TWI539869B - Prepreg, laminate, print circuit board and semiconductor device - Google Patents

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

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TWI539869B
TWI539869B TW101102467A TW101102467A TWI539869B TW I539869 B TWI539869 B TW I539869B TW 101102467 A TW101102467 A TW 101102467A TW 101102467 A TW101102467 A TW 101102467A TW I539869 B TWI539869 B TW I539869B
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prepreg
resin
woven fabric
glass
mass
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TW101102467A
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TW201251534A (en
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大東範行
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住友電木股份有限公司
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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

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  • 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)

Description

預浸體，積層板，印刷佈線板及半導體裝置 Prepreg, laminate, printed wiring board and semiconductor device

本發明係關於預浸體、積層板、印刷佈線板及半導體裝置。 The present invention relates to a prepreg, a laminate, a printed wiring board, and a semiconductor device.

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(via hole)的縮小化。 In recent years, with the demand for high functionality of electronic devices, high-density integration of electronic components and high-density mounting are progressing. Therefore, the printed wiring board corresponding to the high-density mounting used in these is required to be finer in circuit wiring, and to reduce the through holes and the via holes.

穿孔及通孔係使用鑽頭、二氧化碳雷射等之雷射等而形成，但在特別小徑的打孔時係使用雷射。由雷射所進行的打孔加工中，形成孔之絕緣層壁面的凹凸越大，則孔徑或形狀越容易偏差，而加工精度降低。 The perforations and through holes are formed using a laser such as a drill or a carbon dioxide laser, but a laser is used for punching a particularly small diameter. In the punching process by the laser, the larger the unevenness of the wall surface of the insulating layer forming the hole, the more easily the hole diameter or the shape is deviated, and the processing accuracy is lowered.

印刷佈線板之絕緣層可藉由對預浸體之一片或重疊了複數片者進行加熱加壓而形成。預浸體一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，含浸於玻璃布等之基材中，使其加熱乾燥而製作。在藉雷射加工而形成孔之絕緣層壁面中，於基材部分與樹脂組成物部分有因雷射所造成的熔融性差。因此，若基材之密度較小而質地較粗，則有孔徑、形狀容易偏差的傾向。另一方面，藉由使用質地細緻之高密度基材，則可提升絕緣層之由雷射所進行的打孔加工性(專利文獻1、2)。 The insulating layer of the printed wiring board can be formed by heating and pressurizing one of the prepregs or a plurality of sheets. The prepreg is usually produced by impregnating a base material such as a glass cloth with a varnish containing a resin composition containing a thermosetting resin as a main component in a solvent, and drying it by heating. In the wall surface of the insulating layer in which the hole is formed by laser processing, the substrate portion and the resin composition portion are inferior in meltability due to laser irradiation. Therefore, when the density of the base material is small and the texture is coarse, the pore diameter and the shape tend to be deviated. On the other hand, by using a high-density substrate having a fine texture, the punching workability of the insulating layer by the laser can be improved (Patent Documents 1 and 2).

另外，為了對應零件安裝於印刷佈線板上的高密度化，而 要求減小由印刷佈線板之熱膨脹所造成之曲翹以確保連接可靠性。半導體裝置(半導體封裝)係將半導體元件搭載於印刷佈線板，但半導體元件之熱膨脹率為3~6ppm/℃，較一般之半導體封裝用印刷佈線板的熱膨脹率小。因此，在對半導體封裝施加了熱衝擊時，有因半導體元件與半導體封裝用印刷佈線板之熱膨脹率差，而於半導體封裝發生曲翹的情形。此時，在半導體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形。 In addition, in order to increase the density of the components mounted on the printed wiring board, It is required to reduce the warpage caused by the thermal expansion of the printed wiring board to ensure connection reliability. In a semiconductor device (semiconductor package), a semiconductor element is mounted on a printed wiring board, but the thermal expansion coefficient of the semiconductor element is 3 to 6 ppm/° C., which is smaller than that of a general printed wiring board for semiconductor package. Therefore, when a thermal shock is applied to the semiconductor package, the thermal expansion coefficient of the semiconductor element and the printed wiring board for semiconductor package is inferior, and the semiconductor package is warped. At this time, a connection failure may occur between the semiconductor element and the printed wiring board for semiconductor package or between the semiconductor package and the printed wiring board to be mounted.

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)。 Since the insulating layer is made of 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 order to make the prepreg which is an insulating material have a low-line expansion, the resin composition used for the production of the prepreg is used for high-filling of the inorganic filler (Patent Document 3).

專利文獻1：日本專利特開2001-38836號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2001-38836

專利文獻2：日本專利特開2000-22302號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2000-22302

專利文獻3：日本專利特開2009-138075號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2009-138075

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 形。 However, when a prepreg is produced using a high-density substrate, the resin composition is inferior in impregnation to the substrate, and in particular, the resin composition containing the filler in a large amount, since the filler does not enter the fibers of the substrate. Therefore, impregnation of the resin composition is difficult. Moreover, 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. shape.

本發明係為了消除上述問題點而完成者，本發明之目的在於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於纖維織布的含浸性優越的預浸體。又，本發明之目的在於提供使用了該預浸體的金屬箔積層板，進而提供使用其等所得之印刷佈線板及半導體裝置。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a prepreg excellent in impregnation of a thermosetting resin composition with a fiber woven fabric while maintaining various characteristics of the prepreg. . Moreover, an object of the present invention is to provide a metal foil laminated board using the prepreg, and to provide a printed wiring board and a semiconductor device obtained by using the same.

根據本發明，係提供一種預浸體，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。 According to the present invention, there is provided a prepreg in which a resin composition is impregnated into a fiber woven fabric composed of strands, and cerium oxide particles are present in the strands.

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。 According to the present invention, it is possible to provide a prepreg excellent in impregnation of a thermosetting resin composition with a fiber woven fabric while maintaining various characteristics of the prepreg.

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。 Further, according to the present invention, a printed wiring board and a semiconductor device can be manufactured by using the above-described prepreg and/or a metal foil laminate produced by using the above prepreg.

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。 The above and other objects, features and advantages of the invention will be apparent from

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。 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.預浸體 Prepreg

本發明之預浸體係使樹脂組成物含浸於由線股所構成之 纖維織布中而成的預浸體。又，構成纖維織布之線股中係存在二氧化矽粒子。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。 The prepreg system of the present invention impregnates the resin composition with the strands A prepreg made of fiber woven fabric. Further, cerium oxide particles are present in the strands constituting the fiber woven fabric. 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.

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，係指例如後述之印刷佈線板之絕緣可靠性、預浸體之雷射加工性、或預浸體之低熱膨脹性等。 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 insulation reliability of a printed wiring board to be described later, the laser processability of a prepreg, or the low thermal expansion property of a prepreg.

在樹脂組成物對纖維織布之含浸性良好時，可抑制所得預浸體中發生空隙。藉此，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。 When the impregnation property of the resin composition with the fiber woven fabric is good, voids in the obtained prepreg can be suppressed. Thereby, the insulation reliability can be improved in the printed wiring board obtained by using the prepreg for the insulating layer.

另外，即使在使用了高密度之纖維織布的情況，仍可得到高含浸性。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。 Further, even in the case where a high-density fiber woven fabric is used, high impregnation properties can be obtained. Therefore, a high-density fiber woven fabric can be used to form a prepreg excellent in laser workability.

再者，藉由提升樹脂組成物對纖維織布的含浸性，可將填充材於纖維織布內進行高填充。因此，可達到預浸體的低熱膨脹化。藉此，可抑制將該預浸體用於絕緣層而得之印刷佈線板發生曲翹。因此，可使半導體裝置之連接可靠性提升。 Further, by increasing the impregnation property of the resin composition to the fiber woven fabric, the filler can be highly filled in the fiber woven fabric. Therefore, low thermal expansion of the prepreg can be achieved. Thereby, it is possible to suppress the warpage of the printed wiring board obtained by using the prepreg for the insulating layer. Therefore, the connection reliability of the semiconductor device can be improved.

構成預浸體的樹脂組成物，係至少含有熱硬化性樹脂及填充材的熱硬化性樹脂組成物(以下有時簡稱為「樹脂組成物」)。 The resin composition constituting the prepreg is a thermosetting resin composition containing at least a thermosetting resin and a filler (hereinafter sometimes simply referred to as "resin composition").

構成預浸體之樹脂組成物，較佳係例如依填充材之1~20 質量%之比例含有平均粒徑5~100nm之二氧化矽粒子。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5~100nm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5~100nm之二氧化矽粒子進入至纖維織布之纖維間、亦即線股內並擴散至纖維間，故平均粒徑5~100nm之二氧化矽粒子以外的填充材亦可進入至纖維織布中所致。如此，藉由使用平均粒徑5~100nm之奈米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預浸體。 The resin composition constituting the prepreg is preferably, for example, 1 to 20 depending on the filler. The proportion by mass% contains cerium oxide particles having an average particle diameter of 5 to 100 nm. The present inventors have found that a prepreg obtained by impregnating a resin composition containing a large amount of a filler into a high-density fiber woven fabric has an average particle diameter of 5 to 20% by mass based on the above filler. When the cerium oxide particles are ~100 nm, the impregnation property of the resin composition is good. For this reason, it is considered that since the above-mentioned cerium oxide particles having an average particle diameter of 5 to 100 nm enter the fibers of the fiber woven fabric, that is, in the strands and diffuse between the fibers, the cerium oxide particles having an average particle diameter of 5 to 100 nm are considered. The filler other than the filler can also enter into the fiber woven fabric. As described above, by using nano-sized cerium oxide particles having an average particle diameter of 5 to 100 nm as a filler, a prepreg having cerium oxide particles in the strands can be obtained.

另外，由於平均粒徑5~100nm之二氧化矽粒子之表面電位與其他之填充材之表面電位的差異，而使平均粒徑5~100nm之二氧化矽粒子與上述填充材藉由相互作用而拉附。因此，平均粒徑5~100nm之二氧化矽粒子存在於上述填充材之周圍，平均粒徑5~100nm之二氧化矽粒子具有間隔件般之作用。如此，平均粒徑5~100nm之二氧化矽粒子存在於上述填充材之周圍，藉由發揮作為間隔件之作用，使上述填充材之凡得瓦力所造成的拉附力減低，防止凝集。藉此，上述填充材成為更高分散狀態，可防止流動性的降低。 Further, since the surface potential of the cerium oxide particles having an average particle diameter of 5 to 100 nm is different from the surface potential of the other filler, the cerium oxide particles having an average particle diameter of 5 to 100 nm are caused to interact with the filler. Pull attached. Therefore, cerium oxide particles having an average particle diameter of 5 to 100 nm exist around the above-mentioned filler, and cerium oxide particles having an average particle diameter of 5 to 100 nm have a function as a spacer. As described above, the cerium oxide particles having an average particle diameter of 5 to 100 nm are present around the filler, and act as a spacer to reduce the pulling force caused by the wattage of the filler, thereby preventing aggregation. Thereby, the above-mentioned filler is in a state of higher dispersion, and it is possible to prevent a decrease in fluidity.

上述平均粒徑5~100nm之二氧化矽粒子較佳係作成事先分散於有機溶媒中的漿料而使用。藉此，可提升填充材之分 散性，可抑制使用其他填充材時所發生之流動性降低。其理由可認為如下。首先，如奈米尺寸之二氧化矽般之奈米尺寸的粒子大多容易凝集，在調配至樹脂組成物中時形成二次凝集體等，但藉由使用漿料狀物，則可防止此種二次凝集，藉此可防止流動性的降低。又，本發明中所使用之填充材，由於凝集防止及分散性高，故較佳係事先施行表面處理。 The cerium oxide particles having an average particle diameter of 5 to 100 nm are preferably used as a slurry which is previously dispersed in an organic solvent. Thereby, the filling material can be improved The bulkiness can suppress the decrease in fluidity that occurs when other filler materials are used. The reason can be considered as follows. First, particles of a nanometer size such as a nanometer-sized cerium oxide are likely to aggregate, and a secondary aggregate or the like is formed when formulated into a resin composition, but this can be prevented by using a slurry. Secondary agglomeration, whereby the decrease in fluidity can be prevented. Moreover, since the filler used in the present invention has high aggregation prevention and dispersibility, it is preferred to perform surface treatment in advance.

尚且，本發明中所謂高密度之纖維織布，係指不僅提高紗之織入根數，並經過使一根根纖維均質地進行高開纖化、藉由扁平化而減低厚度等之處理的纖維織布。高密度之纖維織布係例如體積密度為1.05g/cm3以上。藉此，由於可使樹脂組成物含浸於一根根纖維之間，故可達到填充材的更高填充化。再者，由於可充分確保纖維織布上之樹脂量，故可維持在預浸體上積層銅箔而作成銅箔積層板時、或銅箔積層板之表面平滑化時的成形性。 Further, the term "high-density fiber woven fabric" as used in the present invention refers to a process of not only increasing the number of woven fabrics of the yarn, but also performing high-fibrillation of one fiber uniformly, and reducing the thickness by flattening. Fiber woven fabric. The high-density fiber woven fabric has a bulk density of, for example, 1.05 g/cm 3 or more. Thereby, since the resin composition can be impregnated between the individual fibers, a higher filling of the filler can be achieved. In addition, since the amount of the resin on the fiber woven fabric can be sufficiently ensured, the moldability can be maintained when the copper foil is laminated on the prepreg to form a copper foil laminate, or when the surface of the copper foil laminate is smoothed.

如此，本發明之預浸體由於樹脂組成物對纖維織布的含浸性良好，故空隙的發生較少。又，由於在樹脂組成物中含有多量的填充材，故為低熱膨脹性，使用本發明之預浸體而得的印刷佈線板的曲翹較小。又，本發明中，所謂預浸體之熱膨脹性，係指使預浸體硬化之狀態下的熱膨脹性。 As described above, in the prepreg of the present invention, since the impregnation property of the resin composition to the fiber woven fabric is good, the occurrence of voids is small. Moreover, since a large amount of filler is contained in the resin composition, it has low thermal expansion property, and the printed wiring board obtained by using the prepreg of the present invention has a small warp. In the present invention, the thermal expansion property of the prepreg refers to the thermal expansion property in a state in which the prepreg is cured.

另外，本發明之預浸體係藉由使填充材經高填充化，而耐熱性優越、高剛性。再者，本發明之構成預浸體的纖維織布的體積密度，較佳為1.05~1.30g/cm3。藉由使用體積密度為 1.05~1.30g/cm3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。 Further, the prepreg system of the present invention has excellent heat resistance and high rigidity by highly filling the filler. Further, the fiber woven fabric constituting the prepreg of the present invention preferably has a bulk density of 1.05 to 1.30 g/cm 3 . By using a high-density fiber woven fabric having a bulk density of 1.05 to 1.30 g/cm 3 , when an insulating layer as a printed wiring board is used, the precision of the aperture and shape can be improved by laser processing, and the suppression is suppressed. A hole in which the fiber protrudes.

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浸體，由於樹脂組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。另一方面，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，故纖維織布可依均勻厚度保持樹脂組成物，表面平滑性或與導體層間之密黏性良好，進而亦可對應薄型化。又，本發明之預浸體係藉由使用多量地含有填充材之樹脂組成物，而成為高耐熱性、高剛性。 Further, in general, a prepreg obtained by using a large amount of a resin composition containing a filler material has a poor impregnation property of the resin composition on the substrate, so that it is difficult for the substrate to maintain the resin composition in a uniform thickness. When the dip 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 woven fabric can maintain the resin composition in a uniform thickness, and the surface smoothness or the adhesion to the conductor layer is good, and further It can also be thinned. Moreover, the prepreg system of the present invention has high heat resistance and high rigidity by using a resin composition containing a large amount of a filler.

首先，針對本發明所使用之纖維織布進行說明。 First, the fiber woven fabric used in the present invention will be described.

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、聚酯、芳香族聚酯、氟樹脂等之合成纖維、金屬纖維、碳纖維、礦物纖維等所構成的纖維織布。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。 The fiber woven fabric to be used in the present invention is not particularly limited, and examples thereof include synthetic fibers such as glass fibers, linaloamine, polyester, aromatic polyester, and fluororesin, metal fibers, carbon fibers, and mineral fibers. The fiber woven fabric is composed. 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.

上述玻璃纖維並無特別限定，較佳係依SiO2為50質量%~100質量%、Al2O3為0質量%~30質量%、CaO為0質量 %~30質量%的比例含有上述各者，特佳為使用從T玻璃(有時亦稱為「S玻璃」)、D玻璃、E玻璃、NE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T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T玻璃(S玻璃)、石英玻璃。 The glass fiber is not particularly limited, and is preferably a ratio of 50% by mass to 100% by mass of SiO 2 , 0% by mass to 30% by mass of Al 2 O 3 , and 0% by mass to 30% by mass of CaO. It is particularly preferable to use at least one type of glass selected from the group consisting of T glass (sometimes referred to as "S glass"), D glass, E glass, NE glass, and quartz glass; among them, more preferably T Glass (S glass), quartz glass, and D glass are preferably T glass (S glass) or quartz glass from the viewpoint of excellent low thermal expansion property and high strength.

尚且，本發明中，T玻璃(S玻璃)係指依SiO2為62質量%~65質量%、Al2O3為20質量%~25質量%、CaO為0質量%~0.01質量%、MgO為10質量%~15質量%、B2O3為0質量%~0.01質量%、Na2O及K2O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SiO2為72質量%~76質量%、Al2O3為0質量%~5質量%、CaO為0質量%~1質量%、MgO為0質量%~1質量%、B2O3為20質量%~25質量%、Na2O及K2O合計為3質量%~5質量%的比例含有上述各者之組成的玻璃；E玻璃係指依SiO2為52質量%~56質量%、Al2O3為12質量%~16質量%、CaO為15質量%~25質量%、MgO為0質量%~6質量%、B2O3為5質量%~10質量%、Na2O及K2O合計為0質量%~0.8質量%的比例含有上述各者之組成的玻璃；NE玻璃係指依SiO2為52質量%~56質量%、Al2O3為10質量%~15質量%、CaO為0質量%~10質量%、MgO為0質量%~5質量%、B2O3為15質量%~20質量%、Na2O及K2O合計為0質量%~1質量%、TiO2為0.05質量%~5質量%的比例含有上述各者之組成的 玻璃；石英玻璃係指依99.0質量%~100質量%之比例含有SiO2之組成的玻璃。 Further, in the present invention, T glass (S glass) means 62% by mass to 65% by mass based on SiO 2 , 20% by mass to 25% by mass of Al 2 O 3 , and 0% by mass to 0.01% by mass of CaO, MgO. Glass having a composition of 10% by mass to 15% by mass, B 2 O 3 of 0% by mass to 0.01% by mass, and a total of 0% by mass to 1% by mass of Na 2 O and K 2 O; SiO 2 glass by means of 72 mass% to 76 mass%, Al 2 O 3 0 mass% to 5 mass%, CaO 0 mass% to 1 mass%, MgO is 0 mass% to 1 mass%, B 2 O 3 is 20% by mass to 25% by mass, and the total of Na 2 O and K 2 O is 3% by mass to 5% by mass, and the glass having the composition of each of the above is used; and the E glass is 52% by mass based on SiO 2 . 56% by mass, Al 2 O 3 is 12% by mass to 16% by mass, CaO is 15% by mass to 25% by mass, MgO is 0% by mass to 6% by mass, and B 2 O 3 is 5% by mass to 10% by mass. The total composition of Na 2 O and K 2 O is 0% by mass to 0.8% by mass, and the glass of the composition of each of the above is contained; the NE glass means 52% by mass to 56% by mass of SiO 2 and 10% by mass of Al 2 O 3 . %~15% by mass, CaO is 0% by mass to 10% by mass, MgO is 0% by mass to 5% by mass, B 2 O 3 is 15% by mass to 20% by mass, and Na 2 O and K 2 O are 0 mass. %~1% by mass TiO 2 ratio of 0.05 mass% to 5 mass% of the glass composition containing the above-mentioned persons; quartz glass by means 99.0 mass% to 100 mass% of SiO 2 containing glass composition.

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50~100GPa、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80~100GPa、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點彎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 R3420，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。 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, a tensile strength of 25 GPa or more when formed into a plate shape, and a length direction of the fiber woven fabric. The tensile strength is 30 N/25 mm or more, and the Young's ratio is preferably 80 to 100 GPa when formed into a plate shape, 35 GPa or more when formed into a plate shape, and 45 N in the longitudinal direction when the fiber woven fabric is formed. /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, and the tensile strength in the longitudinal direction is a value measured by the same constant-speed elongation type tensile tester as described above in accordance with JIS R3420.

尚且，上述楊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厚0.5~1.0mm之玻璃板的狀態。又，在上述長度方向之拉張強度測定中，所謂「長度方向」係指經線(縱線)方向。 In the measurement of the Young's rate and the measurement of the tensile strength, the "plate shape" refers to a state in which a glass composition having the same composition as the glass fiber is formed into a glass plate having a thickness of 0.5 to 1.0 mm. Moreover, in the measurement of the tensile strength in the longitudinal direction, the "longitudinal direction" means the warp (vertical line) direction.

上述玻璃纖維並無特別限定，根據JIS R3102所測定之經線方向之熱膨脹係數較佳為10ppm/℃以下，特佳為3ppm/℃以下。藉此，可減小印刷佈線板之熱膨脹所造成的曲翹。 The glass fiber is not particularly limited, and the coefficient of thermal expansion in the warp direction measured according to JIS R3102 is preferably 10 ppm/° C. or less, and particularly preferably 3 ppm/° C. or less. Thereby, the warpage caused by the thermal expansion of the printed wiring board can be reduced.

上述纖維織布之厚度並無特別限定，較佳為10~200μm、 更佳10~140μm、再更佳20~90μm。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。 The thickness of the fiber woven fabric is not particularly limited, but is preferably 10 to 200 μm. More preferably 10 to 140 μm, and even more preferably 20 to 90 μm. Thereby, the resin composition is excellent in impregnation with the fiber woven fabric, and can be made thinner.

上述纖維織布之體積密度較佳為1.05~1.30g/cm3、特佳1.10~1.25g/cm3。若體積密度未滿上述下限值，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，係藉由調整經線與橫線之織入根數、與經開纖、扁平處理之纖維厚度而進行。 The fiber woven fabric preferably has a bulk density of 1.05 to 1.30 g/cm 3 and particularly preferably 1.10 to 1.25 g/cm 3 . When the bulk density is less than the above lower limit value, the laser processing property of the insulating layer is inferior, and if it exceeds the above upper limit value, the impregnation property of the resin composition to the fiber woven fabric is deteriorated. Further, the adjustment of the bulk density of the fiber woven fabric is carried out by adjusting the number of woven fibers of the warp and the cross threads, and the fiber thickness of the fiber-opening and flat processing.

上述纖維織布並無特別限定，通氣度較佳為1~80cc/cm2/sec、更佳3~50cc/cm2/sec。若通氣度未滿上述下限值，則樹脂組成物對纖維織布的含浸性惡化，若超過上述上限值，則絕緣層之雷射加工性差。 The fiber woven fabric is not particularly limited, and the air permeability is preferably from 1 to 80 cc/cm 2 /sec, more preferably from 3 to 50 cc/cm 2 /sec. When the air permeability is less than the above lower limit value, the impregnation property of the resin composition to the fiber woven fabric is deteriorated, and if it exceeds the above upper limit value, the laser processing property of the insulating layer is inferior.

上述纖維織布並無特別限定，基重較佳為10~160g/m2、特佳15~130g/m2。若基重未滿上述下限值，則預浸體之低熱膨脹性差，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、或絕緣層之雷射加工性差。 The fiber woven fabric is not particularly limited, and the basis weight is preferably from 10 to 160 g/m 2 and particularly preferably from 15 to 130 g/m 2 . When the basis weight is less than the above lower limit value, the low thermal expansion property of the prepreg is inferior, and if it exceeds the above upper limit value, the impregnation property of the resin composition to the fiber woven fabric is deteriorated, or the laser processing property of the insulating layer is inferior.

另外，上述纖維織布所使用之纖維並無特別限定，扁平率較佳為1：2~1：50、特佳1：5~1：30。藉由使纖維織布所使用之纖維的扁平率為上述範圍內，則由於樹脂組成物對上述纖維織布的含浸性/濕潤性更優越，故可提升穿孔間之絕緣可靠性、以及提升絕緣層之雷射加工性。又，本發明中所謂扁平率，係指由線之厚度：線之寬度所表示的值。 Further, the fiber used in the above-mentioned fiber woven fabric is not particularly limited, and the flatness ratio is preferably from 1:2 to 1:50, particularly preferably from 1:5 to 1:30. When the flatness of the fiber used for the fiber woven fabric is within the above range, the impregnation/wet property of the resin composition to the fiber woven fabric is superior, so that the insulation reliability between the perforations can be improved, and the insulation can be improved. Laser processing of the layer. Further, the flatness ratio in the present invention means a value represented by the thickness of the line: the width of the line.

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，其中由雷射加工性、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。 Further, the woven fabric structure of the above-mentioned fiber woven fabric is not particularly limited, and examples thereof include a woven fabric structure such as plain weave, twill weave, woven woven fabric, and twill weave, and the interlayer insulating property of the laser processing property, the strength, and the through hole is excellent. From the viewpoint, it is preferably a plain weave structure.

接著，說明本發明所使用之熱硬化性樹脂組成物。 Next, the thermosetting resin composition used in the present invention will be described.

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充材。上述填充材係依上述熱硬化性樹脂組成物之固形份之50~85質量%的比例含有。又，上述熱硬化性樹脂組成物係依上述填充材之1~20質量%的比例含有平均粒徑5~100nm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。 The thermosetting resin composition used in the present invention 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 thermosetting resin composition. Further, the thermosetting resin composition contains cerium oxide particles having an average particle diameter of 5 to 100 nm in a ratio of 1 to 20% by mass of the filler. Further, the thermosetting resin composition may further contain a curing agent, a coupling agent, or the like as needed.

(填充材) (filler)

上述填充材係依上述填充材整體之1~20質量%的比例含有平均粒徑5~100nm之二氧化矽粒子。 The filler contains cerium oxide particles having an average particle diameter of 5 to 100 nm in a ratio of 1 to 20% by mass based on the entire filler.

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。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，則可調整所得之二氧化矽微粒子 的粒徑。又，作為上述二氧化矽粒子，亦可使用NSS-5N(TOKUYAMA(股)製)、Sicastar43-00-501(Micromod公司製)等之市售物。 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, and sedimentation can be used. Manufacturers of methods such as methods and gel methods. Among them, the best is the VMC method. The VMC method is a method in which a cerium powder is introduced into a chemical flame formed in an oxygen-containing gas, burned, and then cooled to form cerium oxide fine particles. In the VMC method, the obtained cerium oxide microparticles can be adjusted by adjusting the particle size, the input amount, the flame temperature, and the like of the ruthenium powder to be charged. Particle size. Further, as the cerium oxide particles, commercially available products such as NSS-5N (manufactured by TOKUYAMA Co., Ltd.) and Sicastar 43-00-501 (manufactured by Micromod Co., Ltd.) can be used.

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。二氧化矽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100nm時，則有無法進入纖維間的情形。 The 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. When the average particle diameter of the cerium oxide particles is less than 5 nm, it is not possible to diffuse between the fibers of the fiber woven fabric, and when it is larger than 100 nm, the fibers 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5~100nm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(HORIBA製，LB-550)，依體積基準測定粒子之粒度分佈，以其中徑(D50)作為平均粒徑。 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, and the particles are measured by a dynamic light scattering type particle size distribution measuring apparatus (LB-550, manufactured by HORIBA). The particle size distribution has a diameter (D50) as an average particle diameter.

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。 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.

作為使二氧化矽粒子成為疏水性的方法，可舉例如對二氧化矽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矽烷類可使用公 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、巰基矽烷、異氰酸酯矽烷、硫化矽烷、脲矽烷等。作為上述烷基矽氮烷類，可舉例如六甲基二矽氮烷(HMDS)、1,3-二乙烯基-1,1,3,3-四甲基二矽氮烷、八甲基三矽氮烷、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。 As a method of making the cerium oxide particles hydrophobic, for example, a method in which the cerium oxide particles are surface-treated by a functional group-containing decane and/or a alkyl decazane is used. As the above-mentioned functional group-containing decane, it is possible to use a public The known substance may, for example, be an epoxy decane, an amino decane, a vinyl decane, an acrylic decane, a decyl decane, an isocyanate decane, a decane sulfide or a urea decane. Examples of the alkyl oxazane include hexamethyldiazepine (HMDS), 1,3-divinyl-1,1,3,3-tetramethyldiazepine, and octamethyl group. Trioxane, hexamethylcyclotriazane, and the like. Moreover, 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.

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，相對於上述二氧化矽粒子100重量份，較佳為0.01重量份以上且5重量份以下。更佳為0.1重量份以上且3重量份以下。若含有官能基之矽烷類及/或烷基矽氮烷類的含量超過上述上限值，則印刷佈線板製造時有於絕緣層發生裂痕的情形，未滿上述下限值時，則有樹脂成分與二氧化矽粒子間之結合力降低的情形。 The amount of the functional group-containing decane and/or the alkyl decazane to be surface-treated in advance with respect to the above cerium oxide particles is not particularly limited, and is preferably 0.01 parts by weight based on 100 parts by weight of the cerium oxide particles. Above and 5 parts by weight or less. More preferably, it is 0.1 part by weight or more and 3 parts by weight or less. When the content of the functional group-containing decane and/or alkyl decane alkane exceeds the above upper limit, the printed wiring board may be cracked in the insulating layer during production, and if it is less than the lower limit, the resin may be present. The case where the binding force between the component and the cerium oxide particles is lowered.

對上述二氧化矽粒子事先藉由含有官能基之矽烷類及/或烷基矽氮烷類進行表面處理的方法，並無特別限定，較佳為濕式方法或乾式方法。特佳為濕式方法。相較於乾式方法，濕式方法可對上述二氧化矽粒子之表面進行均勻處理。 The method of surface-treating the above-mentioned ceria particles by a functional group-containing decane and/or alkyl decazane is not particularly limited, and a wet method or a dry method is preferred. Especially good for wet methods. The wet method can uniformly treat the surface of the above cerium oxide particles compared to the dry method.

另外，上述表面處理較佳係進行至比表面積的50%以上。 Further, the above surface treatment is preferably carried out to 50% or more of the specific surface area.

上述平均粒徑5~100nm之二氧化矽粒子係依填充材整體之1~20質量%的比例含有。若含量未滿上述下限值，則有 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%。 The cerium oxide particles having an average particle diameter of 5 to 100 nm are contained in a proportion of 1 to 20% by mass based on the entire filler. If the content is less than the above lower limit, then there is When the effect of improving the impregnation property is insufficient, if the content exceeds the above upper limit value, the impregnation property may be deteriorated, or the moldability of the prepreg may be poor. Further, the content of the cerium oxide particles having an average particle diameter of 5 to 100 nm is more preferably from 3 to 15% by mass based on the entire filler.

本發明所使用之填充材中，除了上述平均粒徑5~100nm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100nm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(AlO(OH)，通常稱為「類」水鋁土之水鋁土(亦即，Al2O3．xH2O，於此，x=1至2)、氫氧化鎂、氫氧化鈣等之氫氧化物，硫酸鋇、硫酸鈣、亞硫酸鈣等之硫酸鹽或亞硫酸鹽，硼酸鋅、甲基硼酸鋇、硼酸鋁、硼酸鈣、硼酸鈉等之硼酸鹽，氮化鋁、氮化硼、氮化矽、氮化碳等之氮化物，鈦酸鍶、鈦酸鋇等之鈦酸鹽等之無機填充材。上述無機填充材可單獨使用此等中之一種，亦可併用2種以上。此等之中，較佳為氫氧化鎂、氫氧化鋁、水鋁土、平均粒徑大於100nm之球狀二氧化矽粒子、滑石、燒成滑石、氧化鋁；由低熱膨脹性、含浸性的觀點而言，特佳為水鋁土、平均粒徑大於100nm之球狀二氧化矽粒子、球狀氧化鋁。 The filler used in the present invention is not particularly limited as long as the above-mentioned ceria particles having an average particle diameter of 5 to 100 nm, and may contain tannic acid such as talc, calcined clay, unfired clay, mica or glass. Salt, 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, and hydrotalcite, aluminum hydroxide, and bauxite (AlO(OH), usually Water bauxite called "aqua" bauxite (ie, Al 2 O 3 .xH 2 O, here, x=1 to 2), hydroxide of magnesium hydroxide, calcium hydroxide, etc., barium sulfate Sulfate or sulfite of calcium sulfate, calcium sulfite, etc., borate of zinc borate, barium methylborate, aluminum borate, calcium borate, sodium borate, aluminum nitride, boron nitride, tantalum nitride, nitrogen An inorganic filler such as a nitride such as carbon, or a titanate such as barium titanate or barium titanate. The inorganic filler may be used alone or in combination of two or more. Preferred are magnesium hydroxide, aluminum hydroxide, bauxite, spherical cerium oxide particles having an average particle diameter of more than 100 nm, and slippery Calcined talc, alumina; of expanded, impregnating the viewpoint of low heat, the water is particularly preferably alumina, average particle size greater than 100nm spherical particles of silicon dioxide, aluminum oxide spherical.

作為上述平均粒徑5~100nm之二氧化矽粒子以外的無機填充材(以下有時稱為「其他之無機填充材」)並無特別限 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10%以下者，所謂多分散係指粒徑之標準偏差為10%以上者。 The inorganic filler other than the above-mentioned ceria particles having an average particle diameter of 5 to 100 nm (hereinafter sometimes referred to as "other inorganic filler") is not particularly limited. The inorganic filler having an average particle diameter of monodisperse may be used, or an inorganic filler having an average particle diameter of polydisperse may be used. In addition, one type or two or more types of inorganic fillers having an average particle diameter of monodisperse and/or polydisperse may be used in combination. In the present invention, the average particle diameter is monodisperse, and the standard deviation of the particle diameter is 10% or less, and the polydispersity means that the standard deviation of the particle diameter is 10% or more.

上述其他之無機填充材之平均粒徑並無特別限定，較佳為0.1μm~5.0μm，特佳0.1μm~3.0μm。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。 The average particle diameter of the other inorganic filler is not particularly limited, but is preferably 0.1 μm to 5.0 μm, particularly preferably 0.1 μm to 3.0 μm. When the particle diameter of the other inorganic filler is less than the above lower limit, the viscosity of the resin composition becomes high, which may affect the workability at the time of preparation of the prepreg. Moreover, when it exceeds the above-mentioned upper limit, the phenomenon of sedimentation of an inorganic filler, etc. may arise in the resin composition. In addition, the average particle diameter can be measured using a laser diffraction/scattering particle size distribution measuring apparatus (manufactured by Shimadzu Corporation, general equipment such as SALD-7000).

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45μm以上的粗粒分割、更佳為20μm以上的粗粒分割、特佳為10μm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。 Further, in the case of processing small diameter holes, narrow pitch processing of holes, and fine wire processing, the above other inorganic fillers are preferably divided into coarse particles. Among them, it is preferably divided into coarse particles of 45 μm or more, more preferably coarse particles of 20 μm or more, and particularly coarse particles of 10 μm or more. Further, the term "coarse grain division" means that coarse particles having a large particle size or larger are excluded.

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、交聯丙烯腈丁二烯橡膠粒子、交聯苯乙烯丁二烯橡膠粒子、丙烯酸系橡膠粒子、聚矽氧粒子等。 Moreover, it is preferable that the filler used in the present invention 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, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and polyoxyl Particles, etc.

核殼型橡膠粒子係具有核層與殼層的橡膠粒子，可舉例如：外層之殼層為由玻璃狀聚合物所構成，內層之核層為由橡膠狀聚合物所構成的2層構造；或外層之殼層為由玻璃狀聚合物所構成，中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酯之聚合物等所構成，橡膠狀聚合物層係例如由丙烯酸丁酯聚合物(丁基橡膠)等所構成。作為核殼型橡膠粒子之具體例，可舉例如Stafiloid AC3832、AC3816N(商品名Ganz化成(股)製)，METABLEN KW-4426(商品名三菱嫘縈(股)製)。作為交聯丙烯腈丁二烯橡膠(NBR)粒子的具體例，可舉例如XER-91(平均粒徑0.5μm，JSR(股)製)等。 The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and the shell layer of the outer layer is composed of a glassy polymer, and the core layer of the inner layer is a two-layer structure composed of a rubber-like polymer. Or the outer shell layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery 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 butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Stafiloid AC 3832, AC3816N (trade name: Ganz Chemical Co., Ltd.), and METABLEN KW-4426 (trade name: Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.).

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0.5μm，JSR(股)製)等。作為丙烯酸系橡膠粒子之具體例，可舉例如METABLEN W300A(平均粒徑0.1μm)、W450A(平均粒徑0.2μm)(三菱嫘縈(股)製)等。 Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the acrylic rubber particles include METABLEN W300A (average particle diameter: 0.1 μm), W450A (average particle diameter: 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.), and the like.

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矽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、KMP-600、KMP-597、KMP-594(信越化學(股) 製)、TORAYFIL E-500、TORAYFIL E-600(東麗．道康寧(股)製)等之市售物。 The above-mentioned polyfluorene oxide particles are not particularly limited as long as the rubber elastic fine particles are formed of an organic polysiloxane, and for example, fine particles composed of a polyoxyxylene rubber (organic polyoxyalkylene crosslinked elastomer) itself may be used. And a core-shell structured particle in which a core portion composed of a polyfluorinated oxygen of a two-dimensionally crosslinked body is coated with polyfluorene oxygen of a three-dimensional crosslinked type body. As the above polysiloxane particles, KMP-605, KMP-600, KMP-597, and KMP-594 can be used (Shin-Etsu Chemical Co., Ltd.) (Marketing), TORAYFIL E-500, TORAYFIL E-600 (Dongli. Dow Corning (stock) system) and other commercial products.

本發明所使用之填充材中，對於平均粒徑5~100nm之二氧化矽粒子以外之填充材，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、巰基矽烷等。又，表面處理較佳係進行比表面積的50%以上。 In the filler used in the present invention, in order to prevent aggregation and improve dispersibility, the filler other than the ceria particles having an average particle diameter of 5 to 100 nm is preferably subjected to surface treatment in advance. 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.

本發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50~85質量%、特佳65~75質量%。若填充材含量超過上述上限值，則樹脂組成物之流動性極差，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。 The content of the filler in the resin composition used in the present invention is preferably from 50 to 85% by mass, particularly preferably from 65 to 75% 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 composition is extremely poor, and the workability at the time of producing the prepreg is deteriorated. If the lower limit is not exceeded, the coefficient of thermal expansion is high and the strength of the insulating layer is insufficient.

(熱硬化性樹脂) (thermosetting resin)

作為熱硬化性樹脂並無特別限定，可使用環氧樹脂、氰酸酯樹脂、雙順丁烯二醯亞胺樹脂、苯酚樹脂、苯并樹脂、乙烯基苄基醚樹脂、苯并環丁烯樹脂等，通常係於環氧樹脂中適當組合其他之熱硬化性樹脂而使用。 The thermosetting resin is not particularly limited, and an epoxy resin, a cyanate resin, a bis-butylene diimide resin, a phenol resin, or a benzo can be used. The resin, the vinyl benzyl ether resin, the benzocyclobutene resin, and the like are usually used in combination with other thermosetting resins in an epoxy resin.

作為上述環氧樹脂並無特別限定，較佳係實質上不含鹵原子者。於此，所謂「實質上不含鹵原子」，係容許來自在環氧樹脂之合成過程中所使用之鹵素系成分的鹵素，即使經由鹵素去除步驟仍殘存於環氧樹脂中。通常較佳係於環氧樹脂 中不含有超過30ppm的鹵原子。 The epoxy resin is not particularly limited, and is preferably one which does not substantially contain a halogen atom. Here, the term "substantially does not contain a halogen atom" allows halogen derived from a halogen-based component used in the synthesis of an epoxy resin to remain in the epoxy resin even after the halogen removal step. Usually preferred to epoxy It does not contain more than 30 ppm of halogen atoms.

作為上述實質上不含鹵原子的環氧樹脂，可舉例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚E型環氧樹脂、雙酚S型環氧樹脂、雙酚Z型環氧樹脂(4,4’-環己二烯雙酚型環氧樹脂)、雙酚P型環氧樹脂(4,4’-(1,4)-伸苯基二亞異丙基)雙酚型環氧樹脂)、雙酚M型環氧樹脂(4,4’-(1,3-伸苯基二亞異丙基)雙酚型環氧樹脂)等之環酚型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等之酚醛清漆型環氧樹脂、聯苯型環氧樹脂、二甲苯型環氧樹脂、苯酚芳烷基型環氧樹脂、聯苯基芳烷基型環氧樹脂、聯苯基二亞甲基型環氧樹脂、三酚甲烷酚醛清漆型環氧樹脂、1,1,2,2-(四酚)乙烷之環氧丙基醚類、3官能或4官能之環氧丙基胺類、四甲基聯苯型環氧樹脂等之芳基伸烷基型環氧樹脂、萘骨架改質環氧樹脂、甲氧基萘改質甲酚酚清漆型環氧樹脂、甲氧基萘二亞甲基型環氧樹脂、萘醚型環氧樹脂等之萘型環氧樹脂，蒽型環氧樹脂、苯氧基型環氧樹脂、二環戊二烯型環氧樹脂、降烯型環氧樹脂、金剛烷型環氧樹脂、茀型環氧樹脂、將上述環氧樹脂經鹵化的難燃化環氧樹脂等。 Examples of the epoxy resin which does not substantially contain a halogen atom include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, and bisphenol. Z-type epoxy resin (4,4'-cyclohexadiene bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4)-phenylene diisopropylidene Bisphenol type epoxy resin), bisphenol M type epoxy resin (4,4'-(1,3-phenylene diisopropylidene) bisphenol type epoxy resin), etc. Resin, phenol novolak type epoxy resin, phenol novolak type epoxy resin, such as novolak type epoxy resin, biphenyl type epoxy resin, xylene type epoxy resin, phenol aralkyl type epoxy resin, Biphenyl aralkyl type epoxy resin, biphenyl dimethylene type epoxy resin, trisphenol methane novolak type epoxy resin, epoxy of 1,1,2,2-(tetraphenol)ethane An arylalkylene type epoxy resin such as a propyl ether, a trifunctional or a tetrafunctional epoxypropylamine or a tetramethylbiphenyl type epoxy resin, a naphthalene skeleton modified epoxy resin, or a methoxynaphthalene Modified cresol novolac type epoxy resin, methoxynaphthalene dimethylene ring Resins, ether type epoxy resins of naphthalene naphthalene type epoxy resin, anthracene type epoxy resins, phenoxy type epoxy resins, dicyclopentadiene type epoxy resins, drop An olefin type epoxy resin, an adamantane type epoxy resin, a fluorene type epoxy resin, a flame retardant epoxy resin obtained by halogenating the above epoxy resin, and the like.

此等之中，可單獨使用1種之環氧樹脂，亦可併用具有不同重量平均分子量的2種以上之環氧樹脂，或可併用1種或2種以上之環氧樹脂與環氧樹脂之預聚物。 Among these, one type of epoxy resin may be used alone, or two or more types of epoxy resins having different weight average molecular weights may be used in combination, or one type or two or more types of epoxy resins and epoxy resins may be used in combination. Prepolymer.

此等環氧樹脂中，特佳為選自由聯苯基二亞甲基型環氧樹 脂、酚醛清漆型環氧樹脂、萘改質甲酚酚醛清漆環氧樹脂及蒽型環氧樹脂所組成群之至少1種。藉由使用此等環氧樹脂，可提升所得之積層板及印刷佈線板之吸濕焊錫耐熱性及難燃性。 Among these epoxy resins, it is particularly preferred to be selected from the group consisting of biphenyl dimethylene type epoxy trees. At least one of a group consisting of a fat, a novolak type epoxy resin, a naphthalene modified cresol novolac epoxy resin, and a fluorene type epoxy resin. By using such an epoxy resin, the moisture resistance and flame retardancy of the moisture absorption solder of the obtained laminate and printed wiring board can be improved.

另外，此等環氧樹脂中，藉由使用萘醚型環氧樹脂，則可提升所得之積層板及印刷佈線板的耐熱性、低熱膨脹性及低熱收縮性。 Further, in such an epoxy resin, by using a naphthene ether type epoxy resin, heat resistance, low thermal expansion property, and low heat shrinkability of the obtained laminated board and printed wiring board can be improved.

萘醚型環氧樹脂例如可由下述一般式(1)所表示。 The naphthene ether type epoxy resin can be represented, for example, by the following general formula (1).

(式中，R1表示氫原子或甲基，R2分別獨立表示氫原子、碳原子數1~4之烷基、芳烷基、萘基或含有環氧丙基醚基的萘基，o及m分別為0~2的整數，且o或m之任一者為1以上。) (wherein R1 represents a hydrogen atom or a methyl group, and R2 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aralkyl group, a naphthyl group or a naphthyl group having a glycidyl ether group, o and m Each is an integer from 0 to 2, and either o or m is 1 or more.)

上述環氧樹脂之含量並無特別限定，較佳係以上述樹脂組成物整體之固形份基準計為5~60重量%。若含量未滿上述下限值，則有樹脂組成物之硬化性降低、或使用該樹脂組成物所得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，則有預浸體或印刷佈線板之熱膨脹率變大、或耐熱性降低的情形。上述環氧樹脂之含量特佳係以樹 脂組成物整體之固形份基準計為10~50重量%。 The content of the epoxy resin is not particularly limited, but is preferably 5 to 60% by weight based on the total solid content of the resin composition. When the content is less than the above lower limit, the curing property of the resin composition may be lowered, or the moisture resistance of the prepreg or the printed wiring board obtained by using the resin composition may be lowered. In addition, when the upper limit is exceeded, the thermal expansion coefficient of the prepreg or the printed wiring board may increase or the heat resistance may decrease. The above epoxy resin content is particularly good for the tree The solid content of the whole fat composition is 10 to 50% by weight.

上述環氧樹脂之重量平均分子量並無特別限定，較佳為1.0×102~2.0×104。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內，則可作成此等特性之平衡優越者。 The weight average molecular weight of the above epoxy resin is not particularly limited, but is preferably 1.0 × 10 2 to 2.0 × 10 4 . When the weight average molecular 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, it is possible to achieve a superior balance of these characteristics.

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。 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 weight molecular weight in terms of polystyrene.

上述樹脂組成物並無特別限定，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。 The resin composition is not particularly limited, and by containing a cyanate resin, the flame retardancy can be improved, the thermal expansion coefficient can be reduced, and the electrical characteristics (low dielectric constant, low dielectric loss tangent) of the prepreg can be improved.

上述異氰酸樹脂並無特別限定，例如可使鹵化氰化合物與酚類或萘酚類反應，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。 The isocyanate resin is not particularly limited, and for example, a halogenated cyanide compound can be reacted with a phenol or a naphthol, and if necessary, prepolymerized by a method such as heating. Further, a commercially available product thus prepared can also be used.

作為上述氰酸酯樹脂之種類並無特別限定，可舉例如酚醛清漆型氰酸酯樹脂、雙酚A型氰酸酯樹脂、雙酚E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。 The type of the cyanate resin is not particularly limited, and examples thereof include a novolak type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a tetramethylbisphenol F type cyanate. A bisphenol type cyanate resin such as an acid ester resin.

上述氰酸酯樹脂較佳係於分子內具有2個以上氰酸酯基(-O-CN)。可舉例如2,2’-雙(4-氰氧基苯基)亞異丙基、1,1’-雙(4-氰氧基苯基)乙烷、雙(4-氰氧基-3,5-二甲基苯基)甲 烷、1,3-雙(4-氰氧基苯基-1-(1-甲基亞乙基))苯、二環戊二烯型異氰酸酯、苯酚酚醛清漆型異氰酸酯、雙(4-氰氧基苯基)硫醚、雙(4-氰氧基苯基)醚、1,1,1-參(4-氰氧基苯基)乙烷、參(4-氰氧基苯基)亞磷酸酯、雙(4-氰氧基苯基)碸、2,2-雙(4-氰氧基苯基)丙烷、1,3-、1,4-、1,6-、1,8-、2,6-或2,7-二氰氧基萘、1,3,6-三氰氧基萘、4,4-二氰氧基聯苯及苯酚酚醛清漆型、甲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。 The cyanate resin preferably has two or more cyanate groups (-O-CN) in the molecule. For example, 2,2'-bis(4-cyanooxyphenyl)isopropylidene, 1,1'-bis(4-cyanooxyphenyl)ethane, bis(4-cyanooxy-3) ,5-dimethylphenyl)A Alkane, 1,3-bis(4-cyanooxyphenyl-1-(1-methylethylidene))benzene, dicyclopentadiene isocyanate, phenol novolac type isocyanate, bis(4-cyanate) Phenyl phenyl thioether, bis(4-cyanooxyphenyl)ether, 1,1,1-gin(4-cyanooxyphenyl)ethane, ginseng (4-cyanooxyphenyl)phosphoric acid Ester, bis(4-cyanooxyphenyl)anthracene, 2,2-bis(4-cyanooxyphenyl)propane, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanooxynaphthalene, 1,3,6-tricyanooxynaphthalene, 4,4-dicyanooxybiphenyl and phenol novolak type, cresol novolak type A cyanate resin obtained by a reaction between a phenol and a cyanogen halide, a cyanate resin obtained by a reaction between a naphthol aralkyl type polyheptanol and a cyanogen halide.

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烯型氰酸酯係交聯密度之控制及耐濕可靠性優越。由低熱膨脹性之觀點而言，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。 Among these, the phenol novolac type cyanate resin is excellent in flame retardancy and low thermal expansion property, and 2,2-bis(4-cyanooxyphenyl)isopropylidene and dicyclopentadiene type cyanic acid. The ester crosslink density is controlled and the moisture resistance reliability is superior. From the viewpoint of low thermal expansion property, 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.

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。 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 cyanate resin and the prepolymer may be used in combination.

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。 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.

上述預聚物並無特別限定，於例如使用3聚化率為20~50重量%之預聚物時，可表現良好的成形性、流動性。 The prepolymer is not particularly limited. For example, when a prepolymer having a polymerization ratio of 20 to 50% by weight is used, good formability and fluidity can be exhibited.

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10~50重量%。若氰酸酯樹脂之含量為上述範圍內，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。 The content of the cyanate resin is not particularly limited, but is preferably 5 to 60% by weight, more preferably 10 to 50% by weight based on the total solid content of the resin composition. When the content of the 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, 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.

上述氰酸酯樹脂之重量分子量並無特別限定，較佳為5.0×102~4.5×103、特佳6.0×102~3.0×103。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。 The weight molecular weight of the cyanate resin is not particularly limited, but is preferably 5.0 × 10 2 to 4.5 × 10 3 and particularly preferably 6.0 × 10 2 to 3.0 × 10 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 may deteriorate.

本發明中，上述氰酸酯樹脂之重量平均分子量可藉由例如凝膠滲透層析法(GPC)進行測定，作為聚苯乙烯換算之重量分子量而特定。 In the present invention, the weight average molecular weight of the cyanate resin can be measured by, for example, gel permeation chromatography (GPC), and is specified as a weight molecular weight in terms of polystyrene.

上述樹脂組成物並無特別限定，藉由含有雙順丁烯二醯亞胺樹脂，可提升耐熱性。 The resin composition is not particularly limited, and the heat resistance can be improved by containing a bis-methylene iodide resin.

作為上述雙順丁烯二醯亞胺樹脂並無特別限定，可舉例如N,N’-(4,4’-二苯基甲烷)雙順丁烯二醯亞胺、雙(3-乙基-5-甲基-4-順丁烯二醯亞胺苯基)甲烷、2,2-雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]丙烷等之雙順丁烯二醯亞胺樹脂。上述雙順丁烯二醯亞胺樹脂可進一步併用一種或2種以上之其他雙 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烯二醯亞胺樹脂，或併用上述雙順丁烯二醯亞胺樹脂與其之預聚物。 The bis-m-butylene iminoimide resin is not particularly limited, and examples thereof include N,N'-(4,4'-diphenylmethane)bis-n-butylene diimide and bis(3-ethyl group). 5-5-methyl-4-maleimide phenyl)methane, 2,2-bis[4-(4-maleoximeimide phenoxy)phenyl]propane, etc. Butylene diimide resin. The above-mentioned bis-butylene diimide resin may further be used in combination with one or more other two The maleimide resin is not particularly limited. Further, the above-mentioned bis-butenylene imine resin may be used alone. Further, a bis-butenylene imine resin having a different weight average molecular weight may be used in combination, or the above-mentioned bis-butenylene diimide resin and a prepolymer thereof may be used in combination.

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1~35重量%、特佳5~20重量%。 The content of the above-mentioned bis-butenylenediamine resin is not particularly limited, and is preferably from 1 to 35% by weight, particularly preferably from 5 to 20% by weight, based on the total solid content of the resin composition.

(硬化劑、硬化促進劑) (hardener, hardening accelerator)

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。 The resin composition used in the present invention may be used in combination with a hardener. The curing agent is not particularly limited. For example, when an epoxy resin is used as the thermosetting resin, a phenolic curing agent, an aliphatic amine, an aromatic amine, or a dicyandiamide which is generally used as a curing agent for an epoxy resin can be used. Amidoxime, a dicarboxylic acid diamine compound, an acid anhydride, or the like.

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、鎓鹽化合物等。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。 Further, in the resin composition used in the present invention, a curing accelerator may be added as needed. The hardening 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. As the curing accelerator, one type of the derivative including the above may be used alone, and two or more kinds of derivatives including the same may be used in combination.

(偶合劑) (coupling agent)

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 預浸體之耐熱性、尤其是吸濕後之焊錫耐熱性。 The above resin composition may further contain a coupling agent. The coupling agent is formulated in order to improve the wettability of the interface between the thermosetting resin and the filler. Thereby, the resin and the filler can be uniformly fixed to the fiber woven fabric, and the improvement is improved. The heat resistance of the prepreg, especially the solder heat resistance after moisture absorption.

上述偶合劑並無特別限定，可舉例如環氧基矽烷偶合劑、陽離子性矽烷偶合劑、胺基矽烷偶合劑、鈦酸酯系偶合劑、聚矽氧油型偶合劑等。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。 The coupling agent is not particularly limited, and examples thereof include an epoxy decane coupling agent, a cationic decane coupling agent, an amino decane coupling agent, a titanate coupling agent, and a polyasoxy oil type coupling agent. Thereby, the wettability with the interface of the filler can be improved, whereby the heat resistance of the prepreg can be further improved.

上述偶合劑之添加量並無特別限定，相對於填充材100重量份，較佳為0.05~3重量份、特佳0.1~2重量份。若含量未滿上述下限值，則因無法充分被覆填充材，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，則對反應造成影響，而有彎曲強度等降低的情形。 The amount of the coupling agent to be added is not particularly limited, and is preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight, per 100 parts by weight of the filler. When the content is less than the above lower limit, the filler cannot be sufficiently covered, so that the effect of improving heat resistance is lowered. Moreover, when the content exceeds the above upper limit, the reaction is affected, and the bending strength or the like is lowered.

(其他) (other)

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、磷系、磷腈類等之難燃助劑、離子捕捉劑等之上述成分以外的添加物。 Further, in the above resin composition, an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, a phosphorus-based or a phosphazene-based flame retardant, and an ion may be added as needed. Additives other than the above components such as a capture agent.

本發明之預浸體係將於溶劑中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漿料，於該漿料中添加其他之樹脂組成物之成分，再加入上述溶媒使其溶解、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之二氧化矽粒子容易進入纖維織布 中，可提升樹脂組成物對纖維織布的含浸性。 In the prepreg system of the present invention, the varnish containing the thermosetting resin composition in the solvent is retained in the fiber woven fabric, and then obtained by removing the solvent. The preparation method of the varnish is not particularly limited, and for example, a slurry in which a thermosetting resin and a filler are dispersed in a solvent is prepared, and a component of another resin composition is added to the slurry, and the solvent is added thereto. The method of dissolving and mixing. Thereby, the dispersibility of the filler can be improved, and the cerium oxide particles having an average particle diameter of 5 to 100 nm contained in the filler can easily enter the fiber woven fabric. Among them, the impregnation property of the resin composition to the fiber woven fabric can be improved.

尚且，本發明中所謂於溶劑中含有熱硬化性樹脂組成物，係指上述熱硬化性樹脂組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。 In the present invention, the thermosetting resin composition is contained in the solvent, and the soluble resin or the like contained in the thermosetting resin composition is dissolved in a solvent, and the insoluble filler or the like is dispersed in the solvent.

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)、環己酮(ANON)、甲基異丁基酮(MIBK)、環戊酮、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等。又，在不造成不良影響的範圍內亦可使用不良溶媒(poor 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), cyclohexanone (ANON), and methyl isobutyl ketone. (MIBK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. Further, a poor solvent can be used in a range that does not cause adverse effects.

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)並無特別限定，較佳為30~80重量%、特佳40~70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。 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, but is preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight. Thereby, the impregnation property of the resin composition with the fiber woven fabric is improved. Further, it is possible to suppress surface smoothness, thickness variation, and the like at the time of coating.

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漬於清漆中的方法、由各種塗佈器進行塗佈的方法、由噴霧器進行吹附的方法、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法等。此等之中，較佳為將纖維織布浸漬於清漆中的方法。藉此，可提升熱硬化性樹脂組成物對纖維織布的含浸性。又，在將纖維織布浸漬於清漆中時，可使用通常之含浸塗佈設備。又，可將上述清漆之溶劑於例如90~180℃進行乾燥1~10分鐘，藉此得到半硬化的預 浸體。 The method of impregnating the above-mentioned varnish into the above-mentioned fiber woven fabric may, for example, a method of immersing the fiber woven fabric in the varnish, a method of coating with various applicators, a method of blowing by a sprayer, and a varnish on the base. A method of applying and drying a resin to form a resin sheet, and arranging the resin sheet so as to be in contact with the fiber woven fabric, and to pressurize the resin sheet. Among these, a method of immersing the fiber woven fabric in the varnish is preferred. Thereby, the impregnation property of a thermosetting resin composition with a fiber woven fabric can be improved. Further, when the fiber woven fabric is immersed in the varnish, a usual impregnation coating apparatus can be used. Further, the solvent of the varnish may be dried at, for example, 90 to 180 ° C for 1 to 10 minutes, thereby obtaining a semi-hardened pretreatment. Dip body.

上述預浸體係藉由以纖維織布所構成之纖維織布層、與在該纖維織布層之兩面所形成的由樹脂組成物所構成之樹脂層所構成。上述纖維織布層的厚度並無特別限定，較佳為10~200μm、更佳10~140μm、再佳20~90μm。上述樹脂層之厚度(僅單面之一層份的厚度)並無特別限定，較佳為0.5~20μm、特佳2~10μm。藉由使纖維織布層之厚度及樹脂層之厚度為上述範圍內，則與導體層間之密黏性及表面平滑性更加良好。 The prepreg system is composed of a fiber woven fabric layer composed of a fiber woven fabric and a resin layer composed of a resin composition formed on both surfaces of the fiber woven fabric layer. The thickness of the fiber woven fabric layer is not particularly limited, but is preferably 10 to 200 μm, more preferably 10 to 140 μm, still more preferably 20 to 90 μm. The thickness of the resin layer (only the thickness of one layer on one side) is not particularly limited, but is preferably 0.5 to 20 μm, particularly preferably 2 to 10 μm. When the thickness of the fiber woven fabric layer and the thickness of the resin layer are within the above range, the adhesion to the conductor layer and the surface smoothness are further improved.

上述預浸體之整體厚度並無特別限定，較佳為30~220μm、特佳40~165μm。藉此，則預浸體之操作性良好，且亦可對應薄型化。 The overall thickness of the prepreg is not particularly limited, but is preferably 30 to 220 μm and particularly preferably 40 to 165 μm. Thereby, the workability of the prepreg is good, and it can also be made thinner.

上述預浸體中，在構成纖維織布之線股中，於構成線股之纖維所延伸的方向上不存在具有50μm以上長度的空隙。藉此，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，較佳係於構成線股之纖維所延伸的方向上不存在具有20μm以上、尤其是10μm以上長度的空隙。 In the above-mentioned prepreg, in the strands constituting the fiber woven fabric, voids having a length of 50 μm or more do not exist in the direction in which the fibers constituting the strands extend. Thereby, the insulation reliability of the printed wiring board obtained by using the prepreg for the insulating layer can be improved. Further, it is preferable that the strands constituting the fiber woven fabric have voids having a length of 20 μm or more, particularly 10 μm or more, in a direction in which the fibers constituting the strands extend.

另外，上述預浸體中，構成纖維織布之線股中之直徑為50μm以上之空隙的數密度為50cm-3。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50μm以上之空隙的數密度較佳為 20cm-3以下、特佳10cm-3以下。 Further, in the prepreg, the number density of the voids having a diameter of 50 μm or more in the strands constituting the fiber woven fabric is 50 cm -3 . At this time, the insulation reliability of the printed wiring board obtained by using the prepreg for the insulating layer can be improved. Further, the number density of more than 50μm fiber cloth constituting the strands of the diameter of the voids is preferably 20cm -3 or less, particularly preferably 10cm -3 or less.

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。 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, the bulk density of the fiber woven fabric, and the like.

2.積層板 2. Laminate

接著，說明積層板。 Next, the laminated board will be described.

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。 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.

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。 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. Next, a metal foil laminated board can be obtained by heat-press molding the prepreg and the metal foil.

作為上述金屬箔，可舉例如銅、銅系合金、鋁、鋁系合金、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。 Examples of the metal foil include copper, a copper-based alloy, aluminum, an aluminum-based alloy, silver, a silver-based alloy, gold, a gold-based alloy, zinc, a zinc-based alloy, nickel, a nickel-based alloy, tin, and a tin-based alloy. Metal foil such as iron or iron alloy. Further, a conductor layer such as the above-described copper or copper alloy may be formed by plating.

在製造金屬箔積層板時，加熱溫度並無特別限定，較佳為 120~220℃、特佳150~200℃。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℃之溫度進行後硬化。 In the production of the metal foil laminate, the heating temperature is not particularly limited, and is preferably 120~220°C, especially good 150~200°C. The pressure of the pressurization is not particularly limited, but is preferably 0.5 to 5 MPa, particularly preferably 1 to 3 MPa. Further, it may be post-cured at a temperature of 150 to 300 ° C in a high temperature bath or the like as needed.

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為內側進行配置(圖1(a))，於真空中依加熱60~130℃、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))。 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 in which a uniform resin layer 12 is coated on a metal foil 11 by an applicator is prepared. 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. It is impregnated with lamination at 0.1~5 MPa. Thereby, the 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 (Fig. 1 (c)) can be obtained.

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為內側進行配置(圖2(a))，於真空中依加熱60~130℃、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 片31之面上配置金屬箔11(圖2(d))，進行加熱加壓成形，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，係在經積層之預浸體之最外側的上下兩面或單面上配置金屬箔或高分子薄膜片，藉由進行加熱加壓成形而可得到金屬箔積層板。藉此種製造方法所得之金屬箔積層板係厚度精度高、厚度均勻，進而表面平滑性優越。又，由於可得到成形應變小的金屬箔積層板，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，係曲翹較小、曲翹偏差亦較小。進而可產率佳地製造印刷佈線板及半導體裝置。 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 laminate is impregnated by pressing 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 polymer film is peeled off. The metal foil 11 (Fig. 2 (d)) is placed on the surface of the sheet 31, and is subjected to heat and pressure molding, whereby the metal foil laminate 52 is obtained (Fig. 2(e)). Further, when the polymer film sheets on both sides are peeled off, two or more sheets may be laminated in the same manner as the above-mentioned prepreg. When two or more prepregs are laminated, a metal foil or a polymer film sheet is placed on the upper and lower surfaces or a single surface of the outermost layer of the prepreg of the laminate, and a metal foil is obtained by heat and pressure molding. Laminated board. The metal foil laminated board obtained by the above-mentioned manufacturing method has high thickness precision, uniform thickness, and superior surface smoothness. In addition, since a metal foil laminate having a small strain is obtained, a printed wiring board and a semiconductor device which are produced by using the metal foil laminate obtained by the production method have a small warp and a small variation in warpage. Further, a printed wiring board and a semiconductor device can be manufactured with good yield.

作為上述加熱加壓成形的條件，溫度並無特別限定，較佳為120~250℃、特佳150~220℃。上述加壓之壓力並無特別限定，較佳為0.1~5MPa、特佳0.5~3MPa。進而視需要可於高溫槽等中在150~300℃之溫度進行後硬化。 The temperature is not particularly limited as a condition of the above-described heating and press forming, and is preferably 120 to 250 ° C and particularly preferably 150 to 220 ° C. The pressure of the above pressurization is not particularly limited, but is preferably 0.1 to 5 MPa, particularly preferably 0.5 to 3 MPa. Further, post-hardening can be carried out at a temperature of 150 to 300 ° C in a high temperature bath or the like as needed.

圖1~2等之金屬箔積層板並無特別限定，例如可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。 The metal foil laminate of FIGS. 1 to 2 and the like is not particularly limited, and for example, it can be produced by using an apparatus for producing a metal foil having a resin layer and a device for manufacturing a metal foil laminate.

在製造上述具有樹脂層之金屬箔的裝置中，金屬箔係使用例如將長尺之片材品作成捲物形態者等，藉此可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 明之樹脂組成物溶解、分散於溶劑中而得之塗佈液。樹脂清漆之塗佈量可藉由刮刀輥、與該刮刀輥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箔，係移送至橫搬送型之熱風乾燥裝置之內部，將樹脂清漆中所含有之有機溶劑等實質地乾燥去除，視需要可作成使硬化反應進行至途中的具有樹脂層之金屬箔。具有樹脂層之金屬箔係藉由可直接進行捲取的層合輥，在形成了樹脂層之側上重疊保護薄膜，捲取層合了該保護薄膜之具有樹脂層之金屬箔，得到捲物形態的具有絕緣樹脂層之金屬箔。在使用圖1~2等之製造方法時，相較於習知之使清漆含浸的製造方法，其均勻之樹脂量的控制、以及面內厚度精度優越，故搭載了半導體元件之半導體裝置的曲翹偏差較小、產率提升。 In the apparatus for producing the metal foil having the resin layer described above, the metal foil is used, for example, by using a long-length sheet material as a roll form, whereby the metal foil can be continuously wound up and supplied. The resin varnish is continuously supplied to the metal foil in a predetermined amount by a resin supply device. Here, as a resin varnish, the hair is used. A coating liquid obtained by dissolving and dispersing the resin composition in a solvent. The coating amount of the resin varnish can be controlled by the gap between the doctor roll and the backup roll of the doctor roll. The metal foil coated with the resin varnish of a predetermined amount is transferred to the inside of the hot air drying device of the horizontal transfer type, and the organic solvent or the like contained in the resin varnish is substantially dried and removed, and if necessary, the hardening reaction can be carried out on the way. A metal foil having a resin layer. The metal foil having the resin layer is formed by laminating a roll directly on the side of the resin layer, and a protective film is laminated on the side on which the resin layer is formed, and a metal foil having a resin layer of the protective film is wound up to obtain a roll. A metal foil having an insulating resin layer. When the manufacturing method of FIGS. 1 to 2 and the like is used, the uniform resin amount is controlled and the in-plane thickness precision is superior to the conventional manufacturing method in which the varnish is impregnated, so that the semiconductor device in which the semiconductor element is mounted is curved. The deviation is small and the yield is improved.

另外，藉此種製造方法得到金屬箔積層板時，必須考慮樹脂組成物對纖維織布的含浸性。填充材係藉由使用平均粒徑5~100nm之二氧化矽粒子，而尤其可提升對纖維織布的含浸性，故在加熱加壓成形時，抑制金屬箔積層板內之樹脂組成物的流動，抑制熔融樹脂之不均勻移動，故可防止金屬箔積層板表面之條紋狀的不均，且可作成均勻厚度。 Further, when a metal foil laminate is obtained by such a production method, it is necessary to consider the impregnation property of the resin composition to the fiber woven fabric. The filler is used to suppress the impregnation of the fiber woven fabric by using cerium oxide particles having an average particle diameter of 5 to 100 nm, so that the flow of the resin composition in the metal foil laminate is suppressed during the heat and pressure forming. By suppressing uneven movement of the molten resin, it is possible to prevent streaky unevenness on the surface of the metal foil laminate, and to form a uniform thickness.

3.印刷佈線板 3. Printed wiring board

接著說明本發明之印刷佈線板。 Next, the printed wiring board of the present invention will be described.

本發明之印刷佈線板係將上述預浸體及/或上述積層板用於內層電路基板而成。 In the printed wiring board of the present invention, the prepreg and/or the laminated board are used for an inner layer circuit board.

另外，本發明之印刷佈線板係將上述之預浸體用於內層電路上之絕緣層而成。 Further, in the printed wiring board of the present invention, the above prepreg is used for the insulating layer on the inner layer circuit.

尚且，在將本發明之預浸體或本發明之積層板用於內層電路基板而得的印刷佈線板的情況，使內層電路基板之預浸體硬化而成之層為絕緣層。 In the case of the printed wiring board obtained by using the prepreg of the present invention or the laminated board of the present invention for the inner layer circuit board, the layer obtained by curing the prepreg of the inner layer circuit board is an insulating layer.

本發明中所謂印刷佈線板，係指在絕緣層上設置金屬箔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)之任一種。所謂多層印刷佈線板，係指藉由鍍穿孔法或增層法等重疊了3層以上的印刷佈線板，可藉由於內層電路基板上重疊絕緣層並進行加熱加壓成形而獲得。作為上述內層電路基板，可使用例如使用了本發明之積層板及/或本發明之預浸體而成者。作為使用本發明之積層板而成的內層電路基板，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等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。 In the present invention, a printed wiring board is formed by providing a conductive layer such as a metal foil on an insulating layer to form a conductor circuit layer, and may be a single-sided printed wiring board (single-layer board) or a double-sided printed wiring board (two-layer board). And any of multilayer printed wiring boards (multilayer boards). The multilayer printed wiring board is a printed wiring board in which three or more layers are stacked by a plating hole method or a build-up method, and can be obtained by superposing an insulating layer on an inner layer circuit board and performing heat and pressure molding. As the inner layer circuit board, for example, a laminate using the laminate of the present invention and/or a prepreg of the present invention can be used. As the inner layer circuit board using the laminated board of the present invention, for example, a conductor circuit which forms a predetermined pattern by a semi-additive method or the like on a laminated board of the present invention which does not have a metal foil can be suitably used, and the conductor circuit portion is formed. A blackening process is performed, or a conductor circuit having a predetermined pattern is formed on the metal foil of the metal foil laminate of the present invention, and the conductor circuit portion is blackened.

另外，作為使用本發明之預浸體而成的內層電路基板，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內藏基板，於該零 件內藏基板上藉半加成法等形成既定圖案之導體電路，對該導體電路部分進行了黑化處理者。 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 laminated and heated and pressed to obtain a built-in substrate of the part, and the zero A conductor circuit in which a predetermined pattern is formed by a semi-additive method or the like on a built-in substrate, and the conductor circuit portion is blackened.

再者，本發明中，係在此種使用了本發明之積層板及/或本發明之預浸體而成的內層電路基板、或習知之內層電路基板之導體電路上，進一步積層本發明之預浸體，予以加熱加壓硬化而作成內層電路基板。作為上述內層電路上之絕緣層，可使用本發明之預浸體。又，於使用本發明之預浸體作為上述內層電路上之絕緣層時，上述內層電路基板亦可不使用本發明之預浸體或積層板。 Further, in the present invention, the inner layer circuit board using the laminated board of the present invention and/or the prepreg of the present invention or the conductor circuit of the conventional inner layer circuit board is further laminated. The prepreg of the invention is subjected to heat and pressure hardening to form an inner layer circuit board. As the insulating layer on the above inner layer circuit, the prepreg of the present invention can be used. Further, when the prepreg of the present invention is used as the insulating layer on the inner layer circuit, the inner layer circuit substrate may not use the prepreg or laminate of the present invention.

以下，作為本發明之印刷佈線板的代表例，針對使用本發明之金屬箔積層板作為內層電路基板、使用本發明之預浸體作為絕緣層的情況的多層印刷佈線板進行說明。 In the following, a multilayer printed wiring board in the case where the metal foil laminated board of the present invention is used as an inner layer circuit board and the prepreg of the present invention is used as an insulating layer will be described as a representative example of the printed wiring board of the present invention.

內層電路基板係於上述金屬箔積層板之單面或兩面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而製造。上述導體電路之形成方法並無特別限定，可藉由減去法、加成法、半加成法等之公知方法進行。又，內層電路基板上，可藉由鑽頭加工、雷射加工等形成穿孔，藉鍍覆等進行兩面之電氣連接。由於上述內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、UV雷射及二氧化碳雷射等。 The inner layer circuit board is formed by forming a conductor circuit of a predetermined pattern on one surface or both surfaces of the metal foil laminated board, and manufacturing the conductor circuit portion by blackening. The method for forming the conductor circuit is not particularly limited, and can be carried out by a known method such as a subtractive method, an additive method, or a semi-additive method. Further, on the inner layer circuit board, perforations can be formed by drill processing, laser processing, or the like, and electrical connection between the two surfaces can be performed by plating or the like. Since the inner layer circuit board is composed of the metal foil laminated board of the present invention, it is possible to form a perforation having excellent precision such as a hole diameter and a shape, particularly by laser processing. The above lasers can use excimer lasers, UV lasers, and carbon dioxide lasers.

其次，於該內層電路基板上重疊上述預浸體並進行加熱加 壓成形，再藉由加熱硬化而形成絕緣層。具體而言，係將上述預浸體與上述內層電路基板重疊，使用真空加壓式層合裝置等進行真空加熱加壓成形，其後，藉熱風乾燥裝置等對絕緣層進行加熱硬化。於此，作為加熱加壓成形條件並無特別限定，若列舉其一例，可依溫度60~160℃、壓力0.2~3MPa實施。又，作為加熱硬化之條件並無特別限定，若列舉其一例，可依溫度140~240℃、時間30~120分鐘實施。 Next, the prepreg is superposed on the inner circuit substrate and heated Press forming, and then hardening by heat to form an insulating layer. Specifically, the prepreg is superposed on the inner layer circuit board, and vacuum heat press molding is performed using a vacuum pressure type laminating apparatus or the like, and thereafter, the insulating layer is heat-hardened by a hot air drying device or the like. Here, the heating and press forming conditions are not particularly limited, and an example thereof can be carried out at a temperature of 60 to 160 ° C and a pressure of 0.2 to 3 MPa. Further, the conditions for the heat curing are not particularly limited, and an example thereof can be carried out at a temperature of 140 to 240 ° C for 30 to 120 minutes.

接著，對經積層之絕緣層照射雷射，形成開孔部(通孔)。上述雷射可使用與穿孔形成時所使用之雷射相同者。由於上述絕緣層為由本發明之預浸體所構成，故可藉由雷射加工，形成孔徑、形狀等之精度優越的開孔部。 Next, the laminated insulating layer is irradiated with a laser to form an opening portion (through hole). The above laser can be used in the same manner as the laser used in the formation of the perforations. Since the insulating layer is composed of the prepreg of the present invention, it is possible to form an opening portion having excellent precision such as a hole diameter and a shape by laser processing.

雷射照射後之樹脂殘渣(污跡)等，較佳係進行藉由過錳酸鹽、重鉻酸鹽等之氧化劑等予以去除的處理、亦即去污處理。若去污處理不足、未充分確保去污性，則即使於開孔部進行金屬鍍覆處理，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，由於可對平滑之絕緣層表面同時進行粗化，故在藉金屬鍍覆處理於絕緣層表面上形成導體層時，絕緣層表面與導體層間之密黏性優越。又，在藉雷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。 The resin residue (smudge) or the like after the laser irradiation is preferably subjected to a treatment of removing it by an oxidizing agent such as permanganate or dichromate, that is, a desmutting treatment. If the decontamination treatment is insufficient and the decontamination property is not sufficiently ensured, even if the metal plating treatment is performed on the opening portion, the electrical conductivity between the upper conductor circuit layer and the lower conductor circuit layer cannot be sufficiently ensured due to the stain. Moreover, by performing the desmear treatment, since the surface of the smooth insulating layer can be simultaneously roughened, when the conductor layer is formed on the surface of the insulating layer by metal plating, 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 opening portion is formed by laser irradiation.

接著，於開孔部及絕緣層表面進行金屬鍍覆處理，形成導體層。於上述絕緣層表面，係進一步藉由上述公知方法進行 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。 Next, metal plating treatment is performed on the surface of the opening portion and the insulating layer to form a conductor layer. The surface of the insulating layer is further subjected to the above known method. A conductor circuit is formed. 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.

亦可進而積層絕緣層，進行上述同樣的導體電路形成，但在多層印刷佈線板中，係於導體電路形成後，於最外層形成抗焊膜。抗焊膜之形成方法並無特別限定，例如可藉由積層(層合)乾薄膜型之抗焊劑，藉由曝光及顯影而予以形成的方法；或對印刷了液狀抗焊劑者藉由曝光及顯影而予以形成的方法。在將所得之多層印刷佈線板用於半導體裝置的情況，係為了安裝半導體元件而設置連接用電極部。連接用電極部可由鍍金、鍍鎳及焊錫鍍覆等之金屬皮膜所適當被覆。 Further, the same conductor circuit can be formed by laminating an insulating layer. However, in the multilayer printed wiring board, after the conductor circuit is formed, a solder resist film is formed on the outermost layer. The method for forming the solder resist film is not particularly limited, and may be, for example, a method of forming a laminated (laminated) dry film type solder resist by exposure and development; or by exposing a liquid solder resist. And a method of forming it by development. In the case where the obtained multilayer printed wiring board is used for a semiconductor device, a connection electrode portion is provided in order to mount a semiconductor element. The electrode portion for connection can be appropriately covered with a metal film such as gold plating, nickel plating, or solder plating.

4.半導體裝置 4. Semiconductor device

接著說明本發明之半導體裝置。 Next, a semiconductor device of the present invention will be described.

於上述所得之印刷佈線板上安裝具有焊錫凸塊的半導體元件，經由焊錫凸塊，達成與上述印刷佈線板的連接。然後，於印刷佈線板與半導體元件之間填充密封樹脂，形成半導體裝置。焊錫凸塊較佳係由以錫、鉛、銀、銅、鉍等所構成之合金所構成。 A semiconductor element having solder bumps is mounted on the printed wiring board obtained as described above, and connection to the printed wiring board is achieved via solder bumps. Then, a sealing resin is filled between the printed wiring board and the semiconductor element to form a semiconductor device. Preferably, the solder bumps are made of an alloy composed of tin, lead, silver, copper, tantalum or the like.

半導體元件與印刷佈線板的連接方法，係使用倒裝晶片接合器等，進行印刷佈線板上之連接用電極部與半導體元件之焊錫凸塊的位置對準，其後，使用IR迴焊裝置、熱板、其他加熱裝置將焊錫凸塊加熱至熔點以上，藉由使印刷佈線板 與焊錫凸塊進行熔融接合而予以連接。又，為了使連接可靠性良好，亦可事先於印刷佈線板上之連接用電極部形成焊錫膏等熔點較低的金屬層。於此接合步驟前，亦可藉由於焊錫凸塊及/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。 The method of connecting the semiconductor element to the printed wiring board is to perform alignment of the connection electrode portion on the printed wiring board and the solder bump of the semiconductor element by using a flip chip bonder or the like, and thereafter, using an IR reflow device, Hot plates and other heating devices heat the solder bumps above the melting point by making the printed wiring board The solder bumps are joined by fusion bonding. Moreover, in order to improve the connection reliability, a metal layer having a low melting point such as solder paste may be formed in advance on the electrode portion for connection on the printed wiring board. Before the bonding step, the solder may be applied to the surface layer of the solder bump and/or the connection electrode portion on the printed wiring board to improve the connection reliability.

(實施例) (Example)

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。 Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited thereto.

實施例及比較例所使用之纖維織布，係將JIS R3413所規定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。 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130μm，基重155g/m2 A: T glass, using E110 1/0 glass fiber yarn, the number of woven roots 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 130μm, and the basis weight is 155g/ m 2

B：E玻璃，使用DE150 1/0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95μm，基重121g/m2 B: E glass, using glass fiber yarn of DE150 1/0, the number of woven roots per 25mm of the warp and the horizontal line is 46.5, 44, and the thickness of the open fiber and flat processing is 95μm, and the basis weight is 121g/ m 2

C：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65根、64根，經開纖、扁平處理的厚度為95μm，基重121g/m2 C: T glass, using E225 1/0 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 65, 64, the thickness of the open fiber and flat processing is 95μm, the basis weight is 121g/ m 2

D：D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65根、64根，經開纖、扁平處理的 厚度為95μm，基重121g/m2 D: D glass, using E225 1/0 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 65, 64, the thickness of the open fiber and flat processing is 95μm, the basis weight is 121g/ m 2

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46μm，基重53g/m2 E: T glass, using D450 1/0 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 59, 59, the thickness of the open fiber and flat processing is 46μm, the basis weight is 53g/ m 2

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20μm，基重24g/m2 F: T glass, using BC1500 1/0 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 90, 90, the thickness of the open fiber, flat treatment is 20μm, the basis weight is 24g/ m 2

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25μm，基重31g/m2 G: T glass, using C1200 1/0 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 74, 77, and the thickness of the open fiber and flat processing is 25μm, and the basis weight is 31g/ m 2

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115μm，基重155g/m2 H:T glass, using E110 1/0 glass fiber yarn, the number of woven roots 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 115μm, and the basis weight is 155g/ m 2

I：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43根、40根，經開纖、扁平處理的厚度為145μm，基重150g/m2 I: T glass, using E110 1/0 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 43 and 40, and the thickness of the open fiber and flat processing is 145μm, and the basis weight is 150g/ m 2

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97μm，基重100g/m2 J: T glass, using E225 1/0 glass fiber yarn, the number of weaving roots per 25mm of the warp and the horizontal line is 59, 54 pieces, and the thickness of the open fiber and flat processing is 97μm, and the basis weight is 100g/ m 2

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50μm，基重48g/m2 K:T glass, using D450 1/0 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 60, 47, the thickness of the open fiber, flat processing is 50μm, the basis weight is 48g/ m 2

L：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68根、72根，經開纖、扁平處理的厚度為27μm，基重25g/m2 L:T glass, using C1200 1/0 glass fiber yarn, the number of woven roots per 25mm of the warp and the horizontal line is 68, 72, the thickness of the open fiber and flat processing is 27μm, the basis weight is 25g/ m 2

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。 The varnish used in the examples and the comparative examples was produced by mixing and mixing the resin composition in the following varnish production examples 1 to 7.

(清漆製造例1) (varnish manufacturing example 1)

將環氧樹脂(DIC公司製HP-5000)6重量份、苯酚酚醛清漆型氰酸酯樹脂(Ronza公司製PT30)12重量份、酚系硬化劑(明和化成公司製MEH-7851-4L)6重量份、二氧化矽粒子(TOKUYAMA公司製NSS-5N，平均粒徑70nm)10重量份、球狀二氧化矽(Admatechs公司製SO-31R，平均粒徑1.0μm)65重量份、環氧基矽烷(信越化學工業公司製KBM-403E)1.0重量份，於甲基乙基酮中含有、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70重量%的清漆。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體設為100質量%，則該填充材中所含之二氧化矽粒子為13質量%，球狀二氧化矽為87質量%。 6 parts by weight of an epoxy resin (HP-5000 manufactured by DIC Corporation), 12 parts by weight of a phenol novolac type cyanate resin (PT30 manufactured by Ronza Co., Ltd.), and a phenol-based curing agent (MEH-7851-4L manufactured by Megumi Kasei Co., Ltd.) 6 10 parts by weight of cerium oxide particles (NSS-5N, manufactured by TOKUYAMA Co., Ltd., average particle diameter: 70 nm), spherical cerium oxide (SO-31R, average particle diameter: 1.0 μm, manufactured by Admatech Co., Ltd.), 65 parts by weight, epoxy group 1.0 part by weight of decane (KBM-403E, manufactured by Shin-Etsu Chemical Co., Ltd.), contained in methyl ethyl ketone, mixed, and stirred using a high-speed stirring device to obtain an epoxy resin composition of 70% by weight based on the solid content. Varnish. 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 13% by mass, and the spherical cerium oxide is 87% by mass.

(清漆製造例2) (varnish manufacturing example 2)

將作為環氧樹脂之聯苯基芳烷基型環氧樹脂(日本化藥公司製NC-3000)9重量份、雙順丁烯二醯亞胺樹脂(KI化成工業公司製BMI-70)17重量份、4,4’-二胺基二苯基甲烷3重量 份、二氧化矽粒子(TOKUYAMA公司製NSS-5N，平均粒徑70nm)10重量份、水鋁土(河合石灰公司製BMB，平均粒徑0.5μm)60重量份、環氧基矽烷(信越化學工業公司製KBM-403E)1.0重量份，於二甲基甲醯胺中含有、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%，水鋁土為86質量%。 9 parts by weight of a biphenyl aralkyl type epoxy resin (NC-3000, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, and a bis-butylene diimide resin (BMI-70, manufactured by KI Kasei Kogyo Co., Ltd.) 17 Parts by weight, 4,4'-diaminodiphenylmethane 3 weight 10 parts by weight of cerium oxide particles (NSS-5N, manufactured by TOKUYAMA Co., Ltd., average particle diameter: 70 nm), water-alumina (BMB, manufactured by Kawasaki Co., Ltd., average particle diameter: 0.5 μm), 60 parts by weight, epoxy decane (Shin-Etsu Chemical Co., Ltd.) 1.0 part by weight of KBM-403E) manufactured by Industrial Co., Ltd., contained and mixed in dimethylformamide. 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 entire filler contained in the resin composition contained in the varnish is 100% by mass, the cerium oxide particles contained in the filler are 14% by mass, and the bauxite is 86% by mass. %.

(清漆製造例3) (varnish manufacturing example 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(DIC(股)公司製HP4032D)5重量份、氰酸酯樹脂(東都化成(股)製SN485之衍生物，萘酚型)17重量份、雙順丁烯二醯亞胺樹脂(KI化成工業公司製BMI-70)7.5重量份、二氧化矽粒子(TOKUYAMA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1.0μm)35.5重量份、聚矽氧粒子(信越化學工業(股)製KMP600，平均粒徑5μm)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KBM-403E)0.5重量份，於甲基乙基酮中含有、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 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%，球狀二氧化矽為71質量%，聚矽氧粒子為15質量%。 20 parts by weight of a biphenyl aralkyl type epoxy resin (NC-3000FH manufactured by Nippon Kayaku Co., Ltd.), 5 parts by weight of a naphthalene type epoxy resin (HP4032D manufactured by DIC Co., Ltd.), and a cyanate resin (Dongdu Chemical Co., Ltd.) (Stock) SN485 derivative, naphthol type) 17 parts by weight, bis-butylene quinone imine resin (BMI-70, manufactured by KI Chemical Industry Co., Ltd.) 7.5 parts by weight, cerium oxide particles (NSS-made by TOKUYAMA Co., Ltd.) 5N, average particle diameter: 70 nm), 7 parts by weight, spherical cerium oxide (SO-31R, manufactured by Admatech Co., Ltd., average particle diameter: 1.0 μm), 35.5 parts by weight, polyfluorene oxide particles (Kimoshi, Shin-Etsu Chemical Co., Ltd., average particle size) 7.5 parts by weight of a diameter of 5 μm, 0.01 parts by weight of zinc octoate, and 0.5 parts by weight of epoxy decane (KBM-403E, manufactured by Shin-Etsu Chemical Co., Ltd.) were contained and mixed in methyl 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. Moreover, if the filler contained in the resin composition contained and mixed in the varnish is completed When the amount is 100% by mass, the cerium oxide particles contained in the filler are 14% by mass, the spherical cerium oxide is 71% by mass, and the polyfluorene oxide particles are 15% by mass.

(清漆製造例4) (varnish manufacturing example 4)

將作為環氧樹脂之聯苯基芳烷基型環氧樹脂(日本化藥公司製NC-3000)18.5重量份、雙順丁烯二醯亞胺樹脂(KI化成工業公司製BMI-70)34.9重量份、4,4’-二胺基二苯基甲烷6.1重量份、二氧化矽粒子(TOKUYAMA公司製NSS-5N，平均粒徑70nm)5重量份、水鋁土(河合石灰公司製BMB，平均粒徑0.5μm)35重量份、環氧基矽烷(信越化學工業公司製KBM-403E)0.5重量份，於二甲基甲醯胺中含有、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體設為100質量%，則該填充材中所含之二氧化矽粒子為12.5質量%，水鋁土為87.5質量%。 18.5 parts by weight of a biphenyl aralkyl type epoxy resin (NC-3000, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, and a bis-butylene diimide resin (BMI-70, manufactured by KI Kasei Kogyo Co., Ltd.) 34.9重量 parts by weight, 4 parts by weight of 4,4'-diaminodiphenylmethane, 5 parts by weight of cerium oxide particles (NSS-5N, manufactured by TOKUYAMA Co., Ltd., average particle diameter: 70 nm), and bauxite (BMB, manufactured by Kawasaki Co., Ltd.) 0.5 parts by weight of an average particle diameter of 0.5 μm, and 0.5 parts by weight of epoxy decane (KBM-403E, manufactured by Shin-Etsu Chemical Co., Ltd.) was contained and mixed in dimethylformamide. 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 entire filler contained in the resin composition contained in the varnish is 100% by mass, the cerium oxide particles contained in the filler are 12.5% by mass, and the bauxite is 87.5% by mass. %.

(清漆製造例5) (varnish manufacturing example 5)

將作為環氧樹脂之聯苯基芳烷基型環氧樹脂(日本化藥公司製NC-3000)2.80重量份、雙順丁烯二醯亞胺樹脂(KI化成工業公司製BMI-70)5.27重量份、4,4’-二胺基二苯基甲烷0.93重量份、二氧化矽粒子(TOKUYAMA公司製NSS-5N，平均粒徑70nm)10重量份、水鋁土(河合石灰公司製BMB， 平均粒徑0.5μm)80重量份、環氧基矽烷(信越化學工業公司製KBM-403E)1.0重量份，於二甲基甲醯胺中含有、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體設為100質量%，則該填充材中所含之二氧化矽粒子為11質量%，水鋁土為89質量%。 2.80 parts by weight of a biphenyl aralkyl type epoxy resin (NC-3000, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, and a bis-butylene diimide resin (BMI-70, manufactured by KI Chemical Industry Co., Ltd.) 5.27 Parts by weight, 0.93 parts by weight of 4,4'-diaminodiphenylmethane, 10 parts by weight of cerium oxide particles (NSS-5N, manufactured by TOKUYAMA Co., Ltd., average particle diameter: 70 nm), and bauxite (BMB, manufactured by Kawasaki Co., Ltd.) 100 parts by weight of an average particle diameter of 0.5 μm, and 1.0 part by weight of epoxy decane (KBM-403E, manufactured by Shin-Etsu Chemical Co., Ltd.) was contained and mixed in dimethylformamide. 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 entire filler contained in the resin composition contained in the varnish is 100% by mass, the cerium oxide particles contained in the filler are 11% by mass, and the bauxite is 89% by mass. %.

(清漆製造例6) (varnish manufacturing example 6)

將環氧樹脂(DIC公司製HP-5000)6重量份、苯酚酚醛清漆型氰酸酯樹脂(Ronza公司製PT30)12重量份、酚系硬化劑(明和化成公司製MEH-7851-4L)6重量份、二氧化矽粒子(TOKUYAMA公司製NSS-5N，平均粒徑70nm)30重量份、球狀二氧化矽(Admatechs公司製SO-31R，平均粒徑1.0μm)45重量份、環氧基矽烷(信越化學工業公司製KBM-403E)1.0重量份，於甲基乙基酮中含有、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70重量%的清漆。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體設為100質量%，則該填充材中所含之二氧化矽粒子為40質量%，球狀二氧化矽為60質量%。 6 parts by weight of an epoxy resin (HP-5000 manufactured by DIC Corporation), 12 parts by weight of a phenol novolac type cyanate resin (PT30 manufactured by Ronza Co., Ltd.), and a phenol-based curing agent (MEH-7851-4L manufactured by Megumi Kasei Co., Ltd.) 6 30 parts by weight of cerium oxide particles (NSS-5N, manufactured by TOKUYAMA Co., Ltd., average particle diameter: 70 nm), spherical cerium oxide (SO-31R, average particle diameter: 1.0 μm, manufactured by Admatech Co., Ltd.), 45 parts by weight, epoxy group 1.0 part by weight of decane (KBM-403E, manufactured by Shin-Etsu Chemical Co., Ltd.), contained in methyl ethyl ketone, mixed, and stirred using a high-speed stirring device to obtain an epoxy resin composition of 70% by weight based on the solid content. Varnish. 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 40% by mass, and the spherical cerium oxide is 60% by mass.

(清漆製造例7) (varnish manufacturing example 7)

將環氧樹脂(日本化藥公司製NC-3000)6重量份、苯酚酚醛清漆型氰酸酯樹脂(Ronza公司製PT30)12重量份、酚系 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1.0μm)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，於甲基乙基酮中含有、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70重量%的清漆。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體設為100質量%，則該填充材中所含之二氧化矽粒子為0質量%，球狀二氧化矽為100質量%。 6 parts by weight of an epoxy resin (Nippon Chemical Co., Ltd. NC-3000), 12 parts by weight of a phenol novolac type cyanate resin (PT30 manufactured by Ronza Co., Ltd.), and a phenol system 6 parts by weight of sclerosing agent (MEH-7851-4L, manufactured by Megumi Kasei Co., Ltd.), 75 parts by weight of spherical cerium oxide (SO-31R, average particle diameter: 1.0 μm, manufactured by Admatech Co., Ltd.), and epoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 part by weight of KBM-403E) was contained and mixed in methyl ethyl ketone, and stirred using a high-speed stirring apparatus to obtain a varnish having an epoxy resin composition of 70% by weight based on the solid content. 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 0% by mass, and the spherical cerium oxide is 100% by mass.

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，各成分之調配量係以重量份表示。 The composition of the resin composition used in the varnish production examples 1 to 7 is shown in Table 1. Moreover, the compounding amount of each component is shown by weight part.

使用上述玻璃纖維織布及上述清漆，製作預浸體、金屬箔積層板、印刷佈線板(內層電路基板)、多層印刷佈線板及半 導體裝置。 Using the above-mentioned glass fiber woven fabric and the above varnish, a prepreg, a metal foil laminated board, a printed wiring board (inner layer circuit board), a multilayer printed wiring board, and a half are produced. Conductor device.

<實施例1> <Example 1> (1)預浸體之製作 (1) Production of prepreg

將製造例1所得之清漆流延塗佈於厚38μm之聚對苯二甲酸乙二酯基材(以下稱為PET基材)上，依溫度140℃、時間10分鐘使溶劑揮發乾燥，使樹脂層厚度成為30μm。將上述具有樹脂層之基材，依於玻璃織布A之兩面上使樹脂層接觸玻璃織布的方式進行配置，以壓力0.5MPa、溫度140℃、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150μm之預浸體(樹脂層(單面)：10μm，纖維織布層：130μm)。 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, and the solvent was evaporated and dried at a temperature of 140 ° C for 10 minutes to form a resin. The layer thickness was 30 μm. The base material having the resin layer was placed so as to contact the glass woven fabric on both surfaces of the glass woven fabric A, and was vacuum laminated by a pressure of 0.5 MPa, a temperature of 140 ° C, and 1 minute. The MLVP-500 manufactured by Nihon Seisakusho Co., Ltd. was heated and pressurized to impregnate the resin composition. Thus, a prepreg having a thickness of 150 μm having a PET substrate on both sides (resin layer (single side): 10 μm, fiber woven layer: 130 μm) was obtained.

(2)金屬箔積層板之製作 (2) Production of metal foil laminate

於上述預浸體之兩面上重疊具有載體之2μm的銅箔(三井金屬礦業公司製，MICROSIN MT18Ex-2)，依壓力3MPa、溫度220℃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150μm之絕緣層的兩面上具有銅箔的金屬箔積層板。 A 2 μm copper foil (MICROSIN MT18Ex-2, manufactured by Mitsui Mining and Mining Co., Ltd.) having a carrier was placed on both surfaces of the prepreg, and heated and pressed for 2 hours under a pressure of 3 MPa and a temperature of 220 °C. Thereby, a metal foil laminated board having copper foil on both surfaces of an insulating layer having a thickness of 150 μm which was obtained by curing the prepreg was obtained.

(3)多層印刷佈線板絕緣層用預浸體的製作 (3) Fabrication of prepreg for multilayer printed wiring board insulation layer

將上述製造例1所得之清漆含浸於玻璃織布(厚16μm，Unichika公司製E玻璃織布，E02Z，基重17.5g/m2)，於180℃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 份基準計為約78重量%的預浸體(厚40μm)。又，上述玻璃織布係體積密度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90N/25mm的玻璃纖維所構成者。 The varnish obtained in the above Production Example 1 was impregnated into a glass woven fabric (16 μm thick, E glass woven fabric manufactured by Unichika Co., Ltd., E02Z, basis weight: 17.5 g/m 2 ), and dried in a heating oven at 180 ° C for 2 hours to obtain a prepreg. The resin composition in the body was about 78% by weight of a prepreg (thickness: 40 μm) on a solid content basis. Further, the glass woven fabric had a bulk density of 1.09 g/cm 3 , a gas permeability of 41 cc/cm 2 /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 it is a plate shape, and a tensile strength of 90 N/25 mm when the fiber woven fabric is formed into a longitudinal direction. Constitute.

(4)印刷佈線板(內層電路基板)之製造 (4) Manufacturing of printed wiring board (inner circuit board)

由上述金屬箔積層板剝離載體箔，使用二氧化碳雷射(三菱電機公司製，ML605GTX3-5100U2)，依孔徑 1.4mm、光束徑約120μm、能量7~9mJ、射數6之條件，形成 100μm之貫通穿孔。接著，將該金屬箔積層板浸漬於70℃之膨潤液(ATOTECH JAPAN公司製，Swelling Dip Securiganth P)中5分鐘，再浸漬於80℃之過錳酸鉀水溶液(ATOTECH JAPAN公司製Concentrate Compact CP)中10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。 The carrier foil is peeled off from the above-mentioned metal foil laminated board, and a carbon dioxide laser (ML605GTX3-5100U2, manufactured by Mitsubishi Electric Corporation) is used. 1.4mm, beam diameter of about 120μm, energy of 7~9mJ, and number of shots 6 100 μm through perforation. Next, the metal foil laminate was immersed in a swelling solution (Swelling Dip Securiganth P, manufactured by ATOTECH JAPAN Co., Ltd.) at 70 ° C for 5 minutes, and then immersed in an aqueous solution of potassium permanganate at 80 ° C (Concentrate Compact CP manufactured by ATOTECH JAPAN Co., Ltd.). After 10 minutes, it was neutralized and roughened. Then, electroless plating (THUR-CUP PEA process manufactured by Uemura Industrial Co., Ltd.) was used to achieve conduction between the upper and lower copper foils.

接著，於該無電解鍍覆的表面上，將厚25μm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，對準描畫了最小線寬/線間為20/20μm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 電解鍍覆層作為給電層電極，依3A/dm2、25分鐘進行電鍍銅(奧野製藥公司製81-HL)。藉此，形成厚約20μm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蝕刻(荏原電產公司製SAC-702M與SAC-701R35之純水溶液)予以去除，形成L/S=20/20μm之圖案。 Next, on the surface of the electroless plating, a UV-sensitive dry film (SUNFORT UFG-255, manufactured by Asahi Kasei Corporation) having a thickness of 25 μm was bonded by a heating roll laminator. Next, the position of the glass mask (manufactured by Topic Co., Ltd.) in which the minimum line width/line is 20/20 μm was drawn. Subsequently, the glass mask was used, and exposure was performed by an exposure apparatus (Ono Tester EV-0800), and then developed in an aqueous solution of sodium carbonate to form a plating resist. Next, the electroless plating layer as an electrode to the dielectric layer, a copper plating (Okuno Pharmaceutical Co., Ltd. 81-HL) in accordance with 3A / dm 2, 25 minutes. Thereby, a copper wiring pattern having a thickness of about 20 μm was formed. Next, the above-mentioned plating mask was peeled off by a monoethanolamine solution (R-100, manufactured by Mitsubishi Gas Chemical Co., Ltd.) using a peeling machine. Then, the unnecessary copper foil and the electroless plating layer other than the pattern shape of the power supply layer are removed by rapid etching (a pure aqueous solution of SAC-702M and SAC-701R35 manufactured by Ebara Electric Co., Ltd.) to form L/S=. 20/20 μm pattern.

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℃、噴霧壓0.15MPa之條件進行噴霧器噴霧處理，對銅表面實施粗度3μm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℃、浸漬時間20秒之條件進行浸漬，對銅表面進行防銹處理。如此製作印刷佈線板(內層電路基板)。 Next, the conductor circuit was roughened (MECetchBOND CZ-8100, manufactured by Mec Corporation). This roughening treatment was carried out by spraying the sprayer under the conditions of a liquid temperature of 35 ° C and a spray pressure of 0.15 MPa, and roughening the surface of the copper to a thickness of about 3 μm. Next, the surface treatment of the conductor circuit (MECetchBOND CL-8300, manufactured by Mec Corporation) was performed. In the surface treatment, immersion was carried out under the conditions of a temperature of 25 ° C and an immersion time of 20 seconds, and the copper surface was subjected to rustproof treatment. A printed wiring board (inner circuit board) was produced in this manner.

(5)多層印刷佈線板之製造 (5) Manufacturing of multilayer printed wiring board

接著，以上述所得之印刷佈線板作為內層電路基板，於其兩面上重疊配置上述多層印刷佈線板絕緣層用預浸體與具有載體之2μm銅箔(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200℃、壓力3MPa、時間120分鐘進行加熱硬化，得到多層積層體。接著，與上述(4)印刷佈線板(內層電路基板)之製造方法同樣 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。 Then, the printed wiring board obtained above was used as an inner layer circuit board, and the prepreg for the multilayer printed wiring board insulating layer and the 2 μm copper foil having the carrier (Microsin MT18Ex-2, manufactured by Mitsui Mining Co., Ltd.) were placed on both surfaces of the printed circuit board. The laminate was laminated by a vacuum laminating apparatus, and heat-hardened by a temperature of 200 ° C, a pressure of 3 MPa, and a time of 120 minutes to obtain a multilayered laminate. Next, it is the same as the manufacturing method of the above (4) printed wiring board (inner layer circuit board). The outer layer circuit was formed, 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.

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[1]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。 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 treated 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)半導體裝置之製造 (6) Manufacturing of semiconductor devices

半導體裝置係在經ENEPIG處理之印刷佈線板上，藉由倒裝晶片接合器裝置，將具有焊錫凸塊之半導體元件(TEG晶片，尺寸10mm×10mm，厚0.1mm)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150℃、120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14mm×14mm之尺寸，得到半導體裝置。 The semiconductor device is mounted on a printed wiring board treated with an ENEPIG, and a semiconductor device having a solder bump (a TEG wafer, size: 10 mm × 10 mm, thickness: 0.1 mm) is mounted by heating and pressing by a flip chip bonder device. Next, the solder bumps were melt-bonded in an IR reflow furnace, and then filled with a liquid sealing resin (CRP-4152S, manufactured by Sumitomo Bakelite Co., Ltd.) to obtain a liquid sealing resin. Further, the liquid sealing resin was cured under the conditions of a temperature of 150 ° C for 120 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-cutting machine into a size of 14 mm × 14 mm.

<實施例2~3及比較例1~6> <Examples 2 to 3 and Comparative Examples 1 to 6>

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150μm之絕緣層之兩面具有銅箔的金屬箔積層板、印刷佈線板(內層電路基板)、多層印刷佈線板及半導體裝置。 Using the fiber woven fabric shown in Table 4 and the varnish obtained by the production example of the varnish, a prepreg, a metal foil laminated board having copper foil on both sides of an insulating layer having a thickness of 150 μm, and printing were obtained in the same manner as in Example 1. A wiring board (inner circuit board), a multilayer printed wiring board, and a semiconductor device.

<實施例4~6及比較例7> <Examples 4 to 6 and Comparative Example 7>

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100μm之絕緣層之兩面具有銅箔的金屬箔積層板、印刷佈線板(內層電路基板)、多層印刷佈線板及半導體裝置。 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 woven fabric shown in Table 5 and the varnish obtained by the production example of the varnish were used, and Examples In the same manner, a prepreg, a metal foil laminate having copper foil on both sides of an insulating layer having a thickness of 100 μm, a printed wiring board (inner circuit board), a multilayer printed wiring board, and a semiconductor device were obtained.

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 1.1mm、光束徑約110μm、能量7~9mJ、射數6之條件進行，形成直徑100μm之貫通穿孔。 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. A through-hole of 100 μm in diameter was formed under conditions of 1.1 mm, a beam diameter of about 110 μm, an energy of 7 to 9 mJ, and a number of shots of 6.

<實施例7、8及比較例8> <Examples 7, 8 and Comparative Example 8>

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60μm之絕緣層之兩面具有銅箔的金屬箔積層板、印刷佈線板(內層電路基板)、多層印刷佈線板及半導體裝置。 In the case of producing the 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 varnish were used. 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 60 μm, a printed wiring board (inner layer circuit board), and a multilayer printed wiring board. And a semiconductor device.

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1同樣地進行而得到預浸體(整體厚30μm)、積層2片該30μm之預浸體並硬化而成之厚60μm之絕緣層之兩面具有銅箔的金屬箔積層 板、內層電路基板、多層印刷佈線板及半導體裝置。 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 1 to obtain a prepreg (the overall thickness of 30 μm), two sheets of the 30 μm prepreg and two layers of the insulating layer having a thickness of 60 μm, and a metal foil layer having copper foil on both sides. A board, an inner layer circuit board, a multilayer printed wiring board, and a semiconductor device.

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 1.1mm、光束徑約110μm、能量6~8mJ、射數6之條件進行，形成直徑100μm之貫通穿孔。 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. A through-hole of 100 μm in diameter was formed under conditions of 1.1 mm, a beam diameter of about 110 μm, an energy of 6 to 8 mJ, and a number of shots of 6.

<實施例9及比較例9> <Example 9 and Comparative Example 9>

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40μm之絕緣層之兩面具有銅箔的金屬箔積層板、印刷佈線板(內層電路基板)、多層印刷佈線板及半導體裝置。 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 7, the fiber woven fabric shown in Table 7 and the varnish obtained by the production example of the varnish were used, and Examples In the same manner, 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), a multilayer printed wiring board, and a semiconductor device were obtained.

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 1.1mm、光束徑約110μm、能量6~8mJ、射數6之條件進行，形成直徑100μm之貫通穿孔。 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. A through-hole of 100 μm in diameter was formed under conditions of 1.1 mm, a beam diameter of about 110 μm, an energy of 6 to 8 mJ, and a number of shots of 6.

針對實施例及比較例所得的預浸體、金屬箔積層板、印刷佈線板(內層電路基板)及半導體裝置，進行以下評估。將評估項目與內容一起表示。並將所得之評估結果示於表4~7。 The following evaluations were performed on the prepreg, the metal foil laminate, the printed wiring board (inner layer circuit board), and the semiconductor device obtained in the examples and the comparative examples. The evaluation project is presented along with the content. The evaluation results obtained are shown in Tables 4-7.

尚且，由於後述之PKG曲翹之測定結果依存於金屬箔積層板之絕緣層厚度，故將金屬箔積層板之絕緣層之厚度為150μm的實施例及比較例的評估結果示於表4，將金屬箔積層板之絕緣層之厚度為100μm的實施例及比較例的評估結 果示於表5，將金屬箔積層板之絕緣層之厚度為60μm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40μm的實施例及比較例的評估結果示於表7。 Further, since the measurement result of the PKG curve described later depends on the thickness of the insulating layer of the metal foil laminate, the evaluation results of the examples and comparative examples in which the thickness of the insulating layer of the metal foil laminate is 150 μm are shown in Table 4. The thickness of the insulating layer of the metal foil laminate is 100 μm and the evaluation of the comparative example of the comparative example The results of the examples and comparative examples in which the thickness of the insulating layer of the metal foil laminate was 60 μm are shown in Table 6, and the thickness and thickness of the insulating layer of the metal foil laminate were 40 μm. The evaluation results are shown in Table 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100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100質量%時之各成分的比例。 In addition, in Tables 4-7, the amount (% by mass) of the filler in the resin composition is the amount of the filler when the entire resin composition is 100% by mass, and the composition (mass) % of the filler is The ratio of each component when the filler is 100% by mass in total.

<評估方法> <Evaluation method> (1)樹脂組成物之含浸性 (1) Impregnation of resin composition

將上述實施例及比較例所得之預浸體依170℃之溫度硬化1小時後，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，評估於纖維內部有無空隙。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。 After the prepreg obtained in the above examples and the comparative examples was cured at a temperature of 170 ° C for 1 hour, the cross section (the range of the cross-sectional portion in the width direction of 300 mm) was observed by SEM (scanning electron microscope) to evaluate whether or not the inside of the fiber was present. Void. The voids are attached to the image and are observed in the form of white granular spots of the fiber cross section.

各符號係如下述。 Each symbol is as follows.

○：樹脂組成物全部良好地含浸，於纖維內部無空隙 ○: The resin composition was all well impregnated, and there was no void inside the fiber.

×：於纖維內部有空隙 ×: there is a gap inside the fiber

(2)成形性 (2) Formability

對上述實施例及比較例所得之金屬箔積層板之銅箔進行整面蝕刻後，對500mm×500mm之範圍藉SEM(掃描型電子顯微鏡)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，以白色粒狀的 點之形式被觀察到。 The copper foil of the metal foil laminate obtained in the above examples and comparative examples was subjected to full-surface etching, and observed in the range of 500 mm × 500 mm by SEM (scanning electron microscope), and evaluated on the insulating layer (located in the fiber woven layer). The surface of the resin layer has a void on the surface. The gap is attached to the image and is white granular The form of the point was observed.

各符號係如下述。 Each symbol is as follows.

○：無空隙 ○: no gap

×：有空隙 ×: There is a gap

(3)吸濕焊錫耐熱性 (3) moisture absorption solder heat resistance

使用將上述實施例及比較例所得之金屬箔積層板切斷為50mm×50mm見方的樣本，根據JIS C-6481，將上述樣本之單面之一半以外的所有銅箔予以蝕刻去除，藉由壓力鍋試驗機(ESPEC公司製)依121℃、2氣壓處理2小時後，於260℃之焊錫槽中浸漬30秒，以目視觀察有無外觀變化的異常。 The metal foil laminated plate obtained in the above examples and comparative examples was cut into a sample of 50 mm × 50 mm square, and all copper foils other than one half of the one side of the sample were etched and removed by a pressure cooker according to JIS C-6481. The test machine (manufactured by ESPEC) was treated at 121 ° C for 2 hours, and then immersed in a solder bath at 260 ° C for 30 seconds to visually observe the presence or absence of abnormality in appearance.

各符號係如下述。 Each symbol is as follows.

○：無異常 ○: No abnormality

×：有膨脹、剝離 ×: There is expansion and peeling

(4)線熱膨脹係數(CTE)(ppm/K) (4) Linear thermal expansion coefficient (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4mm×20mm的試驗片，依溫度範圍30~300℃、10℃/分鐘、負重5g之條件測定第2循環之50~100℃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蝕刻去除者。 The linear thermal expansion coefficient (CTE) was prepared using a TMA (thermo-mechanical analysis) device (manufactured by TA Instrument Co., Ltd., Q400) to prepare a test piece of 4 mm × 20 mm, depending on the temperature range of 30 to 300 ° C, 10 ° C / min, and a load of 5 g. The CTE at 50 to 100 ° C of the second cycle was measured. Further, the sample was obtained by etching and removing the copper foil of the metal foil laminate obtained in each of the examples and the comparative examples.

(5)雷射加工性 (5) Laser processing

使用上述實施例及比較例所得之印刷佈線板(內層電路基板)，測定碳酸雷射加工後之貫通穿孔的布料突出量、孔徑 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側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(內層電路基板)，依下述表2所示之二氧化碳雷射條件，對直徑100μm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。 Using the printed wiring board (inner layer circuit board) obtained in the above-described examples and comparative examples, the amount of cloth protrusion and the aperture of the through-perforation after the carbon nanotube laser processing were measured. The true roundness. The measurement of the amount of protrusion of the cloth and the roundness of the cloth were measured by a color 3D laser microscope (manufactured by Keyence Corporation, device name VK-9710), and the measurement of the amount of protrusion of the cloth was observed by directly above the hole on the side of the laser incident side. The length of the hole wall surface is measured. The measurement of the roundness is performed by directly above the hole on the laser incident side, and the long diameter and the short diameter of the hole top diameter are measured, and the long diameter ÷ short diameter is calculated. Further, in the sample, the printed wiring board (inner layer circuit board) obtained in the above-described examples and comparative examples was used, and the substrate after the processing of the hole having a diameter of 100 μm was immediately above the carbon dioxide laser condition shown in Table 2 below. Observation was performed as an average value of 10 through holes.

各符號係如下述。 Each symbol is as follows.

○：布料突出量為10μm以內，真圓度為0.85以上 ○: The cloth protrusion amount is within 10 μm, and the roundness is 0.85 or more.

△：布料突出量為10μm以上、或真圓度為未滿0.85 △: The protruding amount of the cloth is 10 μm or more, or the roundness is less than 0.85.

×：布料突出量為10μm以上，且真圓度為未滿0.85 ×: The protruding amount of the cloth is 10 μm or more, and the roundness is less than 0.85.

(6)貫通穿孔之絕緣可靠性 (6) Insulation reliability of through-hole

使用上述實施例及比較例所得之印刷佈線板(內層電路基板)，評估貫通穿孔間之絕緣可靠性。 Using the printed wiring board (inner layer circuit board) obtained in the above examples and comparative examples, the insulation reliability between the through holes was evaluated.

使用印刷佈線板之穿孔壁間0.1mm部分，依施加電壓 10V、溫度130℃、濕度85%的條件，以連續測定進行評估。又，測定係使用高度加速壽命試驗裝置(ESPEC公司製EHS-211(M)，AMI離子遷移系統)進行，在絕緣電阻值成為未滿108Ω的時點設為結束。 The 0.1 mm portion between the perforated walls of the printed wiring board was evaluated by continuous measurement under the conditions of a voltage of 10 V, a temperature of 130 ° C, and a humidity of 85%. In addition, the measurement was performed using a highly accelerated life tester (EHS-211 (M) manufactured by ESPEC Co., Ltd., AMI ion transport system), and the end of the measurement was made when the insulation resistance value was less than 10 8 Ω.

各符號係如下述。 Each symbol is as follows.

◎：超過200小時 ◎: More than 200 hours

○：100小時以上且200小時以下 ○: 100 hours or more and 200 hours or less

△：50小時以上且未滿100小時 △: 50 hours or more and less than 100 hours

×：未滿50小時 ×: less than 50 hours

(7)PGK曲翹 (7) PGK curved

將實施例及比較例所得之半導體裝置(14mm×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)之樣本室內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℃)及260℃下的曲翹。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13mm×13mm尺寸。 The semiconductor device (14 mm × 14 mm) obtained in the examples and the comparative examples was placed with the semiconductor element facing downward in a sample chamber of a humidity variable laser three-dimensional measuring machine (form LS220-MT100MT50, manufactured by Hitachi, Technology and Service Co., Ltd.). The above measuring machine measures the room temperature (25 ° C) of the semiconductor device and the warp 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 × 13 mm in size.

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。 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.

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所得之預浸體之剖面圖的照片示於圖3，將比較例4所得之預浸體之剖面圖的照片示於圖4。 As a representative example of the observation result of the impregnation property of the above (1) resin composition, the photograph of the cross-sectional view of the prepreg obtained in Example 1 is shown in FIG. 3, and the cross-sectional view of the prepreg obtained in Comparative Example 4 is shown. The photo is shown in Figure 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。 As is clear from Fig. 4, in Comparative Example 4, since the impregnation property of the resin composition was deteriorated, voids were observed in the fiber woven fabric. On the other hand, as is clear from Fig. 3, in Example 1, since the impregnation property of the resin composition was good, there was no void in the fiber woven fabric.

實施例1中，認為係因奈米尺寸之二氧化矽粒子進入至線股中，故提升樹脂組成物的含浸性。相對於此，比較例4 中，可知由於不含有奈米尺寸之二氧化矽粒子，故無法達到樹脂組成物之含浸性提升。 In Example 1, it is considered that the indium-sized cerium oxide particles enter the strands, so that the impregnation property of the resin composition is improved. In contrast, Comparative Example 4 In the meantime, it is understood that since the cerium oxide particles having a nanometer size are not contained, the impregnation property of the resin composition cannot be improved.

作為上述(2)金屬箔積層板之成形性觀察結果的代表例，將對實施例1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示於圖5，將對比較例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SEM照片示於圖7，將圖7所觀察之空隙之剖面的放大圖的SEM照片示於圖8。如圖6、7、8所示般，比較例6中在對金屬箔積層板進行了整面蝕刻的表面上觀察到空隙。另一方面，如圖5所示般，在實施例1中，經整面蝕刻之表面上未有空隙。 As a representative example of the result of the moldability observation of the above-mentioned (2) metal foil laminated board, the surface of the surface of the copper foil of the metal foil laminated board obtained in Example 1 was fully etched, and it is shown in FIG. 6 is a photograph showing the surface of the copper foil of the obtained metal foil laminated board which was etched on the whole surface, and is shown in FIG. 6, and the SEM photograph of the enlarged view of the void (the point which is white granular in the image) which was observed in FIG. Fig. 7 is a SEM photograph showing an enlarged view of a cross section of the void observed in Fig. 7 in Fig. 8. As shown in Figs. 6, 7, and 8, in Comparative Example 6, a void was observed on the surface on which the metal foil laminate was subjected to the entire surface etching. On the other hand, as shown in Fig. 5, in the first embodiment, there was no void on the surface which was etched over the entire surface.

圖9~12係表示實施例1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10~12表示與線股之延伸方向呈垂直的剖面。 9 to 12 are SEM photographs showing a cross-sectional view of a part of the strands of the constituting fiber woven fabric of the prepreg obtained in Example 1. Figure 9 shows a section parallel to the direction in which the strands extend. 10 to 12 show a cross section perpendicular to the direction in which the strands extend.

如圖9~12所示般，可知於實施例1所得之預浸體中，在線股中存在二氧化矽粒子。 As shown in FIGS. 9 to 12, it is understood that in the prepreg obtained in Example 1, cerium oxide particles are present in the strands.

於表4~7所示之實施例1~9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。 In Examples 1 to 9 shown in Tables 4 to 7, good impregnation properties of the prepreg were obtained. In addition, regarding various other characteristics, it was found that all of them obtained good results. The reason for this is considered to be that the prepreg is formed under the condition that the cerium oxide particles enter the strands constituting the fiber woven fabric.

尚且，作為控制二氧化矽粒子進入線股中的因子，可舉例如二氧化矽粒子之平均粒徑、填充材中之二氧化矽粒子含量、樹脂組成物中之填充材含量、纖維織布之體積密度等各種者。 Further, as a factor for controlling the entry of the cerium oxide particles into the strands, for example, the average particle diameter of the cerium oxide particles, the content of the cerium oxide particles in the filler, the content of the filler in the resin composition, and the fiber woven fabric are mentioned. Various types such as bulk density.

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50~85質量%的填充材，該填充材中，含有1~20質量%之平均粒徑5~100nm之二氧化矽粒子，且纖維織布之體積密度為1.05~1.30g/cm3。此時，於上述所有評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、低熱膨脹性，在使用作為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的精度佳，且可形成抑制了纖維突出的孔。再者，本實施例之預浸體由於吸濕焊錫耐熱性優越，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曲翹較小，故本發明之預浸體為低熱膨脹性且高剛性。 In the examples 1 to 9, the resin composition contained in the varnish contains a filler of 50 to 85% by mass of the entire resin composition, and the filler contains 1 to 20% by mass. The cerium oxide particles having an average particle diameter of 5 to 100 nm and the fiber woven fabric have a bulk density of 1.05 to 1.30 g/cm 3 . At this time, it is a superior evaluation result among all the above 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 thermal expansion property, and is excellent in laser processability when using an insulating layer as a printed wiring board, and a hole system formed by laser irradiation. The accuracy of the aperture and shape is good, and a hole that suppresses the protrusion of the fiber can be formed. Further, since the prepreg of the present embodiment is excellent in heat resistance of the moisture-absorbing solder, 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 of the present invention has a small warpage, and therefore the prepreg of the present invention has low thermal expansion property and high rigidity.

比較例1及6中，亦得到良好之預浸體含浸性。 In Comparative Examples 1 and 6, good impregnation impregnation properties were also obtained.

然而，比較例1中，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，故僅有樹脂組成物之樹脂成分進入線股內，而抑制二氧化矽粒子進入線股中所致。藉此，無法使填充材高填充化，預浸體之CTE變高， 發生封裝曲翹。 However, in Comparative Example 1, good results were not obtained in terms of CTE and package warpage. It can be considered that since the content of the filler is low, only the resin component of the resin composition enters the strands, and the cerium oxide particles are inhibited from entering the strands. Therefore, the filler cannot be highly filled, and the CTE of the prepreg becomes high. The package bends.

另外，比較例6中，未得到良好結果。此可認為由於體積密度較低而可使充分量的樹脂組成物含浸，故亦抑制了樹脂組成物中所含之二氧化矽粒子進入線股中所致。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變薄。因此，成形性、吸濕焊錫耐熱性差，CTE雖然良好但發生PKG曲翹。 Further, in Comparative Example 6, good results were not obtained. This is considered to be because the bulk density is low and a sufficient amount of the resin composition can be impregnated, so that the cerium oxide particles contained in the resin composition are also prevented from entering the strands. Further, 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 reduced. Therefore, the moldability and the moisture absorption solder are inferior in heat resistance, and the CTE is good, but the PKG is warped.

比較例4及7~9中，關於預浸體之含浸性，未得到良好結果。比較例4及7~9中，在構成預浸體之樹脂組成物中並不含有奈米尺寸的二氧化矽粒子。因此可認為二氧化矽粒子未進入線股中，未達到樹脂組成物之含浸性提升。又，因此，於CTE及封裝曲翹等其他各種特性方面亦未得到良好結果。 In Comparative Examples 4 and 7 to 9, no good results were obtained regarding the impregnation property of the prepreg. In Comparative Examples 4 and 7 to 9, the nano-sized cerium oxide particles were not contained in the resin composition constituting the prepreg. Therefore, it is considered that the cerium oxide particles do not enter the strands, and the impregnation property of the resin composition is not improved. Moreover, good results have not been obtained in terms of various other characteristics such as CTE and package warp.

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、吸濕焊錫耐熱性差，而發生PKG曲翹。 In Comparative Example 7, since the bulk density of the fiber woven fabric was small, the laser workability was poor, the impregnation property was poor, and the insulation reliability of the through-hole was deteriorated. Further, since a thick fiber woven fabric is used, the thickness of the resin layer of the prepreg is reduced, and the moldability and the moisture resistance of the moisture absorbing solder are inferior, and PKG warpage occurs.

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。 In Comparative Examples 8 and 9, since the thickness of the insulating layer of the metal foil laminated board was thin, the insulating property of the moldability, the moisture absorption solder heat resistance, and the through-hole was excellent. However, since the fiber woven fabric has a small bulk density, good results have not been obtained in terms of laser processability.

比較例2、3及5中，關於預浸體之含浸性未得到良好結 果。又，關於其他各種特性亦未得到良好結果。比較例2中，可認為由於填充材之含量過高，故未得到樹脂組成物中之二氧化矽粒子的流動性，結果抑制二氧化矽粒子朝線股中的進入。比較例3中，可認為由於奈米尺寸之二氧化矽粒子之含量高，故奈米尺寸之二氧化矽粒子凝集，結果抑制二氧化矽粒子朝線股中的進入。比較例5中，可認為由於纖維織布之體積密度較大，故抑制了二氧化矽粒子朝線股中的進入。 In Comparative Examples 2, 3 and 5, the impregnation properties of the prepreg were not well concluded. fruit. Also, good results have not been obtained with respect to various other characteristics. In Comparative Example 2, it was considered that the content of the filler was too high, so that the fluidity of the cerium oxide particles in the resin composition was not obtained, and as a result, the entry of the cerium oxide particles into the strands was suppressed. In Comparative Example 3, it is considered that since the content of the cerium oxide particles having a nanometer size is high, the cerium oxide particles having a nanometer size are aggregated, and as a result, the entry of the cerium oxide particles into the strands is suppressed. In Comparative Example 5, it is considered that since the bulk density of the fiber woven fabric is large, entry of the cerium oxide particles into the strands is suppressed.

比較例5中，認為纖維織布之體積密度過大，故樹脂組成物之含浸性差、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。 In Comparative Example 5, it is considered that the bulk density of the fiber woven fabric is too large, so that the impregnation property of the resin composition is poor, the heat resistance of the moisture absorbing solder is poor, and the laser processing property and the insulation reliability of the through-hole are also inferior.

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曲翹。 In Comparative Example 6, since the bulk density of the fiber woven fabric was small, the laser processability and the through-hole perforation were inferior in insulation reliability. Further, since the fiber woven fabric has a small bulk density and becomes a thick fibrous base material, the thickness of the resin layer on the surface layer of the prepreg is reduced. Therefore, the moldability and the moisture absorption solder are inferior in heat resistance, and PKG warpage occurs.

本申請案係主張以2011年1月24日申請之日本申請案特願2011-012166號為基礎的優先權，將其所有揭示內容引用於此。 The priority of this application is based on Japanese Patent Application No. 2011-012166, filed on Jan.

10‧‧‧金屬箔 10‧‧‧metal foil

11‧‧‧金屬箔 11‧‧‧metal foil

12‧‧‧樹脂層 12‧‧‧ resin layer

20‧‧‧纖維織布 20‧‧‧Fiber weaving

30‧‧‧具有樹脂層之高分子薄膜片 30‧‧‧Polymer film sheet with resin layer

31‧‧‧高分子薄膜片 31‧‧‧ polymer film

32‧‧‧樹脂層 32‧‧‧ resin layer

40‧‧‧預浸體 40‧‧‧Prepreg

41‧‧‧預浸體 41‧‧‧Prepreg

42‧‧‧預浸體 42‧‧‧Prepreg

51‧‧‧金屬箔積層板 51‧‧‧metal foil laminate

52‧‧‧金屬箔積層板 52‧‧‧metal foil laminate

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。 Fig. 1 is a schematic view showing an example of a method for producing a metal foil laminated board of the present invention.

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。 Fig. 2 is a schematic view showing another example of the method for producing a metal foil laminated board of the present invention.

圖3為實施例1所得之預浸體之剖面圖的照片。 Fig. 3 is a photograph showing a cross-sectional view of the prepreg obtained in Example 1.

圖4為比較例4所得之預浸體之剖面圖的照片。 4 is a photograph of a cross-sectional view of a prepreg obtained in Comparative Example 4.

圖5為對實施例1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。 Fig. 5 is a photograph showing the surface of the copper foil of the metal foil laminate obtained in Example 1 which was completely etched.

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。 Fig. 6 is a photograph showing the surface of the copper foil of the metal foil laminate obtained in Comparative Example 6 which was completely etched.

圖7為圖6所觀察點之放大圖的SEM照片。 Figure 7 is a SEM photograph of an enlarged view of the point observed in Figure 6.

圖8為圖7所觀察點之剖面之放大圖的SEM照片。 Figure 8 is a SEM photograph of an enlarged view of a section of the point observed in Figure 7.

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。 Fig. 9 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.

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。 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.

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。 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.

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。 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.

10‧‧‧金屬箔 10‧‧‧metal foil

11‧‧‧金屬箔 11‧‧‧metal foil

12‧‧‧樹脂層 12‧‧‧ resin layer

20‧‧‧纖維織布 20‧‧‧Fiber weaving

40‧‧‧預浸體 40‧‧‧Prepreg

41‧‧‧預浸體 41‧‧‧Prepreg

51‧‧‧金屬箔積層板 51‧‧‧metal foil laminate

Claims (14)

一種預浸體，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；上述纖維織布之體積密度為1.05~1.30g/cm3；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，且依相對於上述填充材為1~20質量%的比例含有平均粒徑5~100nm之二氧化矽粒子；於上述線股中存在上述二氧化矽粒子。 A prepreg obtained by impregnating a resin composition with a fiber woven fabric composed of strands; the fiber woven fabric has a bulk density of 1.05 to 1.30 g/cm 3 ; and the resin composition contains at least heat The curable resin and the filler are contained in a ratio of 50 to 85% by mass based on the solid content of the resin composition, and the average particle diameter is 1 to 20% by mass based on the filler. 5 to 100 nm of cerium oxide particles; the above-mentioned cerium oxide particles are present in the above strands. 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50μm以上長度的空隙。 The prepreg according to claim 1, wherein in the strand, the void having a length of 50 μm or more does not exist in a direction in which the fibers constituting the strand are extended. 如申請專利範圍第1項之預浸體，其中，上述線股中之直徑50μm以上之空隙的數密度為50cm-3以下。 The prepreg according to the first aspect of the invention, wherein the number of the voids having a diameter of 50 μm or more in the strands is 50 cm -3 or less. 如申請專利範圍第1項之預浸體，其中，整體厚度為30~220μm。 For example, the prepreg according to item 1 of the patent application, wherein the overall thickness is 30 to 220 μm. 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SiO2為50~100質量%、Al2O3為0~30質量%、CaO為0~30質量%的比例含有上述各者之玻璃纖維所構成。 The prepreg according to claim 1, wherein the wire strands are at least 50 to 100% by mass of SiO 2 , 0 to 30% by mass of Al 2 O 3 , and 0 to 30% by mass of CaO. It consists of glass fiber containing each of the above. 如申請專利範圍第5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。 For example, the prepreg of claim 5, 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. 如申請專利範圍第5項之預浸體，其中，上述玻璃纖維係作成板狀時之楊氏率為50~100GPa、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。 The prepreg according to the fifth aspect of the invention, wherein the glass fiber has a Young's ratio of 50 to 100 GPa when formed into a plate shape, a tensile strength of 25 GPa or more when the sheet is formed into a plate shape, and a length of the fiber woven fabric. The tensile strength of the direction is 30N/25mm or more. 如申請專利範圍第5項之預浸體，其中，上述纖維織布之通氣度為1~80cc/cm2/sec。 The prepreg according to claim 5, wherein the fiber woven fabric has a gas permeability of 1 to 80 cc/cm 2 /sec. 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烷類施行了表面處理。 The prepreg according to claim 1, wherein the cerium oxide particles are surface-treated by a functional group-containing decane or alkyl decane. 一種積層板，係將申請專利範圍第1至9項中任一項之預浸體進行硬化而獲得。 A laminated board obtained by hardening a prepreg according to any one of claims 1 to 9. 如申請專利範圍第10項之積層板，其中，於上述預浸體之至少一外側面上設置導體層。 The laminate of claim 10, wherein the conductor layer is provided on at least one outer side surface of the prepreg. 一種印刷佈線板，係將申請專利範圍第1至9項中任一項之預浸體、或申請專利範圍第10或11項之積層板用於內層電路基板而成者。 A printed wiring board obtained by using the prepreg according to any one of claims 1 to 9 or the laminated board of claim 10 or 11 for an inner layer circuit substrate. 如申請專利範圍第12項之印刷佈線板，其中，將申請專利範圍第1至9項中任一項之預浸體設於上述內層電路基板上作為絕緣層。 The printed wiring board according to claim 12, wherein the prepreg according to any one of claims 1 to 9 is provided on the inner layer circuit substrate as an insulating layer. 一種半導體裝置，係於申請專利範圍第12或13項之 印刷佈線板上搭載半導體元件而成者。 A semiconductor device is claimed in claim 12 or 13 A semiconductor component is mounted on a printed wiring board.
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