As shown in Figs. 9 to 12, it can be seen that the prepreg obtained in the examples is used. The cerium oxide particles were present in the strands. In the examples 9 shown in Tables 4 to 7, good impregnation properties were obtained. Further, various other characteristics were obtained, and the reason was considered to be good. The prepreg is produced under the condition that the cerium oxide particles enter the strands constituting the fiber woven fabric. ^1102467 60 201251534: As a factor in controlling-oxidizing the particles into the strands, for example, :-The average particle size of the oxygen particles and the filler material make the dioxide dioxide The content of the filler in the composition of the saplings and the bulk density of the fiber woven fabric, etc. It is understood from Table 4 that the resin compositions contained in the varnish contained the resin composition as a whole in Examples 1 to 9. ～5% by mass of the filler, the filler contains 1 to 2% by mass of an average particle diameter of 5 to a fine silica dioxide particle, and the fiber woven fabric has a bulk density of 1〇5 to 13〇 Fine 3. At this time, it is a superior evaluation result in all the above-mentioned evaluation items. That is, the resin composition of the prepreg system of the present embodiment has superior impregnation property to the fiber woven fabric and low heat expansion property, and is used in the material. When the insulating layer of the printed wiring board is excellent in laser processing property, the hole diameter and shape formed by the laser are excellent, and the hole which suppresses the protrusion of the fiber can be formed. Further, the pre-frequency of the present is due to the suction. Since the tin is excellent in heat resistance, it has high heat resistance and excellent moldability, so that the surface smoothness is also excellent, and the adhesion between the conductor layers is excellent. Further, it is understood that the PKG is small in the semiconductor device of the present invention. The body of the invention is low thermal expansion and high Rigidity. In Comparative Examples 1 and 6, 'good prepreg impregnation was also obtained. However, 'Comparative Example 1 t did not give good results in terms of CTE and package warp. This is considered to be due to the low content of filler. Only the resin component of the resin component enters the strands' and inhibits the entry of the dioxide particles into the strands. Therefore, the fillers can not be filled with high-filled 'pre-impregnated CT? 101102467 201251534 In addition, in the comparative example, we obtained good results. It is considered that the resin is impregnated with a sufficient amount of the resin composition because it is slightly smaller than the body, so that the resin and the oxidized impurities contained in the product are also inhibited. In addition, since the fiber woven fabric has a small bulk density and becomes a thick fiber woven fabric, the thickness of the resin layer of the surface layer of the prepreg is M. Therefore, moldability, moisture absorption and heat resistance are inferior, and although the CTE is good, pKG warpage occurs. In Comparative Examples 4 and 7 to 9, the impregnation properties of the prepreg were not obtained well. : In Comparative Examples 4 and 7 to ", there are not nanometer-sized dioxins in the resin composition constituting the prepreg. Therefore, it is considered that the dioxins do not enter the strands and reach the impregnation of the resin composition. Improvement, X, therefore, good results have not been obtained in various other special financial aspects such as CTE and package self-warning. 0 - In Comparative Example 7, since the bulk density of the fiber woven fabric is small, the laser processability is poor and the impregnation property is poor. Further, the insulation reliability of the through-hole is deteriorated. Further, since a thick fiber woven fabric is used, the thickness of the resin layer of the prepreg is reduced, and the formability and the moisture resistance of the moisture-absorbing solder are inferior, and pKG warpage occurs. In 8 and 9, the thickness of the insulating layer of the metal foil laminate is thin, so the moldability, the moisture resistance of the moisture absorption solder, and the insulation reliability of the through-hole are excellent. However, due to the small bulk density of the fiber woven fabric, Good results were not obtained in terms of the filming properties. In Comparative Examples 2, 3 and 5, the impregnation properties of the prepreg did not result in a good knot 101102467 62 201251534. In addition, other various properties were not recovered. The content of the oxidized particles of Comparative Example 2 was suppressed, and the result was suppressed, and the entry into the resin composition was not obtained. In Comparative Example 3, it was considered that the content of the hybrids in the strands was high, so Nano-sized dioxo-depleted dioxon fossil particles in the strands of the strands. In contrast to _ agglutination, the results of inhibition of dioxin cloth, it can be considered that due to fiber woven &amp; In the 0 strands in the strands = in the case of 5, 'the bulk density of the fiber woven fabric is too large, so the resin composition sighs poorly, the moisture absorption solder has poor heat resistance, and the laser processing property and the through-hole perforation insulation reliability are also poor. In Comparative Example 6, 'the fiber density of the fiber woven fabric is small, so the laser processing property and the through-hole perforation have poor insulation reliability. Furthermore, since the fiber woven fabric has a small bulk density, it becomes a thick fiber substrate. Therefore, the thickness of the resin layer on the surface layer of the prepreg is reduced. Therefore, the formability and the moisture resistance of the moisture-absorbing solder are inferior, and the PKG is warped. This application claims to apply for this application on January 24, 2011. -〇12166-based priority BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a method for producing a metal foil laminate according to the present invention. 101102467 63 201251534 Fig. 2 is a view showing a metal foil laminate of the present invention. Fig. 3 is a photograph of a cross-sectional view of a prepreg obtained in Example 1. Fig. 4 is a photograph of a cross-sectional view of a prepreg obtained in Comparative Example 4. Fig. 5 is a pair of examples. A photograph of the surface of the copper ruthenium of the obtained metal delamination layer which was subjected to the entire surface etching. Fig. 6 is a photograph of the surface of the copper foil of the metal foil laminate obtained in Comparative Example 6 which was etched on the entire surface. SEM photograph of an enlarged view of 6 observation points. Fig. 8 is an SEM photograph of an enlarged view of a section of the point observed in Fig. 7. Fig. 9 is a SEM photograph showing a cross-sectional view of a part of a strand of the fiber woven fabric constituting the prepreg obtained in Example 1. Fig. 10 is a SEM photograph showing a cross-sectional view showing a part of a strand of the fiber woven fabric constituting the prepreg obtained in Example 1. Fig. 11 is a SEM photograph showing a cross-sectional view showing a part of a strand of the fiber woven fabric constituting the prepreg obtained in Example 1. Fig. 12 is a SEM photograph showing a cross-sectional view showing a part of a strand of the fiber woven fabric constituting the prepreg obtained in Example 1. [Description of main component symbols] 10 Metal foil 11 Metal foil 12 Resin layer 101102467 64 201251534 20 30 31 32 40 41 42 51 52 Fiber woven fabric polymer film with polymer layer Polymer film sheet Resin layer prepreg prepreg Prepreg metal foil laminated board metal foil laminated board 101102467 65

Claims (1)

201251534 七、申請專利範圍·· 種預:體，係使樹脂組成物含浸於由線股所構成之纖 維織布中而成者，於上述線股中存在二氧化矽粒子。 2. 如申請專利範圍第1項之預浸體，其中， 上述線股中，於構成上述線股之纖維所延伸之方向上不存 在具有50μιη以上長度的空隙。 3. 如申請專利範圍第1項之預浸體，其中， 上述線股中之直徑5〇μιη以上之空隙的數密度為5〇cm_丨 以下。 4. 如申請專利範圍第1項之預浸體，其中， 上述纖維織布之體積密度為1.05〜1.3〇g/cm3。 5. 如申請專利範圍第丨項之預浸體，其中， 上述線股中所存在之上述二氧化矽粒子的平均粒徑為 5〜10〇nm。 6. 如申請專利範圍第1項之預浸體，其中’ 上述樹脂組成物係至少含有熱硬化性樹脂及填充材； 上述填充材係依相對於上述樹脂組成物之固形份為 50〜85質量％的比例含有。 λ如申請專利範圍第6項之預浸體，其中， 上述填充材係依相對於上述填充劑為㈣質量％的比例 含有上述二氧化矽粒子。 8.如申請專利$£圍第〗項之職體，其中， 101102467 66 201251534 整體厚度為30〜220μιη。 9. 如申請專利範圍第1項之預浸體，其中， 上述線股係由至少依si〇2為5〇〜1〇〇質量％、αι2ο3為0〜30 質量％、CaO為〇〜30質量％的比例含有上述各者之玻璃纖 維所構成。 10. 如申請專利範圍第9項之預浸體，其中， 上述玻璃纖維係使用從T玻璃、S玻璃、D玻璃、E玻璃、 NE玻璃、石英玻璃所組成群中選擇之至少一種玻璃而成。 11. 如申請專利範圍第9項之預浸體，其中， 上述玻璃纖維係作成板狀時之楊氏率為50〜lOOGPa、作成 板狀時之拉張強度為25GPa以上、作成纖維織布時之長度 方向之拉張強度為3〇N/25mm以上。 12. 如申請專利範圍第9項之預浸體，其中， 上述纖維織布之通氣度為1〜80cc/cm2/sec。 13. 如申請專利範圍第1項之預浸體，其中， 上述二氧化矽粒子係藉由含有官能基之矽烷類或烷基矽 氮烧類施行了表面處理。 Μ· 一種積層板，係將申請專利範圍第1至13項中任一項 之預浸體進行硬化而獲得。 15. 如申請專利範圍第14項之積層板，其中， 於上述預浸體之至少一外侧面上設置導體層。 16. 種印刷佈線板，係將申請專利範圍第1至丨3項中任 101102467 67 201251534 一項之預浸體、或申請專利範圍第14或15項之積層板用於 内層電路基板而成者。 17. 如申請專利範圍第16項之印刷佈線板，其中， 將申請專利範圍第1至13項中任一項之預浸體設於上述 内層電路基板上作為絕緣層。 18. —種半導體裝置，係於申請專利範圍第16或17項之 印刷佈線板上搭載半導體元件而成者。 101102467 68201251534 VII. Patent application scope · · Pre-form: The resin composition is impregnated with a fiber woven fabric composed of strands, and cerium oxide particles are present in the strands. 2. The prepreg according to claim 1, wherein the strand has no void having a length of 50 μm or more in a direction in which the fibers constituting the strand extend. 3. The prepreg according to claim 1, wherein the number of the voids having a diameter of 5 〇 μm or more in the strands is 5 〇 cm_丨 or less. 4. The prepreg according to claim 1, wherein the fiber woven fabric has a bulk density of 1.05 to 1.3 〇g/cm3. 5. The prepreg according to claim 2, wherein the cerium oxide particles present in the strands have an average particle diameter of 5 to 10 Å. 6. The prepreg according to claim 1, wherein the resin composition contains at least a thermosetting resin and a filler; and the filler is 50 to 85 mass based on the solid content of the resin composition. The percentage of % is contained. The prepreg according to the sixth aspect of the invention, wherein the filler contains the cerium oxide particles in a proportion of (four) by mass based on the filler. 8. For the application of the patent, the body of the article, wherein 101102467 66 201251534 has an overall thickness of 30~220μιη. 9. The prepreg according to claim 1, wherein the above-mentioned strands are at least 5 〇 to 1 〇〇 mass%, αι2ο3 is 0 to 30% by mass, and CaO is 〇 〜 30 mass. The ratio of % consists of the glass fibers of each of the above. 10. The prepreg according to claim 9, wherein the glass fiber is made of at least one selected from the group consisting of T glass, S glass, D glass, E glass, NE glass, and quartz glass. . 11. The prepreg according to claim 9, wherein the glass fiber has a Young's ratio of 50 to 100 GPa when formed into a plate shape, and has a tensile strength of 25 GPa or more when formed into a plate shape, and is formed into a fiber woven fabric. The tensile strength in the longitudinal direction is 3〇N/25mm or more. 12. The prepreg according to claim 9, wherein the fiber woven fabric has a gas permeability of 1 to 80 cc/cm 2 /sec. 13. The prepreg according to claim 1, wherein the cerium oxide particles are surface-treated by a functional group-containing decane or an alkyl hydrazine.积· A laminated board obtained by hardening a prepreg according to any one of claims 1 to 13. 15. The laminate of claim 14, wherein the conductor layer is provided on at least one outer side surface of the prepreg. 16. A printed wiring board, which is a prepreg of any one of the claims 101102467 67 201251534, or a laminated board of claim 14 or 15 for use in an inner layer circuit substrate. . 17. The printed wiring board according to claim 16, wherein the prepreg according to any one of claims 1 to 13 is provided on the inner layer circuit substrate as an insulating layer. A semiconductor device comprising a semiconductor device mounted on a printed wiring board of claim 16 or 17. 101102467 68
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