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TW201739820A - Resin composition, prepreg, metal foil-clad laminate, resin sheet, printed wiring board, and semiconductor device - Google Patents

Resin composition, prepreg, metal foil-clad laminate, resin sheet, printed wiring board, and semiconductor device Download PDF

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TW201739820A
TW201739820A TW106103181A TW106103181A TW201739820A TW 201739820 A TW201739820 A TW 201739820A TW 106103181 A TW106103181 A TW 106103181A TW 106103181 A TW106103181 A TW 106103181A TW 201739820 A TW201739820 A TW 201739820A
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resin composition
resin
group
mass
compound
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TW106103181A
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Chinese (zh)
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TWI781918B (en
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鈴木卓也
浦濱成弘
若林潤
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三菱瓦斯化學股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/12Powdering or granulating
    • C08J3/128Polymer particles coated by inorganic and non-macromolecular organic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/0353Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a resin composition having excellent permittivity, dielectric loss tangent, fine wiring embeddability, heat resistance and developability, and also having physical properties suitable for use as a protective film or interlayer insulating layer in a printed wiring board. The present invention also provides a prepreg, metal foil-clad laminate, resin sheet, printed wiring board and semiconductor device that use this resin composition. The resin composition of the present invention contains fluororesin particles (A) with silica particles adhered to the particle surfaces, and a resin component (B).

Description

樹脂組成物、預浸體、覆金屬箔疊層板、樹脂片、印刷電路板及半導體裝置Resin composition, prepreg, metal foil-clad laminate, resin sheet, printed circuit board, and semiconductor device

本發明係關於樹脂組成物、使用此組成物之預浸體、覆金屬箔疊層板、樹脂片、印刷電路板及半導體裝置。The present invention relates to a resin composition, a prepreg using the composition, a metal foil-clad laminate, a resin sheet, a printed circuit board, and a semiconductor device.

近年來在電子設備、通訊器材、個人電腦等廣泛使用之半導體之高整合化・微細化愈益加速,情報通信使用之數據通信之高速化及大容量化也進展。對於印刷電路板,為了達成信號輸送延遲的縮短、傳送損失的減少,要求低介電常數(低Dk)、及低介電正切(低Df)。為了要達成該等要求,已在探討使用有優良的電特性(低介電常數・低介電正切)的樹脂組成物。In recent years, the integration and miniaturization of semiconductors, which are widely used in electronic equipment, communication equipment, and personal computers, have been accelerating, and the speed and capacity of data communication used for information communication have also progressed. For printed circuit boards, in order to achieve a reduction in signal transmission delay and a reduction in transmission loss, a low dielectric constant (low Dk) and a low dielectric tangent (low Df) are required. In order to achieve such requirements, a resin composition having excellent electrical characteristics (low dielectric constant, low dielectric tangent) has been examined.

又,由於印刷電路板之小型化、高密度化,多層印刷電路板中使用的增建層(build up layer)多層化,要求配線之微細化及高密度化。所以,對於此增建層中使用的樹脂組成物,為了要填埋微細配線要求成形時有高流動性,及要求填埋了微細配線後有高耐熱性。如此的樹脂組成物中,為了使電特性良好,研究採用氟樹脂填料。例如:專利文獻1揭示藉由同時使用氟樹脂填料和聚伸苯醚樹脂,達成電特性優異之樹脂組成物。又,專利文獻2揭示藉由同時使用氟樹脂填料與降莰烯系樹脂,獲得硬化物之電特性及密合性優異、配線填埋性良好的樹脂組成物。In addition, the size of the printed circuit board is reduced and the density is increased. The build-up layer used in the multilayer printed circuit board is multi-layered, and the wiring is required to be finer and higher in density. Therefore, in order to fill the fine wiring, the resin composition used in the build-up layer is required to have high fluidity during molding, and it is required to have high heat resistance after filling the fine wiring. In such a resin composition, in order to improve electrical characteristics, a fluororesin filler was used. For example, Patent Document 1 discloses that a resin composition excellent in electrical characteristics is obtained by using a fluororesin filler and a polyphenylene ether resin at the same time. Further, Patent Document 2 discloses that a resin composition having excellent electrical properties and adhesion of a cured product and excellent wiring filling property is obtained by using a fluororesin filler and a norbornene-based resin at the same time.

[先前技術文獻] [專利文獻] [專利文獻1]日本特表2006-516297號公報 [專利文獻2]日本特開2007-177073號公報[PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Publication No. 2006-516297 (Patent Document 2) JP-A-2007-177073

[發明欲解決之課題] 但是本案發明人了解到使用了習知的氟樹脂填料的硬化物有各式各樣的問題。 例如:專利文獻1中獲得之硬化物的耐熱性不足。 又,專利文獻2中,配線填埋後之吸濕耐熱性不足。[Problem to be Solved by the Invention] However, the inventors of the present invention have learned that there are various problems in using a cured product of a conventional fluororesin filler. For example, the cured product obtained in Patent Document 1 has insufficient heat resistance. Further, in Patent Document 2, the moisture absorption and heat resistance after the wiring is buried is insufficient.

本發明係有鑑於上述問題而生,提供使用在多層印刷電路板時,介電常數、介電正切、微細配線填埋性、耐熱性、顯影性優良的樹脂組成物、使用此組成物之預浸體、覆金屬箔疊層板、樹脂片、印刷電路板及半導體裝置。 [解決問題之方式]The present invention has been made in view of the above problems, and provides a resin composition excellent in dielectric constant, dielectric tangent, fine wiring landfill, heat resistance, and developability when used in a multilayer printed wiring board, and a pretreatment using the composition. Dip, metal foil laminate, resin sheet, printed circuit board and semiconductor device. [The way to solve the problem]

本案發明人等發現藉由使用含有被覆有二氧化矽之氟樹脂粒子(A)及樹脂成分(B)之樹脂組成物,能夠解決上述課題,乃完成本發明。The inventors of the present invention have found that the above problems can be solved by using a resin composition containing fluororesin particles (A) and resin component (B) coated with cerium oxide, and the present invention has been completed.

亦即,本發明包括以下之內容。 [1] 一種樹脂組成物,含有被覆有二氧化矽之氟樹脂粒子(A)及樹脂成分(B)。 [2] 如[1]之樹脂組成物,其中,該被覆有二氧化矽之氟樹脂粒子(A)之一次粒子之體積平均粒徑為5μm以下。 [3] 如[1]或[2]之樹脂組成物,其中,該被覆有二氧化矽之氟樹脂粒子(A)在樹脂組成物中之含量,係相對於樹脂組成物中之樹脂固體成分100質量份為3~ 400質量份。 [4] 如[1]~[3]中任一項之樹脂組成物,其中,該樹脂成分(B)含有選自於由馬來醯亞胺化合物、氰酸酯化合物、環氧樹脂、苯酚樹脂、氧雜環丁烷樹脂、苯并㗁??化合物及具乙烯性不飽和基之化合物構成之群組中之任一種以上。That is, the present invention includes the following contents. [1] A resin composition comprising fluororesin particles (A) coated with cerium oxide and a resin component (B). [2] The resin composition of [1], wherein the primary particles of the fluororesin particles (A) coated with cerium oxide have a volume average particle diameter of 5 μm or less. [3] The resin composition of [1] or [2], wherein the content of the cerium oxide-coated fluororesin particles (A) in the resin composition is relative to the resin solid content in the resin composition 100 parts by mass is 3 to 400 parts by mass. [4] The resin composition according to any one of [1] to [3] wherein the resin component (B) is selected from the group consisting of a maleimide compound, a cyanate compound, an epoxy resin, and a phenol. Any one or more of the group consisting of a resin, an oxetane resin, a benzofluorene compound, and a compound having an ethylenically unsaturated group.

[5] 如[1]~[4]中任一項之樹脂組成物,更含有該被覆有二氧化矽之氟樹脂粒子(A)以外之填充材(C)。 [6] 如[1]~[5]中任一項之樹脂組成物,更含有阻燃劑(D)。 [7] 如[1]~[6]中任一項之樹脂組成物,更含有光硬化起始劑(E)。 [8] 如[4]之樹脂組成物,其中,該具有乙烯性不飽和基之化合物包括選自於由具乙烯基之2官能性伸苯醚寡聚物及α-甲基苯乙烯之寡聚物構成之群組中之至少一種以上。 [9] 如[4]之樹脂組成物,其中,該具有乙烯性不飽和基之化合物包括選自於由酸改性雙酚F型環氧(甲基)丙烯酸酯、下列通式(1)表示之化合物及二新戊四醇六(甲基)丙烯酸酯構成之群組中之至少一種以上;[5] The resin composition according to any one of [1] to [4], further comprising a filler (C) other than the fluororesin particles (A) coated with cerium oxide. [6] The resin composition according to any one of [1] to [5], further comprising a flame retardant (D). [7] The resin composition according to any one of [1] to [6], further comprising a photohardening initiator (E). [8] The resin composition according to [4], wherein the compound having an ethylenically unsaturated group is selected from the group consisting of a bifunctional phenylene ether oligomer having a vinyl group and an α-methyl styrene At least one or more of the group consisting of the polymers. [9] The resin composition according to [4], wherein the compound having an ethylenically unsaturated group is selected from the group consisting of an acid modified bisphenol F type epoxy (meth) acrylate, the following general formula (1) At least one or more of the group consisting of the compound and dipentaerythritol hexa(meth) acrylate;

【化1】 【化1】

式(1)中,多數個R1 各自獨立地表示氫原子或甲基,且多數個R2 各自獨立地表示氫原子或甲基,多數個R3 各自獨立地表示下式(2)表示之取代基、下式(3)表示之取代基或羥基;In the formula (1), a plurality of R 1 each independently represent a hydrogen atom or a methyl group, and a plurality of R 2 each independently represent a hydrogen atom or a methyl group, and a plurality of R 3 each independently represent a formula (2). a substituent, a substituent represented by the following formula (3) or a hydroxyl group;

【化2】 [Chemical 2]

【化3】 [化3]

式(3)中,R4 表示氫原子或甲基。In the formula (3), R 4 represents a hydrogen atom or a methyl group.

[10] 如[9]之樹脂組成物,其中,該具有乙烯性不飽和基之化合物至少包括該通式(1)表示之化合物。 [11] 一種預浸體,具有:基材,及含浸或塗佈於該基材之如[1]~[10]中任一項之樹脂組成物。 [12] 一種覆金屬箔疊層板,具有:至少1片以上之疊層在一起之如[11]之預浸體,及配置在該預浸體之單面或兩面之金屬箔。[10] The resin composition according to [9], wherein the compound having an ethylenically unsaturated group includes at least the compound represented by the formula (1). [11] A prepreg comprising: a substrate, and a resin composition according to any one of [1] to [10] which is impregnated or coated on the substrate. [12] A metal foil-clad laminate comprising: at least one or more prepregs as laminated [11], and a metal foil disposed on one or both sides of the prepreg.

[13] 一種樹脂片,具有:支持體,及配置在該支持體之表面之如[1]~[10]中任一項之樹脂組成物。 [14] 一種印刷電路板,具有如[1]~[10]中任一項之樹脂組成物。 [15] 一種半導體裝置,具有如[1]~[10]中任一項之樹脂組成物。 [發明之效果][13] A resin sheet comprising: a support; and a resin composition according to any one of [1] to [10] disposed on a surface of the support. [14] A printed circuit board having the resin composition according to any one of [1] to [10]. [15] A semiconductor device comprising the resin composition according to any one of [1] to [10]. [Effects of the Invention]

依照本發明,可提供介電常數、介電正切、微細配線填埋性、耐熱性、顯影性優異,具有適合印刷電路板之保護膜、及層間絕緣層之物性之樹脂組成物、使用此組成物之預浸體、覆金屬箔疊層板、樹脂片、印刷電路板及半導體裝置。According to the present invention, it is possible to provide a resin composition which is excellent in dielectric constant, dielectric tangent, fine wiring filling property, heat resistance, and developability, and has a physical property suitable for a protective film of a printed circuit board and an interlayer insulating layer, and uses the composition. Prepreg, metal foil laminate, resin sheet, printed circuit board and semiconductor device.

以下針對本實施方式(以下稱為「本實施形態」)詳細説明。以下之本實施形態係用以說明本發明之例示,並非本發明限於以下之內容之意。本發明可以在其要旨之範圍內適當變形而實施。Hereinafter, the present embodiment (hereinafter referred to as "this embodiment") will be described in detail. The following examples are intended to illustrate the invention and are not intended to limit the invention. The present invention can be carried out with appropriate modifications within the scope of the gist of the invention.

又,本說明書中,「(甲基)丙烯醯基」係指「丙烯醯基」及和其對應之「甲基丙烯醯基」兩者,「(甲基)丙烯酸酯」係指「丙烯酸酯」及和其對應之「甲基丙烯酸酯」兩者,「(甲基)丙烯酸」係指「丙烯酸」及和其對應之「甲基丙烯酸」兩者。又,本實施形態中,「樹脂固體成分」或「樹脂組成物中之樹脂固體成分」,若無特別指明,則係指樹脂組成物中之溶劑及填充材以外的成分,「樹脂固體成分100質量份」係指樹脂組成物中之溶劑及填充材以外的成分之合計為100質量份。In the present specification, "(meth)acryloyl group" means both "acryloyl fluorenyl" and its corresponding "methacryl fluorenyl group", and "(meth) acrylate" means "acrylate" And "methacrylic acid" which corresponds to it, "(meth)acrylic" means both "acrylic acid" and the corresponding "methacrylic acid". In the present embodiment, the "resin solid content" or the "resin solid content in the resin composition" means a component other than the solvent and the filler in the resin composition, unless otherwise specified, "resin solid content 100" The "parts by mass" means that the total amount of the components other than the solvent and the filler in the resin composition is 100 parts by mass.

本實施形態之樹脂組成物之特徵為含有被覆有二氧化矽之氟樹脂粒子(A)及樹脂成分(B)。以下針對各成分説明。The resin composition of the present embodiment is characterized by containing fluororesin particles (A) and resin component (B) coated with cerium oxide. The following describes each component.

<被覆有二氧化矽之氟樹脂粒子(A)> 本實施形態使用之被覆有二氧化矽之氟樹脂粒子(A),係於表面附著了二氧化矽之氟樹脂粒子,具有氟樹脂粒子及附著於此氟樹脂表面之二氧化矽粒子。使二氧化矽粒子附著在氟樹脂粒子之表面之方法不特別限定,可藉由單純混合、 或混合後施以振動以實施。對於氟樹脂粒子表面附著二氧化矽粒子可於乾燥狀態進行。氟樹脂粒子與二氧化矽粒子之混合比例無特殊限定。據認為:即使是少許量,只要二氧化矽粒子存在氟樹脂粒子之表面,即能展現利用二氧化矽粒子所獲致之流動特性增進效果,能夠使本實施形態之樹脂組成物之配線填埋性及配線填埋後之吸濕耐熱性為良好。<Fluororesin particles (A) coated with cerium oxide> The fluororesin particles (A) coated with cerium oxide used in the present embodiment are fluororesin particles having cerium oxide adhered to the surface thereof, and have fluororesin particles and The cerium oxide particles attached to the surface of the fluororesin. The method of attaching the cerium oxide particles to the surface of the fluororesin particles is not particularly limited, and it can be carried out by simply mixing or mixing and applying vibration. The adhesion of the cerium oxide particles to the surface of the fluororesin particles can be carried out in a dry state. The mixing ratio of the fluororesin particles to the cerium oxide particles is not particularly limited. It is considered that even if the amount of the cerium oxide particles is on the surface of the fluororesin particles, the effect of improving the flow characteristics by the cerium oxide particles can be exhibited, and the wiring of the resin composition of the present embodiment can be buried. And the moisture absorption and heat resistance after the wiring is buried.

本實施形態中之被覆有二氧化矽之氟樹脂粒子(A)中使用的氟樹脂粒子不特別限定,可以列舉聚四氟乙烯(PTFE)、四氟化乙烯・全氟烷氧基乙烯共聚物(PF A)、四氟化乙烯・六氟丙烯共聚物(FEP)、乙烯・氯三氟乙烯共聚物(PCTFE)、乙烯・四氟化乙烯共聚物(ETFE)、聚偏二氟乙烯(PVDF)等。其中,考量電特性優異之觀點,PTFE為較佳。此等可以使用1種或將2種以上適當混用。The fluororesin particles used in the cerium oxide-coated fluororesin particles (A) in the present embodiment are not particularly limited, and examples thereof include polytetrafluoroethylene (PTFE), tetrafluoroethylene, and perfluoroalkoxyethylene copolymer. (PF A), tetrafluoroethylene, hexafluoropropylene copolymer (FEP), ethylene/chlorotrifluoroethylene copolymer (PCTFE), ethylene/tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF) )Wait. Among them, PTFE is preferred from the viewpoint of excellent electrical properties. These may be used alone or in combination of two or more.

氟樹脂粒子,考量使微細配線之填埋性為良好之觀點,一次粒子之體積平均粒徑為5μm以下較理想,4μm以下更佳,3μm以下更理想。又,考量電特性為良好之觀點,一次粒子之體積平均粒徑為0.005μm以上較理想,0.01μm以上更佳, 0.02μm以上更理想。 又,本說明書中,「體積平均粒徑」係指體積基準之粒徑分布之算術平均徑。體積平均粒徑可藉由例如:濕式雷射繞射・散射法測定。In view of the fact that the fluororesin particles are excellent in the filling property of the fine wiring, the volume average particle diameter of the primary particles is preferably 5 μm or less, more preferably 4 μm or less, and more preferably 3 μm or less. Further, from the viewpoint of good electrical properties, the volume average particle diameter of the primary particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, and more preferably 0.02 μm or more. In the present specification, the "volume average particle diameter" means the arithmetic mean diameter of the volume distribution based on the volume. The volume average particle diameter can be measured by, for example, a wet laser diffraction/scattering method.

被覆有二氧化矽之氟樹脂粒子(A)中之二氧化矽粒子之含量不特別限定,考量使流動性良好之觀點,相對於氟樹脂粒子之質量宜為0.001質量%以上較佳,0.005質量%以上更佳,0.01質量%以上更理想。又,考量展現氟樹脂粒子之電特性之觀點,10質量%以下較佳,5質量%以下更佳,2質量%以下更理想。The content of the cerium oxide particles in the fluororesin particles (A) coated with cerium oxide is not particularly limited, and from the viewpoint of improving the fluidity, the mass of the fluororesin particles is preferably 0.001% by mass or more, preferably 0.005 by mass. More preferably, % or more, and more preferably 0.01% by mass or more. Moreover, from the viewpoint of exhibiting electrical characteristics of the fluororesin particles, it is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

二氧化矽粒子只要一次粒子之體積平均粒徑小於前述氟樹脂粒子之體積平均粒徑即可,無特殊限制。其中,考量使氟樹脂之電特性展現之觀點,一次粒子之體積平均粒徑為200nm以下較佳,100nm以下較理想,70nm以下更佳,50nm以下更理想。又,考量使流動性良好之觀點,一次粒子之體積平均粒徑為0.3nm以上較理想,0.5nm以上更佳,1nm以上更理想。The cerium oxide particles are not particularly limited as long as the volume average particle diameter of the primary particles is smaller than the volume average particle diameter of the fluororesin particles. In view of the above, the volume average particle diameter of the primary particles is preferably 200 nm or less, more preferably 100 nm or less, more preferably 70 nm or less, and more preferably 50 nm or less. Further, in view of the fact that the fluidity is good, the volume average particle diameter of the primary particles is preferably 0.3 nm or more, more preferably 0.5 nm or more, and more preferably 1 nm or more.

被覆有二氧化矽之氟樹脂粒子(A),考量使微細配線之填埋性良好之觀點,一次粒子之體積平均粒徑為5μm以下較理想,4μm以下更佳,3μm以下更佳,若為2μm以下,考量微細配線之填埋性、介電常數及介電正切更良好之觀點,為更理想。又,考量使電特性為良好之觀點,一次粒子之體積平均粒徑為0.005μm以上較理想,0.01μm以上更佳,0.02μm以上更理想。The fluororesin particles (A) coated with cerium oxide are preferable in view of the fact that the filling property of the fine wiring is good, and the volume average particle diameter of the primary particles is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. 2 μm or less is preferable in view of the fact that the landfill, the dielectric constant, and the dielectric tangent of the fine wiring are better. Further, in view of the fact that the electrical characteristics are good, the volume average particle diameter of the primary particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, and more preferably 0.02 μm or more.

如此的被覆有二氧化矽之氟樹脂粒子也可利用市售品,例如:0.5μm PTFE- YA(商品名)、PTFE-YA4(3.0μm、商品名)(以上為Admatechs(股)製)。Commercially available fluororesin particles coated with cerium oxide can be used, for example, 0.5 μm PTFE-YA (trade name), PTFE-YA4 (3.0 μm, trade name) (above, manufactured by Admatechs Co., Ltd.).

本實施形態之樹脂組成物中之被覆有二氧化矽之氟樹脂粒子(A)之含量不特別限定,考量使樹脂組成物之電特性良好之觀點,相對於樹脂組成物中之樹脂固體成分100質量份,為3質量份以上較佳,5質量份以上更佳,10質量份以上又更佳,15質量份以上更佳,30質量份以上更理想。又,考量使耐熱性為良好之觀點,相對於樹脂組成物中之樹脂固體成分100質量份,為400質量份以下較佳,300質量份以下更佳,200質量份以下又更佳,100質量份以下更理想。The content of the cerium oxide-coated fluororesin particles (A) in the resin composition of the present embodiment is not particularly limited, and the resin solid content of the resin composition is considered to be good in view of the electrical properties of the resin composition. The parts by mass are preferably 3 parts by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 30 parts by mass or more. In view of the fact that the heat resistance is good, the content is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and 100 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. The following is more desirable.

<樹脂成分(B)> 本實施形態使用之樹脂成分(B),除了藉由使用被覆有二氧化矽之氟樹脂粒子(A)而獲得之電特性等以外,尚可因應樹脂組成物使用之領域要求的硬化的硬化物的阻燃性、耐熱性、熱膨脹特性等特性,而使用各式各樣的種類者。例如要求密合性時,可列舉環氧樹脂,要求耐熱性時,可列舉馬來醯亞胺化合物、氰酸酯化合物、苯并㗁??化合物,要求熱硬化性或光硬化性時,可列舉具有乙烯性不飽和基之化合物等,此外也可以使用苯酚樹脂、氧雜環丁烷樹脂等。<Resin component (B)> The resin component (B) used in the present embodiment can be used in accordance with the resin composition, in addition to the electrical properties obtained by using the fluororesin particles (A) coated with cerium oxide. Those who use various types of hardened cured materials required for the field have properties such as flame retardancy, heat resistance, and thermal expansion characteristics. For example, when adhesion is required, an epoxy resin is mentioned, and when heat resistance is required, a maleic imine compound, a cyanate compound, and a benzoxene compound are mentioned, and when thermosetting or photocurability is required, it can be used. A compound having an ethylenically unsaturated group or the like is exemplified, and a phenol resin, an oxetane resin or the like can also be used.

又,此等可使用1種或將2種以上適當混用。 以下針對此等樹脂成分(B)之詳情説明。In addition, one type or two or more types may be used as appropriate. The details of these resin components (B) are described below.

<馬來醯亞胺化合物> 馬來醯亞胺化合物只要是在分子中有1個以上之馬來醯亞胺基之化合物即可,並無特殊限制。其具體例,例如:N-苯基馬來醯亞胺、N-羥基苯基馬來醯亞胺、雙(4-馬來醯亞胺苯基)甲烷、2,2-雙{4-(4-馬來醯亞胺苯氧基)-苯基}丙烷、4,4-二苯基甲烷雙馬來醯亞胺、雙(3,5-二甲基-4-馬來醯亞胺苯基)甲烷、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、雙(3,5-二乙基-4-馬來醯亞胺苯基)甲烷、苯基甲烷馬來醯亞胺、鄰伸苯基雙馬來醯亞胺、間伸苯基雙馬來醯亞胺、對伸苯基雙馬來醯亞胺、鄰伸苯基雙檸康醯亞胺、間伸苯基雙檸康醯亞胺、對伸苯基雙檸康醯亞胺、2,2-雙(4-(4-馬來醯亞胺苯氧基)-苯基)丙烷、3,3-二甲基-5,5-二乙基-4,4-二苯基甲烷雙馬來醯亞胺、4-甲基-1,3-伸苯基雙馬來醯亞胺、1,6-雙馬來醯亞胺-(2,2,4-三甲基)己烷、4,4-二苯醚雙馬來醯亞胺、4,4-二苯基碸雙馬來醯亞胺、1,3-雙(3-馬來醯亞胺苯氧基)苯、1,3-雙(4-馬來醯亞胺苯氧基)苯、4,4-二苯基甲烷雙檸康醯亞胺、2,2-雙[4-(4-檸康醯亞胺苯氧基)苯基]丙烷、雙(3,5-二甲基-4-檸康醯亞胺苯基)甲烷、雙(3-乙基-5-甲基-4-檸康醯亞胺苯基)甲烷、雙(3,5-二乙基-4-檸康醯亞胺苯基)甲烷、聚苯基甲烷馬來醯亞胺、酚醛清漆型馬來醯亞胺化合物、聯苯芳烷基型馬來醯亞胺化合物、下式(4)表示之馬來醯亞胺化合物、下式(5)表示之馬來醯亞胺化合物、及此等馬來醯亞胺化合物之預聚物、或馬來醯亞胺化合物與胺化合物之預聚物等。<Malayimine Compound> The maleic imine compound is not particularly limited as long as it is a compound having one or more of the maleimine groups in the molecule. Specific examples thereof are, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2-double {4-( 4-maleimide phenoxy)-phenyl}propane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimide benzene Methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, Phenyl methane maleimide, o-phenyl bis-maleimide, meta-phenyl bis-maleimide, p-phenylene bismaleimide, o-phenyl-lilycan Imine, meta-phenyl phenyl sulphate, phenyl phenyl sulphate, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane ,3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide 1,6-Bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenyl ether, bismaleimide, 4,4-diphenylfluorene醯iimine, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenyl Methane double citrate Imine, 2,2-bis[4-(4-carbolineimine phenoxy)phenyl]propane, bis(3,5-dimethyl-4-limonium phenyleneimine phenyl)methane, Bis(3-ethyl-5-methyl-4-xankonium phenylene phenyl)methane, bis(3,5-diethyl-4- citraconin phenyl)methane, polyphenylmethane a maleic imine, a novolac type maleic imine compound, a biphenyl aralkyl type maleimide compound, a maleic imine compound represented by the following formula (4), represented by the following formula (5) a maleic imine compound, and a prepolymer of such a maleimide compound, or a prepolymer of a maleimide compound and an amine compound, and the like.

【化4】 【化4】

式(4)中,多個R5 各自獨立地表示氫原子或甲基。n1 表示1以上之整數,較佳為表示1~10之整數,更佳為表示1~5之整數。In the formula (4), a plurality of R 5 each independently represent a hydrogen atom or a methyl group. n 1 represents an integer of 1 or more, preferably represents an integer of 1 to 10, and more preferably represents an integer of 1 to 5.

【化5】 【化5】

式(5)中,多個R6 各自獨立地表示氫原子或甲基。n2 表示1以上之整數,較佳為表示1~5之整數。 該等馬來醯亞胺化合可單獨使用1種或將2種以上適當混用。其中,考量耐熱性優異之觀點,前述式(4)表示之馬來醯亞胺化合物、及前述式(5)表示之化合物較理想,前述式(4)表示之馬來醯亞胺化合物更理想。前述式(4)表示之馬來醯亞胺化合物可以利用市售品,例如:BMI-2300(大和化成工業(股)公司製)。前述式(5)表示之馬來醯亞胺化合物也可利用市售品,例如:MIR-3000(日本化藥(股)公司製)。In the formula (5), a plurality of R 6 each independently represent a hydrogen atom or a methyl group. n 2 represents an integer of 1 or more, and preferably represents an integer of 1 to 5. These maleimide compounds may be used alone or in combination of two or more. In view of the above, the maleidide compound represented by the above formula (4) and the compound represented by the above formula (5) are preferable, and the maleidin compound represented by the above formula (4) is more preferable. . The maleated imine compound represented by the above formula (4) can be used as a commercially available product, for example, BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.). A commercially available product such as MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) can also be used as the maleated imine compound represented by the above formula (5).

本實施形態之樹脂組成物中,馬來醯亞胺化合物之含量無特殊限制,相對於樹脂組成物中之樹脂固體成分100質量份較佳為0.01質量份~50質量份,更佳為0.02質量份~45質量份,又更佳為0.03質量份~20質量份,再更佳為0.1質量份~10質量份,又更佳為1質量份~7質量份。馬來醯亞胺化合物之含量藉由為上述範圍內,硬化物之耐熱性有更提高的傾向。In the resin composition of the present embodiment, the content of the maleimide compound is not particularly limited, and is preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.02% by mass based on 100 parts by mass of the resin solid content in the resin composition. The amount is preferably -45 parts by mass, more preferably 0.03 parts by mass to 20 parts by mass, still more preferably 0.1 parts by mass to 10 parts by mass, still more preferably 1 part by mass to 7 parts by mass. When the content of the maleimide compound is within the above range, the heat resistance of the cured product tends to be further improved.

<氰酸酯化合物> 氰酸酯化合物只要是在分子內有經至少1個氰氧基(氰酸酯基)取代之芳香族部分之樹脂即無特殊限制。<Cyanate ester compound> The cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety substituted with at least one cyanooxy group (cyanate group) in the molecule.

例如通式(6)表示者。For example, the formula (6) represents.

【化6】 【化6】

在此,式中,Ar1 表示苯環、萘環或2個苯環以單鍵鍵結者。有多數個時,彼此可相同也可不同。Ra各自獨立地表示氫原子、碳數1~6之烷基、碳數6~12之芳基、碳數1~4之烷氧基、碳數1~6之烷基與碳數6~12之芳基鍵結而得之基。Ra中之芳香環也可以有取代基,Ar1 及Ra中的取代基可選擇任意位置。p表示鍵結於Ar1 之氰氧基之數目,各自獨立地為1~3之整數。q表示鍵結於Ar1 之Ra之數目,於Ar1 為苯環時係4-p、為萘環時係6-p、為2個苯環以單鍵鍵結者時係8-p。t表示平均重複數,為0~50之整數,氰酸酯化合物亦可為t係不同的化合物之混合物。X有多個時,各自獨立地為單鍵、碳數1~50之2價有機基(氫原子也可取代成雜原子)、氮數1~10之2價有機基(例如-N-R-N-(在此R代表有機基))、羰基(-CO-)、羧基(-C(=O)O-)、二氧化羰基(-OC(=O)O-)、磺醯基(-SO2 -)、2價硫原子或2價氧原子中之任一者。Here, in the formula, Ar 1 represents a benzene ring, a naphthalene ring or two benzene rings bonded by a single bond. When there are a large number, they can be the same or different. Ra independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms, and a carbon number of 6 to 12 The base of the aryl bond. The aromatic ring in Ra may have a substituent, and the substituents in Ar 1 and Ra may be selected at any position. p represents the number of cyano groups bonded to Ar 1 and each independently is an integer of 1 to 3. q represents the number of Ra bonded to Ar 1 , and is 4-p when Ar 1 is a benzene ring, 6-p when it is a naphthalene ring, and 8-p when a benzene ring is bonded by a single bond. t represents the average repeat number, which is an integer from 0 to 50, and the cyanate compound may also be a mixture of compounds having different t systems. When there are a plurality of X, each is independently a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted into a hetero atom), and a divalent organic group having a nitrogen number of 1 to 10 (for example, -NRN-( Here, R represents an organic group)), a carbonyl group (-CO-), a carboxyl group (-C(=O)O-), a carbonyl group (-OC(=O)O-), a sulfonyl group (-SO 2 - Any one of a divalent sulfur atom or a divalent oxygen atom.

通式(6)之Ra之烷基,也可以具有直鏈或分枝之鏈狀結構、及環狀結構(例如環烷基等)中之任一者。 又,通式(6)中之烷基及Ra中之芳基中之氫原子也可以取代為氟原子、氯原子等鹵素原子、甲氧基、苯氧基等烷氧基、或氰基等。 烷基之具體例可以列舉甲基、乙基、丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、1-乙基丙基、2,2-二甲基丙基、環戊基、己基、環己基、及三氟甲基等。 芳基之具體例可以列舉苯基、甲苯基、均三甲苯基、萘基、苯氧基苯基、乙基苯基、鄰,間或對氟苯基、二氯苯基、二氰基苯基、三氟苯基、甲氧基苯基、及鄰,間或對甲苯基等。烷氧基,例如:甲氧基、乙氧基、丙氧基、異丙氧基、正丁氧基、異丁氧基、及第三丁氧基等。The alkyl group of Ra of the formula (6) may have either a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group or the like). Further, the hydrogen atom in the alkyl group in the formula (6) and the aryl group in Ra may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group. . Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethyl Alkyl group, cyclopentyl group, hexyl group, cyclohexyl group, and trifluoromethyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl group, and a dicyanobenzene. A group, a trifluorophenyl group, a methoxyphenyl group, and an o-, m- or p-tolyl group. The alkoxy group is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a third butoxy group or the like.

通式(6)之X之碳數1~50之2價有機基之具體例,可列舉亞甲基、伸乙基、三亞甲基、伸丙基等伸烷基、環伸戊基、環伸己基、三甲基環伸己基等環伸烷基、聯苯基亞甲基、二甲基亞甲基-伸苯基-二甲基亞甲基、茀二基、及酞內酯二基(phth alidediyl)等具有芳香環之2價有機基。該2價有機基中之氫原子,也可以取代成氟原子、氯原子等鹵素原子、甲氧基、苯氧基等烷氧基、氰基等。Specific examples of the divalent organic group having 1 to 50 carbon atoms of X in the formula (6) include a methylene group, an ethylidene group, a trimethylene group, a propyl group, an alkyl group, a cyclopentyl group, and a ring. Cyclohexyl, trimethylcyclohexyl and the like cycloalkyl, biphenylmethylene, dimethylmethylene-phenylene-dimethylmethylene, anthracenyl, and azlactone diyl A divalent organic group having an aromatic ring such as (phth alidediyl). The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group.

通式(6)之X之氮數1~10之2價有機基可以列舉-N-R-N-表示之基(R為有機基)、亞胺基、聚醯亞胺基等。The divalent organic group having a nitrogen number of 1 to 10 in the formula (6) may, for example, be a group represented by -N-R-N- (R is an organic group), an imine group or a polyindenylene group.

又,通式(6)中之X之有機基可以列舉例如:下列通式(7)或下列通式(8)表示之結構。Further, the organic group of X in the formula (6) may, for example, be a structure represented by the following formula (7) or the following formula (8).

【化7】 【化7】

在此,式中,Ar2 表示苯四基、萘四基或聯苯四基,u為2以上時,彼此可相同也可不同。Rb、Rc、Rf、及Rg各自獨立地表示氫原子、碳數1~6之烷基、碳數6~12之芳基、三氟甲基、或至少有1個苯酚性羥基之芳基。Rd及Re各自獨立地選自於氫原子、碳數1~6之烷基、碳數6~12之芳基、碳數1~4之烷氧基、或羥基中之任一種。u表示0~5之整數。Here, in the formula, Ar 2 represents a benzenetetrayl group, a naphthyltetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same or different. Rb, Rc, Rf, and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxyl group. Rd and Re are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. u represents an integer from 0 to 5.

【化8】 【化8】

在此,式中,Ar3 表示苯四基、萘四基或聯苯四基,且於v為2以上時,彼此可相同也可不同。Ri、及Rj各自獨立地表示氫原子、碳數1~6之烷基、碳數6~12之芳基、苄基、碳數1~4之烷氧基、羥基、三氟甲基、或經至少1個氰氧基取代之芳基。v表示0~5之整數,但也可以是v係不同之化合物之混合物。Here, in the formula, Ar 3 represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when v is 2 or more, they may be the same or different. Ri, and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or An aryl group substituted with at least one cyanooxy group. v represents an integer of 0 to 5, but may be a mixture of different compounds of v.

再者,通式(6)中之X可以列舉下式表示之2價基。Further, X in the general formula (6) may be a divalent group represented by the following formula.

【化9】 【化9】

在此,式中,z表示4~7之整數。Rk各自獨立地表示氫原子或碳數1~6之烷基。Here, in the formula, z represents an integer of 4-7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

通式(7)之Ar2 及通式(8)之Ar3 之具體例可以列舉通式(7)所示之2個碳原子、或通式(8)所示之2個氧原子鍵結在1,4位或1,3位之苯四基、上述2個碳原子或2個氧原子鍵結於4,4’位、2,4’位、2,2’位、2,3’位、3,3’位、或3,4’位之聯苯四基、及上述2個碳原子或2個氧原子鍵結於2,6位、1,5位、1,6位、1,8位、1,3位、1,4位、或2,7位之萘四基。Specific examples of Ar 2 of the formula (7) and Ar 3 of the formula (8) include two carbon atoms represented by the formula (7) or two oxygen atoms bonded by the formula (8). The benzenetetrayl group at the 1,4 or 1,3 position, the above 2 carbon atoms or 2 oxygen atoms are bonded to the 4,4' position, the 2,4' position, the 2,2' position, and the 2,3' a biphenyltetrayl group at the 3,3' position or the 3,4' position, and the above 2 carbon atoms or 2 oxygen atoms bonded to the 2,6 position, 1,5 position, 1,6 position, 1 , naphthyltetrayl group of 8, 3, 1, 4, or 2, 7.

通式(7)之Rb、Rc、Rd、Re、Rf及Rg、及通式(8)之Ri、Rj之烷基及芳基,含意同上述通式(6)中者。Rb, Rc, Rd, Re, Rf and Rg of the formula (7), and an alkyl group and an aryl group of Ri, Rj of the formula (8) are intended to be the same as those in the above formula (6).

上述通式(6)表示之氰氧基取代芳香族化合物之具體例可以列舉氰氧基苯、1-氰氧基-2-,1-氰氧基-3-,或1-氰氧基-4-甲基苯、1-氰氧基-2-,1-氰氧基-3-,或1-氰氧基-4-甲氧基苯、1-氰氧基-2,3-,1-氰氧基-2,4-,1-氰氧基-2,5-,1-氰氧基-2,6-,1-氰氧基-3,4-或1-氰氧基-3,5-二甲基苯、氰氧基乙基苯、氰氧基丁基苯、氰氧基辛基苯、氰氧基壬基苯、2-(4-氰氧基苯基)-2-苯基丙烷(4-α-異丙苯基苯酚之氰酸酯)、1-氰氧基-4-環己基苯、1-氰氧基-4-乙烯基苯、1-氰氧基-2-或1-氰氧基-3-氯苯、1-氰氧基-2,6-二氯苯、1-氰氧基-2-甲基-3-氯苯、氰氧基硝基苯、1-氰氧基-4-硝基-2-乙基苯、1-氰氧基-2-甲氧基-4-烯丙基苯(丁香酚之氰酸酯)、甲基(4-氰氧基苯基)硫醚、1-氰氧基-3-三氟甲基苯、4-氰氧基聯苯、1-氰氧基-2-或1-氰氧基-4-乙醯基苯、4-氰氧基苯甲醛、4-氰氧基苯甲酸甲酯、4-氰氧基苯甲酸苯酯、1-氰氧基-4-乙醯基胺基苯、4-氰氧基二苯酮、1-氰氧基-2,6-二-第三丁基苯、1,2-二氰氧基苯、1,3-二氰氧基苯、1,4-二氰氧基苯、1,4-二氰氧基-2-第三丁基苯、1,4-二氰氧基-2,4-二甲基苯、1,4-二氰氧基-2,3,4-三甲基苯、1,3-二氰氧基-2,4,6-三甲基苯、1,3-二氰氧基-5-甲基苯、1-氰氧基或2-氰氧基萘、1-氰氧基4-甲氧基萘、2-氰氧基-6-甲基萘、2-氰氧基-7-甲氧基萘、2,2’-二氰氧基-1,1’-聯萘、1,3-、1,4-、1,5-、1,6-、1,7-、2,3-、2,6-或2,7-二氰氧基萘、2,2’-或4,4’-二氰氧基聯苯、4,4’-二氰氧基八氟聯苯、2,4’-或4,4’-二氰氧基二苯基甲烷、雙(4-氰氧基-3,5-二甲基苯基)甲烷、1,1-雙(4-氰氧基苯基)乙烷、1,1-雙(4-氰氧基苯基)丙烷、2,2-雙(4-氰氧基苯基)丙烷、2,2-雙(4-氰氧基-3-甲基苯基)丙烷、2,2-雙(2-氰氧基-5-聯苯基)丙烷、2,2-雙(4-氰氧基苯基)六氟丙烷、2,2-雙(4-氰氧基-3,5-二甲基苯基)丙烷、1,1-雙(4-氰氧基苯基)丁烷、1,1-雙(4-氰氧基苯基)異丁烷、1,1-雙(4-氰氧基苯基)戊烷、1,1-雙(4-氰氧基苯基)-3-甲基丁烷、1,1-雙(4-氰氧基苯基)-2-甲基丁烷、1,1-雙(4-氰氧基苯基)-2,2-二甲基丙烷、2,2-雙(4-氰氧基苯基)丁烷、2,2-雙(4-氰氧基苯基)戊烷、2,2-雙(4-氰氧基苯基)己烷、2,2-雙(4-氰氧基苯基)-3-甲基丁烷、2,2-雙(4-氰氧基苯基)-4-甲基戊烷、2,2-雙(4-氰氧基苯基)-3,3-二甲基丁烷、3,3-雙(4-氰氧基苯基)己烷、3,3-雙(4-氰氧基苯基)庚烷、3,3-雙(4-氰氧基苯基)辛烷、3,3-雙(4-氰氧基苯基)-2-甲基戊烷、3,3-雙(4-氰氧基苯基)-2-甲基己烷、3,3-雙(4-氰氧基苯基)-2,2-二甲基戊烷、4,4-雙(4-氰氧基苯基)-3-甲基庚烷、3,3-雙(4-氰氧基苯基)-2-甲基庚烷、3,3-雙(4-氰氧基苯基)-2,2-二甲基己烷、3,3-雙(4-氰氧基苯基)- 2,4-二甲基己烷、3,3-雙(4-氰氧基苯基)-2,2,4-三甲基戊烷、2,2-雙(4-氰氧基苯基)- 1,1,1,3,3,3-六氟丙烷、雙(4-氰氧基苯基)苯基甲烷、1,1-雙(4-氰氧基苯基)-1-苯基乙烷、雙(4-氰氧基苯基)聯苯甲烷、1,1-雙(4-氰氧基苯基)環戊烷、1,1-雙(4-氰氧基苯基)環己烷、2,2-雙(4-氰氧基-3-異丙基苯基)丙烷、1,1-雙(3-環己基-4-氰氧基苯基)環己烷、雙(4-氰氧基苯基)二苯基甲烷、雙(4-氰氧基苯基)-2,2-二氯乙烯、1,3-雙[2-(4-氰氧基苯基)-2-丙基]苯、1,4-雙[2-(4-氰氧基苯基)-2-丙基]苯、1,1-雙(4-氰氧基苯基)-3,3,5-三甲基環己烷、4-[雙(4-氰氧基苯基)甲基]聯苯、4,4-二氰氧基二苯酮、1,3-雙(4-氰氧基苯基)-2-丙烯-1-酮、雙(4-氰氧基苯基)醚、雙(4-氰氧基苯基)硫醚、雙(4-氰氧基苯基)碸、4-氰氧基苯甲酸-4-氰氧基苯酯(4-氰氧基苯基-4-氰氧基苯甲酸酯)、雙-(4-氰氧基苯基)碳酸酯、1,3-雙(4-氰氧基苯基)金剛烷、1,3-雙(4-氰氧基苯基)-5,7-二甲基金剛烷、1,3-雙(3-甲基-4-氰氧基苯基)-5,7-二甲基金剛烷、3,3-雙(4-氰氧基苯基)異苯并呋喃-1(3H)-酮(苯酚酚酞之氰酸酯)、3,3-雙(4-氰氧基-3-甲基苯基)異苯并呋喃-1(3H)-酮(o-甲酚酚酞之氰酸酯)、9,9’-雙(4-氰氧基苯基)茀、9,9-雙(4-氰氧基-3-甲基苯基)茀、9,9-雙(2-氰氧基-5-聯苯基)茀、參(4-氰氧基苯基)甲烷、1,1,1-參(4-氰氧基苯基)乙烷、1,1,3-參(4-氰氧基苯基)丙烷、α,α, α’-參(4-氰氧基苯基)-1-乙基-4-異丙基苯、1,1,2,2-肆(4-氰氧基苯基)乙烷、肆(4-氰氧基苯基)甲烷、2,4,6-參(N-甲基-4-氰氧基苯胺基)-1,3,5-三??、2,4-雙(N-甲基-4-氰氧基苯胺基)-6-(N-甲基苯胺基)-1,3,5-三??、雙(N-4-氰氧基-2-甲基苯基)-4, 4’-氧二鄰苯二甲醯亞胺、雙(N-3-氰氧基-4-甲基苯基)-4,4’-氧二鄰苯二甲醯亞胺、 雙(N-4-氰氧基苯基)-4,4’-氧二鄰苯二甲醯亞胺、雙(N-4-氰氧基-2-甲基苯基)-4,4’- (六氟異亞丙基)二鄰苯二甲醯亞胺、參(3,5-二甲基-4-氰氧基苄基)異氰尿酸酯、2-苯基-3,3-雙(4-氰氧基苯基)苄甲內醯胺、2-(4-甲基苯基)-3,3-雙(4-氰氧基苯基)苄甲內醯胺、2-苯基-3,3-雙(4-氰氧基-3-甲基苯基)苄甲內醯胺、1-甲基-3,3-雙(4-氰氧基苯基)吲哚啉-2-酮、及2-苯基-3,3-雙(4-氰氧基苯基)吲哚啉-2-酮、及該等之預聚物。Specific examples of the cyanooxy-substituted aromatic compound represented by the above formula (6) include cyanooxybenzene, 1-cyanooxy-2-, 1-cyanooxy-3-, or 1-cyanooxy- 4-methylbenzene, 1-cyanooxy-2-, 1-cyanooxy-3-, or 1-cyanooxy-4-methoxybenzene, 1-cyanooxy-2,3-,1 -Cyanooxy-2,4-,1-cyanooxy-2,5-,1-cyanooxy-2,6-,1-cyanooxy-3,4- or 1-cyanooxy-3 ,5-dimethylbenzene, cyanooxyethylbenzene, cyanooxybutylbenzene, cyanooxyoctylbenzene, cyanooxyindenylbenzene, 2-(4-cyanooxyphenyl)-2- Phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanooxy-4-cyclohexylbenzene, 1-cyanooxy-4-vinylbenzene, 1-cyanooxy-2 - or 1-cyanooxy-3-chlorobenzene, 1-cyanooxy-2,6-dichlorobenzene, 1-cyanooxy-2-methyl-3-chlorobenzene, cyanooxynitrobenzene, 1-cyanooxy-4-nitro-2-ethylbenzene, 1-cyanooxy-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanide) Oxyphenyl)thioether, 1-cyanooxy-3-trifluoromethylbenzene, 4-cyanooxybiphenyl, 1-cyanooxy-2- or 1-cyanooxy-4-ethenyl Benzene, 4-cyanooxybenzaldehyde, methyl 4-cyanooxybenzoate, phenyl 4-cyanooxybenzoate 1-cyanooxy-4-ethinylaminobenzene, 4-cyanooxybenzophenone, 1-cyanooxy-2,6-di-t-butylbenzene, 1,2-dicyanooxy Benzene, 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene, 1,4-dicyanooxy-2-tert-butylbenzene, 1,4-dicyanooxy-2, 4-dimethylbenzene, 1,4-dicyanooxy-2,3,4-trimethylbenzene, 1,3-dicyanooxy-2,4,6-trimethylbenzene, 1,3 - biscyanooxy-5-methylbenzene, 1-cyanooxy or 2-cyanooxynaphthalene, 1-cyanooxy 4-methoxynaphthalene, 2-cyanooxy-6-methylnaphthalene, 2 -Cyanooxy-7-methoxynaphthalene, 2,2'-dicyanooxy-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanooxynaphthalene, 2,2'- or 4,4'-dicyanoxybiphenyl, 4,4'-dicyandi Oxy octafluorobiphenyl, 2,4'- or 4,4'-dicyanooxydiphenylmethane, bis(4-cyanooxy-3,5-dimethylphenyl)methane, 1,1 - bis(4-cyanooxyphenyl)ethane, 1,1-bis(4-cyanooxyphenyl)propane, 2,2-bis(4-cyanooxyphenyl)propane, 2,2- Bis(4-cyanooxy-3-methylphenyl)propane, 2,2-bis(2-cyanooxy-5-biphenyl)propane, 2,2-bis(4-cyanooxyphenyl) Hexafluoropropane, 2,2-bis(4-cyanooxy-3,5-dimethylphenyl) Propane, 1,1-bis(4-cyanooxyphenyl)butane, 1,1-bis(4-cyanooxyphenyl)isobutane, 1,1-bis(4-cyanooxyphenyl) Pentane, 1,1-bis(4-cyanooxyphenyl)-3-methylbutane, 1,1-bis(4-cyanooxyphenyl)-2-methylbutane, 1, 1-bis(4-cyanooxyphenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanooxyphenyl)butane, 2,2-bis(4-cyanooxyl) Phenyl)pentane, 2,2-bis(4-cyanooxyphenyl)hexane, 2,2-bis(4-cyanooxyphenyl)-3-methylbutane, 2,2-double (4-cyanooxyphenyl)-4-methylpentane, 2,2-bis(4-cyanooxyphenyl)-3,3-dimethylbutane, 3,3-bis(4- Cyanooxyphenyl)hexane, 3,3-bis(4-cyanooxyphenyl)heptane, 3,3-bis(4-cyanooxyphenyl)octane, 3,3-bis (4 -Cyanooxyphenyl)-2-methylpentane, 3,3-bis(4-cyanooxyphenyl)-2-methylhexane, 3,3-bis(4-cyanooxyphenyl) )-2,2-dimethylpentane, 4,4-bis(4-cyanooxyphenyl)-3-methylheptane, 3,3-bis(4-cyanooxyphenyl)-2 -methylheptane, 3,3-bis(4-cyanooxyphenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanooxyphenyl)-2,4- Dimethylhexane, 3,3-bis(4-cyanooxyphenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanooxybenzene) )- 1,1,1,3,3,3-hexafluoropropane, bis(4-cyanooxyphenyl)phenylmethane, 1,1-bis(4-cyanooxyphenyl)-1-benzene Ethylethane, bis(4-cyanooxyphenyl)biphenylmethane, 1,1-bis(4-cyanooxyphenyl)cyclopentane, 1,1-bis(4-cyanooxyphenyl) Cyclohexane, 2,2-bis(4-cyanooxy-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanooxyphenyl)cyclohexane, double (4-cyanooxyphenyl)diphenylmethane, bis(4-cyanooxyphenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanooxyphenyl) -2-propyl]benzene, 1,4-bis[2-(4-cyanooxyphenyl)-2-propyl]benzene, 1,1-bis(4-cyanooxyphenyl)-3, 3,5-trimethylcyclohexane, 4-[bis(4-cyanooxyphenyl)methyl]biphenyl, 4,4-dicyanooxybenzophenone, 1,3-bis(4- Cyanooxyphenyl)-2-propen-1-one, bis(4-cyanooxyphenyl)ether, bis(4-cyanooxyphenyl) sulfide, bis(4-cyanooxyphenyl)碸, 4-cyanooxybenzoic acid-4-cyanooxyphenyl ester (4-cyanooxyphenyl-4-cyanooxybenzoate), bis-(4-cyanooxyphenyl) carbonate , 1,3-bis(4-cyanooxyphenyl)adamantane, 1,3-bis(4-cyanooxyphenyl)-5,7-dimethyladamantane, 1,3-double (3 -methyl-4-cyanooxyphenyl)-5,7-di Methyladamantane, 3,3-bis(4-cyanooxyphenyl)isobenzofuran-1(3H)-one (cyanate of phenol phenolphthalein), 3,3-bis(4-cyanooxyl) -3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresol phenolphthalein), 9,9'-bis(4-cyanooxyphenyl)anthracene, 9, 9-bis(4-cyanooxy-3-methylphenyl)anthracene, 9,9-bis(2-cyanooxy-5-biphenyl)anthracene, ginseng (4-cyanooxyphenyl)methane 1,1,1-parade(4-cyanooxyphenyl)ethane, 1,1,3-glycol(4-cyanooxyphenyl)propane, α,α,α'-para (4-cyano Oxyphenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-indole (4-cyanooxyphenyl)ethane, hydrazine (4-cyanooxyphenyl)methane , 2,4,6-parade (N-methyl-4-cyanoanilino)-1,3,5-tri-, 2,4-bis(N-methyl-4-cyanoaniline) -6-(N-methylanilino)-1,3,5-tri??, bis(N-4-cyanooxy-2-methylphenyl)-4,4'-oxydi-ortho Benzoimine, bis(N-3-cyanooxy-4-methylphenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanooxybenzene) -4,4'-oxydiphthalimide, bis(N-4-cyanooxy-2-methylphenyl)-4,4'-(hexafluoroisopropylidene) Phthaloin imine, ginseng (3,5-dimethyl-4-cyanooxybenzyl) Isocyanurate, 2-phenyl-3,3-bis(4-cyanooxyphenyl)benzylamine, 2-(4-methylphenyl)-3,3-bis (4) -Cyanooxyphenyl)benzylamine, 2-phenyl-3,3-bis(4-cyanooxy-3-methylphenyl)benzylamine, 1-methyl-3, 3-bis(4-cyanooxyphenyl) porphyrin-2-one, and 2-phenyl-3,3-bis(4-cyanooxyphenyl)porphyrin-2-one, and Prepolymers.

其中,考量耐熱性、及介電常數、介電正切優異之觀點,2,2-雙(4-氰氧基苯基)丙烷之預聚物為較佳。Among them, a prepolymer of 2,2-bis(4-cyanooxyphenyl)propane is preferred in view of excellent heat resistance, dielectric constant, and dielectric tangent.

該等氰酸酯化合物可單獨使用1種或將2種以上混用。These cyanate compounds may be used alone or in combination of two or more.

又,作為上述通式(6)表示之化合物之其他具體例,可列舉使如苯酚酚醛清漆樹脂及甲酚酚醛清漆樹脂(依公知之方法,使苯酚、烷基取代苯酚或鹵素取代苯酚、與福馬林、三聚甲醛等甲醛化合物在酸性溶液中反應而得者)、參苯酚酚醛清漆樹脂(使羥基苯甲醛與苯酚於酸性觸媒存在下反應而得者)、茀酚醛清漆樹脂(使茀酮化合物與9,9-雙(羥基芳基)茀類於酸性觸媒存在下反應而得者)、苯酚芳烷基樹脂、甲酚芳烷基樹脂、萘酚芳烷基樹脂及聯苯芳烷基樹脂(依公知之方法,使Ar2 -(CH2 Y)2 (Ar2 表示苯基,Y表示鹵素原子。以下,在此項目皆同。)表示之雙鹵甲烷合物與苯酚化合物於酸性觸媒或無觸媒反應而得者、使如Ar2 -(CH2 OR)2 表示之雙(烷氧基甲基)化合物與苯酚化合物於酸性觸媒存在下反應而得者、或使如Ar2 -(CH2 OH)2 表示之雙(羥基甲基)化合物與苯酚化合物於酸性觸媒存在下反應而得者、或使芳香族醛化合物與芳烷基化合物與苯酚化合物縮聚而得者)、苯酚改性二甲苯甲醛樹脂(依公知之方法,使二甲苯甲醛樹脂與苯酚化合物於酸性觸媒存在下反應而得者)、改性萘甲醛樹脂(依公知之方法,使萘甲醛樹脂與羥基取代芳香族化合物在酸性觸媒存在下反應而得者)、苯酚改性二環戊二烯樹脂、具有聚伸萘醚結構之苯酚樹脂(依公知之方法,使在1分子中具有2個以上的苯酚性羥基的多價羥基萘化合物於鹼性觸媒存在下脱水縮合而得者)等苯酚樹脂依照和上述同樣的方法進行氰酸酯化者等、及該等之預聚物等。它們並無特殊限制。該等氰酸酯化合物可以單獨使用1種或混用2種以上。又,若該等氰酸酯化合物和上述通式(6)表示之氰酸酯化合物同時使用的話,從耐熱性、介電常數、介電正切優異之觀點為較理想。Further, as another specific example of the compound represented by the above formula (6), a phenol novolac resin and a cresol novolak resin (a phenol, an alkyl-substituted phenol or a halogen-substituted phenol, and a known method) may be mentioned. A compound such as formalin or trioxane which reacts in an acidic solution), a phenol novolac resin (a reaction obtained by reacting hydroxybenzaldehyde with phenol in the presence of an acidic catalyst), and a phenol novolak resin (made 茀) a ketone compound reacted with a 9,9-bis(hydroxyaryl) hydrazine in the presence of an acidic catalyst), a phenol aralkyl resin, a cresol aralkyl resin, a naphthol aralkyl resin, and a biphenyl aryl group. Alkyl resin (Ar 2 -(CH 2 Y) 2 (Ar 2 represents a phenyl group, and Y represents a halogen atom. Hereinafter, the same applies to this item), and a bisphenol compound and a phenol compound are represented by a known method. In the presence of an acidic catalyst or a non-catalytic reaction, a bis(alkoxymethyl) compound represented by Ar 2 —(CH 2 OR) 2 is reacted with a phenol compound in the presence of an acidic catalyst, or so as Ar 2 - (CH 2 OH) 2 represented by the bis (hydroxymethyl) compound and a phenol compound a phenol-modified xylene-formaldehyde resin obtained by reacting in the presence of an acidic catalyst or a polycondensation of an aromatic aldehyde compound and an aralkyl compound with a phenol compound (by a known method, a xylene formaldehyde resin and a phenol) a compound obtained by reacting a compound in the presence of an acid catalyst), a modified naphthaldehyde resin (a method in which a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound are reacted in the presence of an acidic catalyst according to a known method), and a phenol-modified second a cyclopentadiene resin or a phenol resin having a poly(naphthyl ether) structure (a known method of dehydrating and condensing a polyvalent hydroxynaphthalene compound having two or more phenolic hydroxyl groups in one molecule in the presence of a basic catalyst) The phenol resin is obtained by the same method as described above, and the prepolymer or the like. They are not subject to any special restrictions. These cyanate compounds may be used alone or in combination of two or more. In addition, when the cyanate compound and the cyanate compound represented by the above formula (6) are used together, it is preferable from the viewpoint of excellent heat resistance, dielectric constant, and dielectric tangent.

其中,苯酚酚醛清漆型氰酸酯化合物、萘酚芳烷基型氰酸酯化合物、聯苯芳烷基型氰酸酯化合物、伸萘醚型氰酸酯化合物、二甲苯樹脂型氰酸酯化合物、金剛烷骨架型氰酸酯化合物較理想,萘酚芳烷基型氰酸酯化合物,從耐熱性之觀點特別理想。Among them, a phenol novolak type cyanate compound, a naphthol aralkyl type cyanate compound, a biphenyl aralkyl type cyanate compound, a naphthyl ether type cyanate compound, a xylene resin type cyanate compound The adamantane skeleton type cyanate compound is preferable, and the naphthol aralkyl type cyanate compound is particularly preferable from the viewpoint of heat resistance.

該等氰酸酯化合物之製造方法不特別限定,可以使用公知之方法。該製法,例如取得或合成有所望骨架之含羥基之化合物,將該羥基依公知之方法予以修飾而氰酸酯化之方法。將羥基予以氰酸酯化之方法,例如可列舉在Ian Hamerton, “Chemistry and Technology of Cyanate Ester Resins, ”Blackie Academic & Professio nal記載的方法。The method for producing the cyanate compound is not particularly limited, and a known method can be used. This production method is, for example, a method of obtaining or synthesizing a hydroxyl group-containing compound of a desired skeleton, and modifying the hydroxyl group by a known method to cyanate. A method of cyanating a hydroxyl group can be exemplified by the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

使用了該等氰酸酯化合物之樹脂硬化物,具有玻璃轉移溫度、低熱膨脹性、鍍敷密合性等優異之特性。 本實施形態之樹脂組成物中,氰酸酯化合物之含量不特別限定,考量耐熱性、介電常數、介電正切優異之觀點,相對於樹脂組成物中之樹脂固體成分100質量份較佳為0.1質量份~50質量份,更佳為0.2質量份~40質量份,又更佳為0.3質量份~20質量份,更佳為0.5質量份~10質量份,又更佳為1質量份~5質量份。The resin cured product using these cyanate compounds has excellent characteristics such as glass transition temperature, low thermal expansion property, and plating adhesion. In the resin composition of the present embodiment, the content of the cyanate compound is not particularly limited, and from the viewpoint of excellent heat resistance, dielectric constant, and dielectric tangent, it is preferably 100 parts by mass based on the resin solid content in the resin composition. 0.1 parts by mass to 50 parts by mass, more preferably 0.2 parts by mass to 40 parts by mass, still more preferably 0.3 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, still more preferably 1 part by mass. 5 parts by mass.

<環氧樹脂> 環氧樹脂只要是在1分子中具有2個以上之環氧基之化合物即可,可適當使用公知品,其種類無特殊限制。其具體例,例如:雙酚A型環氧樹脂、雙酚E型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、聯苯型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、二甲苯酚醛清漆型環氧樹脂、多官能苯酚型環氧樹脂、萘型環氧樹脂、萘骨架改性酚醛清漆型環氧樹脂、伸萘醚型環氧樹脂、苯酚芳烷基型環氧樹脂、蒽型環氧樹脂、3官能苯酚型環氧樹脂、4官能苯酚型環氧樹脂、異氰尿酸三環氧丙酯、環氧丙酯型環氧樹脂、脂環族環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂、聯苯酚醛清漆型環氧樹脂、苯酚芳烷基酚醛清漆型環氧樹脂、萘酚芳烷基酚醛清漆型環氧樹脂、芳烷基酚醛清漆型環氧樹脂、聯苯芳烷基型環氧樹脂、萘酚芳烷基型環氧樹脂、二環戊二烯型環氧樹脂、多元醇型環氧樹脂、含磷之環氧樹脂、環氧丙胺、將丁二烯等的雙鍵予以環氧化而得之化合物、含有羥基之聚矽氧樹脂類與表氯醇反應而獲得之化合物、及該等之鹵化物。 其中,聯苯芳烷基型環氧樹脂、伸萘醚型環氧樹脂、多官能苯酚型環氧樹脂、萘型環氧樹脂、溴化雙酚A型環氧樹脂,於阻燃性、耐熱性方面較理想。 此等環氧樹脂可以單獨使用1種或將2種以上適當混用。<Epoxy resin> The epoxy resin may be a compound having two or more epoxy groups in one molecule, and a known product may be appropriately used, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl. Epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, xylenol varnish type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified phenolic Varnish type epoxy resin, naphthene ether type epoxy resin, phenol aralkyl type epoxy resin, fluorene type epoxy resin, trifunctional phenol type epoxy resin, 4-functional phenol type epoxy resin, isocyanuric acid tricyclic Oxypropyl propyl ester, glycidyl epoxide type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl aldehyde varnish type epoxy resin, phenol aralkyl phenol varnish type epoxy Resin, naphthol aralkyl novolac type epoxy resin, aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type Epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin, epoxy propylamine, will A compound obtained by epoxidizing a double bond such as butadiene, a compound obtained by reacting a hydroxyl group-containing polyoxyl resin with epichlorohydrin, and the like. Among them, biphenyl aralkyl type epoxy resin, naphthene ether type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, flame retardant, heat resistant The sexual aspect is ideal. These epoxy resins may be used alone or in combination of two or more.

環氧樹脂之含量無特殊限制,相對於樹脂組成物中之樹脂固體成分100質量份較佳為0.1質量份~50質量份,更佳為0.2質量份~45質量份,更佳為5質量份~40質量份,又更佳為10質量份~25質量份,更佳為15質量份~25質量份,最佳為12質量份~20質量份。環氧樹脂之含量藉由為上述範圍內,阻燃性及耐熱性有更為提升的傾向。The content of the epoxy resin is not particularly limited, and is preferably 0.1 parts by mass to 50 parts by mass, more preferably 0.2 parts by mass to 45 parts by mass, even more preferably 5 parts by mass, per 100 parts by mass of the resin solid content in the resin composition. ~40 parts by mass, more preferably 10 parts by mass to 25 parts by mass, more preferably 15 parts by mass to 25 parts by mass, most preferably 12 parts by mass to 20 parts by mass. When the content of the epoxy resin is within the above range, the flame retardancy and heat resistance tend to be further improved.

<苯酚樹脂> 苯酚樹脂只要是在1分子中具有2個以上之羥基之苯酚樹脂即可,可以使用一般公知者。例如:雙酚A型苯酚樹脂、雙酚E型苯酚樹脂、雙酚F型苯酚樹脂、雙酚S型苯酚樹脂、苯酚酚醛清漆樹脂、雙酚A酚醛清漆型苯酚樹脂、環氧丙酯型苯酚樹脂、芳烷基酚醛清漆型苯酚樹脂、聯苯芳烷基型苯酚樹脂、甲酚酚醛清漆型苯酚樹脂、多官能苯酚樹脂、萘酚樹脂、萘酚酚醛清漆樹脂、多官能萘酚樹脂、蒽型苯酚樹脂、萘骨架改性酚醛清漆型苯酚樹脂、苯酚芳烷基型苯酚樹脂、萘酚芳烷基型苯酚樹脂、二環戊二烯型苯酚樹脂、聯苯型苯酚樹脂、脂環族苯酚樹脂、多元醇型苯酚樹脂、含磷之苯酚樹脂、含聚合性不飽和烴基之苯酚樹脂及含羥基之聚矽氧樹脂類等,但無特殊限制。該等苯酚樹脂之中,考量阻燃性之觀點,聯苯芳烷基型苯酚樹脂、萘酚芳烷基型苯酚樹脂、含磷之苯酚樹脂、含羥基之聚矽氧樹脂較理想。該等苯酚樹脂可單獨使用1種或適當混用2種以上。<Phenol Resin> The phenol resin may be a phenol resin having two or more hydroxyl groups in one molecule, and generally known ones can be used. For example: bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolak type phenol resin, glycidyl phenol type Resin, aralkyl novolac type phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, hydrazine Type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol The resin, the polyol type phenol resin, the phosphorus-containing phenol resin, the phenol resin containing a polymerizable unsaturated hydrocarbon group, and the hydroxyl group-containing polyoxyl resin are not particularly limited. Among these phenol resins, from the viewpoint of flame retardancy, a biphenyl aralkyl type phenol resin, a naphthol aralkyl type phenol resin, a phosphorus-containing phenol resin, and a hydroxyl group-containing polyoxymethylene resin are preferable. These phenol resins may be used alone or in combination of two or more.

苯酚樹脂之含量無特殊限制,相對於樹脂組成物中之樹脂固體成分100質量份較佳為0.1質量份~50質量份,更佳為0.2質量份~45質量份,又更佳為0.3質量份~40質量份。苯酚樹脂之含量藉由為上述範圍內,耐熱性有更提升的傾向。The content of the phenol resin is not particularly limited, and is preferably 0.1 parts by mass to 50 parts by mass, more preferably 0.2 parts by mass to 45 parts by mass, even more preferably 0.3 parts by mass, per 100 parts by mass of the resin solid content in the resin composition. ~40 parts by mass. When the content of the phenol resin is within the above range, the heat resistance tends to be further improved.

<氧雜環丁烷樹脂> 氧雜環丁烷樹脂可以使用一般公知者。例如:氧雜環丁烷、2-甲基氧雜環丁烷、2,2-二甲基氧雜環丁烷、3-甲基氧雜環丁烷、3,3-二甲基氧雜環丁烷等烷基氧雜環丁烷、3-甲基-3-甲氧基甲基氧雜環丁烷、3,3-二(三氟甲基)全氟氧雜環丁烷、2-氯甲基氧雜環丁烷、3,3-雙(氯甲基)氧雜環丁烷、聯苯型氧雜環丁烷、OXT- 101(東亞合成製,商品名)、OXT-121(東亞合成製,商品名)等,無特殊限制。此等可以使用單獨1種或將2種以上適當混用。<Oxetane Resin> The oxetane resin can be generally used. For example: oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxa Alkyloxetane such as cyclobutane, 3-methyl-3-methoxymethyloxetane, 3,3-bis(trifluoromethyl)perfluorooxetane, 2 -Chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (made by East Asia Synthetic, trade name), OXT-121 (East Asian synthetic system, trade name), etc., without special restrictions. These may be used alone or in combination of two or more.

氧雜環丁烷樹脂之含量無特殊限制,相對於樹脂組成物中之樹脂固體成分100質量份較佳為0.1質量份~50質量份,更佳為0.2質量份~45質量份,又更佳為0.3質量份~40質量份。氧雜環丁烷樹脂之含量藉由為上述範圍內,耐熱性有更為提升的傾向。The content of the oxetane resin is not particularly limited, and is preferably 0.1 parts by mass to 50 parts by mass, more preferably 0.2 parts by mass to 45 parts by mass, even more preferably 100 parts by mass of the resin solid content in the resin composition. It is 0.3 parts by mass to 40 parts by mass. When the content of the oxetane resin is within the above range, the heat resistance tends to be further improved.

<苯并㗁??化合物> 就苯并㗁??化合物而言,只要是在1分子中有2個以上之二氫苯并㗁??環之化合物即可,可使用一般公知者。例如:雙酚A型苯并㗁??BA-BXZ(小西化學製、商品名)雙酚F型苯并㗁??BF-BXZ(小西化學製、商品名)、雙酚S型苯并㗁??BS- BXZ(小西化學製、商品名)、苯酚酚酞型苯并㗁??等,無特殊限制。此等可以使用1種或將2種以上適當混用。<Benzene hydrazine compound> The benzoxanthene compound may be a compound which has two or more dihydrobenzoxene rings in one molecule, and generally known ones can be used. For example: bisphenol A type benzopyrene?? BA-BXZ (made by Xiaoxi Chemical, trade name) bisphenol F type benzopyrene?? BF-BXZ (made by Xiaoxi Chemical, trade name), bisphenol S type benzopyrene ?? BS-BXZ (small West chemical system, trade name), phenol phenolphthalein type benzopyrene, etc., without special restrictions. These may be used alone or in combination of two or more.

苯并㗁??化合物之含量無特殊限制,相對於樹脂組成物中之樹脂固體成分100質量份較佳為0.1質量份~50質量份,更佳為0.2質量份~45質量份,又更佳為0.3質量份~40質量份。苯并㗁??化合物之含量藉由為上述範圍內,耐熱性有更為提升的傾向。The content of the benzopyrene compound is not particularly limited, and is preferably 0.1 part by mass to 50 parts by mass, more preferably 0.2 part by mass to 45 parts by mass, even more preferably 100 parts by mass of the resin solid content in the resin composition. It is 0.3 parts by mass to 40 parts by mass. When the content of the benzopyrene compound is within the above range, the heat resistance tends to be further improved.

<具有乙烯性不飽和基之化合物> 本實施形態之樹脂組成物中,為了提高熱硬化性及利用活性能量射線之硬化性(例如利用紫外線之光硬化性等),也可以併用具有乙烯性不飽和基之化合物。本實施形態使用之具有乙烯性不飽和基之化合物,只要是在1分子中具有1個以上之乙烯性不飽和基之化合物即可,並不特別限定,例如具有(甲基)丙烯醯基、乙烯基等之化合物。此等可以使用1種或適當混用2種以上。<Compound having an ethylenically unsaturated group> In the resin composition of the present embodiment, in order to improve the thermosetting property and the curability of the active energy ray (for example, photocurability by ultraviolet light), it may be used in combination with ethylene. A compound of a saturated group. The compound having an ethylenically unsaturated group used in the present embodiment is not particularly limited as long as it has one or more ethylenically unsaturated groups in one molecule, and has, for example, a (meth) acrylonitrile group. A compound such as a vinyl group. These may be used alone or in combination of two or more.

作為具有(甲基)丙烯醯基之化合物,可以列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸月桂酯、聚乙二醇(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯單甲醚、(甲基)丙烯酸苯基乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸四氫呋喃甲酯、二(甲基)丙烯酸丁二醇酯、己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、壬二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二甘醇酯、二(甲基)丙烯酸二乙烯酯、聚乙二醇二(甲基)丙烯酸酯、參(甲基)丙烯醯氧基乙基異氰尿酸酯、聚丙二醇二(甲基)丙烯酸酯、己二酸環氧二(甲基)丙烯酸酯、雙酚氧乙烯二(甲基)丙烯酸酯、氫化雙酚氧乙烯(甲基)丙烯酸酯、雙酚二(甲基)丙烯酸酯、ε-己內酯改性羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、ε-己內酯改性二新戊四醇六(甲基)丙烯酸酯、 ε-己內酯改性二新戊四醇聚(甲基)丙烯酸酯、二新戊四醇聚(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥乙基丙烷三(甲基)丙烯酸酯、及其之環氧乙烷加成物、三(甲基)丙烯酸新戊四醇酯、及其之環氧乙烷加成物、新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、及其之環氧乙烷加成物等。Examples of the compound having a (meth)acryl fluorenyl group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, and polyethylene glycol. (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenyl ethyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Benzyl (meth) acrylate, tetrahydrofuran (meth) acrylate, butylene glycol di (meth) acrylate, hexane diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Decylene di(meth)acrylate, diethylene glycol di(meth)acrylate, divinyl (meth)acrylate, polyethylene glycol di(meth)acrylate, cis (meth) propylene Ethoxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenoloxyethylene di(meth)acrylate, hydrogenated bisphenol oxygen Ethylene (meth) acrylate, bisphenol di(meth) acrylate, ε-caprolactone modified hydroxytrimethylacetic acid neopentyl glycol di(meth) acrylate, ε-caprolactone modified New Tetraol hexa(meth) acrylate, ε-caprolactone-modified dipentaerythritol poly(meth) acrylate, dipentaerythritol poly(meth) acrylate, trimethylolpropane tri Methyl) acrylate, triethylolpropane tri(meth) acrylate, ethylene oxide adduct thereof, neopentyl glycol tri(meth)acrylate, and ethylene oxide plus The product, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, an ethylene oxide adduct thereof, and the like.

此外,尚可列舉在同一分子內同時具有(甲基)丙烯醯基與胺甲酸乙酯鍵之胺甲酸乙酯(甲基)丙烯酸酯類、同樣在同一分子內同時具有(甲基)丙烯醯基與酯鍵之聚酯(甲基)丙烯酸酯、從環氧樹脂衍生且同時具有(甲基)丙烯醯基之環氧(甲基)丙烯酸酯類、該等鍵結複合地使用之反應性寡聚物等。Further, an urethane (meth) acrylate having both a (meth) acrylonitrile group and an urethane bond in the same molecule, and also having (meth) propylene oxime in the same molecule Polyester (meth) acrylate having an ester bond and an epoxy (meth) acrylate derived from an epoxy resin and having a (meth) acrylonitrile group, and reactivity of the bonds Oligomers, etc.

上述胺甲酸乙酯(甲基)丙烯酸酯類,係含有羥基之(甲基)丙烯酸酯與聚異氰酸酯、與視需要使用之其他醇類之反應物。例如:(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯等(甲基)丙烯酸羥基烷酯類、甘油單(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯等甘油(甲基)丙烯酸酯類、二(甲基)丙烯酸新戊四醇酯、三(甲基)丙烯酸新戊四醇酯、五(甲基)丙烯酸二新戊四醇酯等糖醇(甲基)丙烯酸酯類,與甲苯二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、降莰烯二異氰酸酯、二甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、二環己烷亞甲基二異氰酸酯、及它們的異氰尿酸酯、雙縮脲反應物等聚異氰酸酯等反應,成為胺甲酸乙酯(甲基)丙烯酸酯類。The urethane (meth) acrylate is a reaction product of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols as needed. For example: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, glycerol Glycerol (meth) acrylate such as (meth) acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate Sugar alcohol (meth) acrylates such as alcohol esters, with toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, decene diisocyanate, xylene Reaction of diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane methylene diisocyanate, and polyisocyanate such as isocyanurate or biuret reactant to form ethyl urethane (meth) acrylate class.

上述環氧(甲基)丙烯酸酯類,係具有環氧基之化合物與(甲基)丙烯酸之羧酸酯化合物。例如:苯酚酚醛清漆型環氧(甲基)丙烯酸酯、甲酚酚醛清漆型環氧(甲基)丙烯酸酯、參羥基苯基甲烷型環氧(甲基)丙烯酸酯、二環戊二烯苯酚型環氧(甲基)丙烯酸酯、雙酚A型環氧(甲基)丙烯酸酯、雙酚F型環氧(甲基)丙烯酸酯、聯苯酚型環氧(甲基)丙烯酸酯、雙酚A酚醛清漆型環氧(甲基)丙烯酸酯、萘骨架含有環氧(甲基)丙烯酸酯、乙二醛型環氧(甲基)丙烯酸酯、雜環族環氧(甲基)丙烯酸酯、及該等之酸酐改性環氧(甲基)丙烯酸酯、前述通式(1)表示之化合物等。The above epoxy (meth) acrylate is a compound having an epoxy group and a carboxylic acid ester compound of (meth)acrylic acid. For example: phenol novolac type epoxy (meth) acrylate, cresol novolak type epoxy (meth) acrylate, hydroxy phenyl methane type epoxy (meth) acrylate, dicyclopentadienyl phenol Epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, biphenol epoxy (meth) acrylate, bisphenol A novolac type epoxy (meth) acrylate, naphthalene skeleton containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy (meth) acrylate, And the acid anhydride-modified epoxy (meth) acrylate, the compound represented by the above formula (1), and the like.

前述通式(1)中,多個R1 各自獨立地表示氫原子或甲基。其中,考量使光硬化反應之反應性提高的觀點,含有氫原子較佳,更佳為R1 皆為氫原子。In the above formula (1), a plurality of R 1 each independently represent a hydrogen atom or a methyl group. Among them, the viewpoint of improving the reactivity of the photo-curing reaction is preferably a hydrogen atom, and more preferably R 1 is a hydrogen atom.

多個R2 各自獨立地表示氫原子或甲基。其中,考量使硬化物之耐熱性提高的觀點,宜含有甲基較佳,更佳為R2 皆是甲基。A plurality of R 2 each independently represent a hydrogen atom or a methyl group. Among them, from the viewpoint of improving the heat resistance of the cured product, it is preferred to contain a methyl group, and it is more preferred that both of R 2 are a methyl group.

多個R3 各自獨立地表示前述式(2)表示之取代基、前述式(3)表示之取代基或羥基。其中,考量使耐熱性增進之觀點,宜含有羥基較佳。又,本實施形態中,使用多個R3 當中包括前述式(2)表示之取代基之化合物的話,考量使顯影性提升的觀點,為較理想。本實施形態中,使用多個R3 當中包括前述式(3)表示之取代基之化合物的話,從使耐熱性提升的觀點,較為理想。前述式(3)中,R4 表示氫原子或甲基。其中,考量使光硬化反應之反應性提高的觀點,氫原子較佳。The plurality of R 3 each independently represent a substituent represented by the above formula (2), a substituent represented by the above formula (3) or a hydroxyl group. Among them, in view of the viewpoint of improving heat resistance, it is preferred to contain a hydroxyl group. In the present embodiment, when a plurality of compounds including the substituent represented by the above formula (2) among R 3 are used, it is preferable from the viewpoint of improving developability. In the present embodiment, when a plurality of compounds including the substituent represented by the above formula (3) among R 3 are used, it is preferable from the viewpoint of improving heat resistance. In the above formula (3), R 4 represents a hydrogen atom or a methyl group. Among them, a hydrogen atom is preferred from the viewpoint of improving the reactivity of the photohardening reaction.

考量使顯影性增進之觀點,多個R3 的全部R3 的取代基當中,前述式(2)表示之取代基之比率為20%以上85%以下、前述式(3)表示之取代基之比率為5%以上70%以下、羥基之比率為10%以上75%以下較佳。 前述通式(1)表示之化合物若含有以下之化合物(A1)~(A5)中任一種以上,則能使光硬化反應之反應性、硬化物之耐熱性及顯影性提升,較為理想至少含有化合物(A1)更佳,含有(A1)~(A5)中之任2種以上更理想,含有化合物(A1)及化合物(A2)~(A5)中之任1種以上又更佳。至少含有化合物(A2)及(A3)作為化合物(A)亦為理想。In view of the improvement of the developability, among the substituents of all R 3 of the plurality of R 3 , the ratio of the substituent represented by the above formula (2) is 20% or more and 85% or less, and the substituent represented by the above formula (3) The ratio is preferably 5% or more and 70% or less, and the ratio of the hydroxyl group is preferably 10% or more and 75% or less. When the compound represented by the above formula (1) contains at least one of the following compounds (A1) to (A5), the reactivity of the photocuring reaction and the heat resistance and developability of the cured product can be improved, and it is preferable to contain at least The compound (A1) is more preferably contained in any one or more of (A1) to (A5), and more preferably one or more of the compound (A1) and the compound (A2) to (A5). It is also preferable to contain at least the compound (A2) and (A3) as the compound (A).

【化10】 【化10】

【化11】 【化11】

【化12】 【化12】

【化13】 【化13】

【化14】 【化14】

考量使顯影性提升的觀點,前述通式(1)表示之化合物之酸價為30mgKOH/g以上,考量使顯影性更提高之觀膽,50mgKOH/g以上較佳。又,考量防止以活性能量射線硬化後由於顯影液導致溶解之觀點,前述通式(1)表示之化合物之酸價為120mgKOH/g以下,考量更能防止溶解之觀點,110mgKOH/g以下較佳。又,本實施形態中之「酸價」代表依循JISK 0070:1992之方法測定之値。In view of the improvement of the developability, the acid value of the compound represented by the above formula (1) is 30 mgKOH/g or more, and the effect of improving the developability is considered to be 50 mgKOH/g or more. In addition, the acid value of the compound represented by the above formula (1) is 120 mgKOH/g or less, and the viewpoint of preventing dissolution more is considered from the viewpoint of preventing dissolution by the developer after the active energy ray is hardened, and 110 mgKOH/g or less is preferable. . Further, the "acid value" in the present embodiment represents the enthalpy measured by the method according to JIS K 0070:1992.

酸酐改性環氧丙烯酸酯可以列舉酸改性雙酚F型環氧丙烯酸酯。 它們也可使用市售品,可以列舉前述通式(1)表示者,例如:日本化藥(股)製之、KAYARAD(註冊商標)ZCR-6001H、KAYARAD(註冊商標)ZCR-6002H、KAYARAD(註冊商標)ZCR-6006H、KAYARAD(註冊商標)ZCR-6007H、KAYAR AD(註冊商標)ZCA-601H(以上,為商品名)等。又,就酸改性雙酚F型環氧丙烯酸酯而言,可以列舉日本化藥(股)製之KAYARAD(註冊商標)ZFR-1553H(商品名)。The acid anhydride-modified epoxy acrylate may, for example, be an acid-modified bisphenol F-type epoxy acrylate. Commercially available products can also be used, and those represented by the above formula (1) can be used, for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD ( Registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR-6007H, KAYAR AD (registered trademark) ZCA-601H (above, trade name), etc. In addition, as for the acid-modified bisphenol F-type epoxy acrylate, KAYARAD (registered trademark) ZFR-1553H (trade name) manufactured by Nippon Kayaku Co., Ltd. can be cited.

作為具有乙烯基之化合物,可以列舉乙基乙烯醚、丙基乙烯醚、羥基乙基乙烯醚、乙二醇二乙烯醚、具有乙烯基之2官能性伸苯醚寡聚物等乙烯醚類。苯乙烯類可列舉苯乙烯、甲基苯乙烯、乙基苯乙烯、二乙烯基苯、α-甲基苯乙烯、及該等之寡聚物等。其他乙烯基化合物可以列舉異氰尿酸三烯丙酯、異氰尿酸三甲基烯丙酯、雙烯丙基納迪克醯亞胺等。Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and a bifunctional phenylene ether oligomer having a vinyl group. Examples of the styrene include styrene, methyl styrene, ethyl styrene, divinyl benzene, α-methyl styrene, and the like. Examples of the other vinyl compound include triallyl isocyanurate, trimethylallyl isocyanurate, bisallyl nadicylimine, and the like.

該等之中,宜為選自於由具乙烯基之2官能性伸苯醚寡聚物、α-甲基苯乙烯之寡聚物、酸改性雙酚F型環氧(甲基)丙烯酸酯、前述通式(1)表示之化合物、四(甲基)丙烯酸新戊四醇酯、六(甲基)丙烯酸二新戊四醇酯、甲酚酚醛清漆型環氧(甲基)丙烯酸酯、雙酚A型環氧(甲基)丙烯酸酯、萘骨架含有環氧(甲基)丙烯酸酯、雙烯丙基納迪克醯亞胺構成之群組中之至少1種以上較佳。若為選自於由具乙烯基之2官能性伸苯醚寡聚物、α-甲基苯乙烯之寡聚物、酸改性雙酚F型環氧(甲基)丙烯酸酯、前述通式(1)表示之化合物及六(甲基)丙烯酸二新戊四醇酯構成之群組中的1種以上,從可獲得良好耐熱性、介電常數、介電正切之觀點,更為理想。Among these, it is preferably selected from the group consisting of a bifunctional phenylene oxide oligomer having a vinyl group, an oligomer of α-methylstyrene, and an acid-modified bisphenol F-type epoxy (meth)acrylic acid. Ester, a compound represented by the above formula (1), neopentyl tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, cresol novolac epoxy (meth) acrylate At least one of the group consisting of bisphenol A epoxy (meth) acrylate and naphthalene skeleton containing epoxy (meth) acrylate and bisallyl nadic ylideneimide is preferred. If it is selected from a bifunctional phenylene oxide oligomer having a vinyl group, an oligomer of α-methylstyrene, an acid-modified bisphenol F-type epoxy (meth) acrylate, the above formula One or more of the group of the compound represented by the above (1) and the neopentyl glycol hexa(meth)acrylate are more preferable from the viewpoint of obtaining good heat resistance, dielectric constant, and dielectric tangent.

需要熱硬化性時,具乙烯基之2官能性伸苯醚寡聚物及/或α-甲基苯乙烯之寡聚物,因為會良好地熱硬化且有良好的微細配線的填埋性、焊料耐熱性、介電常數、介電正切優異,故為理想。需要光硬化性時,若含有選自於由酸改性雙酚F型環氧(甲基)丙烯酸酯、前述通式(1)表示之化合物及六(甲基)丙烯酸二新戊四醇酯構成之群組中之至少1種以上,則有良好的微細配線的填埋性及焊料耐熱性、且介電常數、介電正切及顯影性也優良,故為理想,使用前述通式(1)表示之化合物的話,耐熱性更優異,故為理想。藉由含有如此的種類具乙烯性不飽和基的化合物,獲得之硬化物的耐熱性有更為提升的傾向。 該等具乙烯性不飽和基之化合物可使用1種或將2種以上適當混用。又,該等具乙烯性不飽和基之化合物也可以含有結構異構物及立體異構物等異構物,也可將2種以上之結構彼此相異之化合物適當組合使用。When a thermosetting property is required, a bifunctional phenylene oxide oligomer having a vinyl group and/or an oligomer of α-methyl styrene is well thermally hardened and has good landfill properties of fine wiring, solder It is excellent in heat resistance, dielectric constant, and dielectric tangent. When photocurability is required, it is selected from an acid-modified bisphenol F-type epoxy (meth) acrylate, a compound represented by the above formula (1), and dipentaerythritol hexa(meth)acrylate. At least one or more of the groups are excellent in the filling property of the fine wiring and the solder heat resistance, and also excellent in dielectric constant, dielectric tangent, and developability. Therefore, it is preferable to use the above formula (1). When the compound is represented, it is more excellent in heat resistance. By containing such a compound having an ethylenically unsaturated group, the heat resistance of the cured product obtained tends to be further improved. These compounds having an ethylenically unsaturated group may be used alone or in combination of two or more. Further, the compound having an ethylenically unsaturated group may contain an isomer such as a structural isomer or a stereoisomer, or two or more compounds having different structures may be used in combination as appropriate.

具乙烯性不飽和基之化合物之含量無特殊限制,相對於樹脂組成物中之樹脂固體成分100質量份較佳為0.1質量份~90質量份,更佳為0.2質量份~85質量份。 具乙烯性不飽和基之化合物藉由為上述範圍內,焊料耐熱性有更為提升的傾向。 尤其,於要求熱硬化性時,可良好地熱硬化,考量獲得良好的微細配線的填埋性及焊料耐熱性、介電常數、介電正切,具乙烯性不飽和基之化合物之含量相對於樹脂組成物中之樹脂固體成分100質量份較佳為5質量份~90質量份,更佳為7質量份~85質量份,又更佳為10質量份~83質量份。又,於要求光硬化性時,考量可獲得良好的微細配線的填埋性及焊料耐熱性、介電常數、介電正切及顯影性的觀點,具乙烯性不飽和基之化合物之含量相對於樹脂組成物中之樹脂固體成分100質量份較佳為5質量份~90質量份,更佳為7質量份~85質量份,又更佳為10質量份~80質量份,更佳為10質量份~73質量份。The content of the compound having an ethylenically unsaturated group is not particularly limited, and is preferably from 0.1 part by mass to 90 parts by mass, more preferably from 0.2 part by mass to 85 parts by mass, per 100 parts by mass of the resin solid content in the resin composition. When the compound having an ethylenically unsaturated group is in the above range, the solder heat resistance tends to be further improved. In particular, when thermosetting property is required, it can be thermally cured favorably, and it is considered that good filling property of fine wiring, solder heat resistance, dielectric constant, dielectric tangent, and content of compound having ethylenic unsaturated group relative to resin are obtained. The resin solid content in the composition is preferably from 5 parts by mass to 90 parts by mass, more preferably from 7 parts by mass to 85 parts by mass, even more preferably from 10 parts by mass to 83 parts by mass, based on 100 parts by mass of the resin solid content. In addition, when photocurability is required, the content of a compound having an ethylenically unsaturated group is compared with respect to the viewpoint of obtaining a good filling property of a fine wiring, solder heat resistance, dielectric constant, dielectric tangent, and developability. 100 parts by mass of the resin solid content in the resin composition is preferably 5 parts by mass to 90 parts by mass, more preferably 7 parts by mass to 85 parts by mass, still more preferably 10 parts by mass to 80 parts by mass, still more preferably 10 parts by mass. Parts ~ 73 parts by mass.

<被覆有二氧化矽之氟樹脂粒子(A)以外之填充材(C)> 本實施形態之樹脂組成物中,在無損本實施形態之特性之範圍中,也可以含有被覆有二氧化矽之氟樹脂粒子(A)以外之填充材(C)(以下稱為其他填充材(C))。藉由併用其他填充材(C),能夠使硬化物之阻燃性、耐熱性、熱膨脹特性等所望特性增進。<Filling material (C) other than fluororesin particles (A) coated with cerium oxide> The resin composition of the present embodiment may contain a ruthenium dioxide coated portion insofar as it does not impair the characteristics of the present embodiment. A filler (C) other than the fluororesin particles (A) (hereinafter referred to as another filler (C)). By using other fillers (C) in combination, it is possible to improve the desired properties such as flame retardancy, heat resistance, and thermal expansion characteristics of the cured product.

其他填充材(C)只要是有絕緣性者即可,不特別限定,例如:天然二氧化矽、熔融二氧化矽、合成二氧化矽、非晶質二氧化矽、Aerosil、中空二氧化矽等二氧化矽類、白碳、鈦白、氧化鋅、氧化鎂、氧化鋯等氧化物、氮化硼、凝聚氮化硼、氮化矽、氮化鋁、硫酸鋇、氫氧化鋁、氫氧化鋁加熱處理品(將氫氧化鋁進行加熱處理,減少了一部分結晶水者)、軟水鋁石、氫氧化鎂等金屬水合物、氧化鉬、鉬酸鋅等鉬化合物、硼酸鋅、錫酸鋅、氧化鋁、黏土、高嶺土、滑石、煅燒黏土、煅燒高嶺土、煅燒滑石、雲母、E-玻璃、A-玻璃、NE-玻璃、C-玻璃、L-玻璃、D-玻璃、S-玻璃、M-玻璃G20、玻璃短纖維(包括E玻璃、T玻璃、D玻璃、S玻璃、Q玻璃等玻璃微粉末類)、中空玻璃、球狀玻璃等無機系之填充材,以外,可列舉苯乙烯型、丁二烯型、丙烯酸型等橡膠粉末、核殼型之橡膠粉末、及聚矽氧樹脂粉末、聚矽氧橡膠粉末、聚矽氧複合粉末等有機系之填充材等。其中,選自於由二氧化矽、氫氧化鋁、軟水鋁石、氧化鎂、氫氧化鎂、及硫酸鋇構成之群組中之1種以上較佳。此等可以使用1種或適當混用2種以上。 該等其他填充材(C)也可以經後述矽烷偶聯劑等表面處理。The other filler (C) is not particularly limited as long as it is insulating, and examples thereof include natural cerium oxide, molten cerium oxide, synthetic cerium oxide, amorphous cerium oxide, Aerosil, hollow cerium oxide, and the like. Oxide such as cerium oxide, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, condensed boron nitride, tantalum nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide Heat treated products (heat treated with aluminum hydroxide to reduce some of the water of crystallization), metal hydrates such as soft boehmite and magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, and oxidation Aluminum, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass micro-powders such as E glass, T glass, D glass, S glass, and Q glass), inorganic filler materials such as hollow glass and spherical glass, and styrene type and butyl Rubber powder such as diene type or acrylic type, core-shell type Gum powder, silicone and polyethylene powder, polyethylene oxide rubber, silicone powder, polyethylene silicon oxide composite powder of an organic filler and the like. Among them, one or more selected from the group consisting of cerium oxide, aluminum hydroxide, boehmite, magnesium oxide, magnesium hydroxide, and barium sulfate are preferred. These may be used alone or in combination of two or more. These other fillers (C) may be subjected to surface treatment such as a decane coupling agent to be described later.

尤其,考量使硬化物之耐熱性增進之觀點,二氧化矽較理想,熔融二氧化矽特別理想。二氧化矽之具體例可列舉Denka(股)製之SFP-130MC等、Admatechs (股)製之SC2050-MB、SC2050-MNU、SC1050-MLE、YA010C-MFN、YA050C-MJA等。In particular, in view of improving the heat resistance of the cured product, cerium oxide is preferable, and molten cerium oxide is particularly preferable. Specific examples of the cerium oxide include SFP-130MC manufactured by Denka Co., Ltd., SC2050-MB, SC2050-MNU, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Co., Ltd., and the like.

其他填充材(C)之平均粒徑不特別限定,考量使樹脂組成物中之其他填充材(C)之分散性為良好之觀點,中位徑宜為15μm以下較佳。又,考量使樹脂組成物中之其他填充材(C)之分散性為良好之觀點,中位徑為0.005μm以上較佳。The average particle diameter of the other filler (C) is not particularly limited, and the dispersibility of the other filler (C) in the resin composition is considered to be good, and the median diameter is preferably 15 μm or less. Moreover, from the viewpoint of making the dispersibility of the other filler (C) in the resin composition good, the median diameter is preferably 0.005 μm or more.

又,本說明書中,「中位徑」係指將某粒徑作為基準,將粉體之粒度分布分為2邊時,粒徑較大側之粒子之個數或質量與粒徑較小側之個數或質量佔全部粉體之各50%之粒徑。中位徑可利用濕式雷射繞射・散射法測定。In the present specification, the "median diameter" refers to the number of particles having a larger particle diameter or the smaller side of the mass and the particle diameter when the particle size distribution of the powder is divided into two sides using a certain particle diameter as a reference. The number or mass accounts for 50% of the particle size of all the powders. The median diameter can be measured by wet laser diffraction/scattering.

本實施形態之樹脂組成物中,其他填充材(C)之含量不特別限定,考量使硬化物之耐熱性增進之觀點,相對於樹脂組成物100質量份為5質量份以上較佳,10質量份以上更佳,20質量份以上又更理想。又,考量使樹脂組成物之顯影性、微細配線之填埋性良好之觀點,相對於樹脂組成物100質量份為400質量份以下較佳,350質量份以下更佳,300質量份以下又更佳、100質量份以下更理想。In the resin composition of the present embodiment, the content of the other filler (C) is not particularly limited, and from the viewpoint of improving the heat resistance of the cured product, it is preferably 5 parts by mass or more, and 10 parts by mass, based on 100 parts by mass of the resin composition. More preferably, more than 20 parts by mass is more desirable. In addition, it is preferable that it is 400 parts by mass or less, more preferably 350 parts by mass or less, and more preferably 300 parts by mass or less with respect to 100 parts by mass of the resin composition, from the viewpoint of the improvement of the developability of the resin composition and the filling property of the fine wiring. Good, 100 parts by mass or less is more desirable.

<矽烷偶聯劑及濕潤分散劑> 本實施形態之樹脂組成物中,在無損本實施形態之特性之範圍內,也可以含有矽烷偶聯劑及/或濕潤分散劑。藉由併用矽烷偶聯劑及/或濕潤分散劑,能夠使填充材之分散性、樹脂與填充材之黏著強度等所望特性提升。<Heterane Coupling Agent and Wetting Dispersing Agent> The resin composition of the present embodiment may contain a decane coupling agent and/or a wetting dispersing agent within a range not impairing the characteristics of the present embodiment. By using a decane coupling agent and/or a wetting dispersing agent together, it is possible to improve the dispersibility of the filler, the adhesive strength of the resin and the filler, and the like.

矽烷偶聯劑只要是一般使用在填充材之表面處理之矽烷偶聯劑即可,並無特殊限制。具體例,例如:乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等乙烯基矽烷系、γ-胺基丙基三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷等胺基矽烷系;γ-環氧丙氧基丙基三甲氧基矽烷等環氧矽烷系;γ-丙烯醯氧基丙基三甲氧基矽烷等丙烯酸基矽烷系;N-β-(N-乙烯基苄胺基乙基)-γ-胺基丙基三甲氧基矽烷鹽酸鹽、N-(乙烯基苯)-2-胺基乙基-3-胺基丙基三甲氧基矽烷之鹽酸鹽等陽離子性矽烷系;苯基矽烷系之矽烷偶聯劑等。該等矽烷偶聯劑可單獨使用1種或適當組合使用2種以上。The decane coupling agent is not particularly limited as long as it is a decane coupling agent which is generally used for the surface treatment of the filler. Specific examples are, for example, vinyl decane such as vinyl trimethoxy decane or vinyl triethoxy decane, γ-aminopropyl triethoxy decane, and N-β-(aminoethyl)-γ-. An alkyl decane series such as aminopropyltrimethoxy decane; an epoxy decane system such as γ-glycidoxypropyltrimethoxy decane; and an acryl decane series such as γ-acryloxypropyltrimethoxydecane N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane hydrochloride, N-(vinylbenzene)-2-aminoethyl-3-amine a cationic decane type such as a propyl trimethoxy decane hydrochloride; a phenyl decane-based decane coupling agent. These decane coupling agents may be used alone or in combination of two or more.

本實施形態之樹脂組成物中,矽烷偶聯劑之含量不特別限定,通常相對於樹脂組成物100質量份為0.1~10質量份。In the resin composition of the present embodiment, the content of the decane coupling agent is not particularly limited, and is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition.

濕潤分散劑只要是在塗料用途使用之分散安定劑即可,並無特殊限制。具體例,例如:BYK Chemie Japan(股)製之DISPERBYK(註冊商標)-110、111、118、180、161、BYK(註冊商標)-W996、W9010、W903等濕潤分散劑。此等濕潤分散劑可單獨使用1種或將2種以上適當混用。 本實施形態之樹脂組成物中,濕潤分散劑之含量不特別限定,通常相對於樹脂組成物100質量份為0.1~10質量份。The wetting dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for coating applications. Specific examples are, for example, DISPERBYK (registered trademark)-110, 111, 118, 180, 161, BYK (registered trademark)-W996, W9010, W903, etc., manufactured by BYK Chemie Japan Co., Ltd., and the like. These wetting dispersing agents may be used alone or in combination of two or more. In the resin composition of the present embodiment, the content of the wetting dispersant is not particularly limited, and is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition.

<阻燃劑(D)> 本實施形態之樹脂組成物中,在無損本實施形態之特性之範圍內也可以含有阻燃劑(D)。藉由併用阻燃劑(D),能夠使硬化物之阻燃性、耐熱性、熱膨脹特性等所望特性增進。<Flame Retardant (D)> The resin composition of the present embodiment may contain the flame retardant (D) within the range which does not impair the characteristics of the present embodiment. By using the flame retardant (D) in combination, the desired properties such as flame retardancy, heat resistance, and thermal expansion properties of the cured product can be improved.

阻燃劑(D)只要是有絕緣性者即可,可使用一般公知者。例如:溴化聚碳酸酯、十溴二苯基乙烷、4,4-二溴聯苯、乙烯雙四溴鄰苯二甲醯亞胺等溴化有機化合物,並無特殊限制。它們可單獨使用1種或將2種以上適當混用。 本實施形態之樹脂組成物中,阻燃劑(D)之含量不特別限定,通常相對於樹脂組成物中之樹脂組成物100質量份為0.1~10質量份,較佳為1~10質量份。The flame retardant (D) may be any one as long as it has insulation properties, and generally known ones can be used. For example, a brominated organic compound such as brominated polycarbonate, decabromodiphenylethane, 4,4-dibromobiphenyl or ethylene bistetrabromophthalimide is not particularly limited. These may be used alone or in combination of two or more. In the resin composition of the present embodiment, the content of the flame retardant (D) is not particularly limited, and is usually 0.1 to 10 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the resin composition in the resin composition. .

<光硬化起始劑(E)> 本實施形態之樹脂組成物中,當使用能利用紫外線等予以光硬化之樹脂成分(馬來醯亞胺化合物、環氧樹脂、具乙烯性不飽和基之化合物、苯酚樹脂、氧雜環丁烷樹脂等)作為樹脂成分(B)時,為了使其光硬化性增進,也可在無損本實施形態之特性之範圍內含有光硬化起始劑(E)。 光硬化起始劑(E)不特別限定,可使用一般在光硬化性樹脂組成物中使用的領域中公知者。<Photohardening initiator (E)> In the resin composition of the present embodiment, a resin component (maleimide compound, epoxy resin, or ethylenically unsaturated group) which can be photocured by ultraviolet rays or the like is used. When the compound (B) is used as the resin component (B), the photocuring initiator (E) may be contained in the range which does not impair the characteristics of the embodiment. . The photohardening initiator (E) is not particularly limited, and those generally used in the photocurable resin composition can be used.

例如:苯偶因、苯偶因甲醚、苯偶因乙醚、苯偶因丙醚、苯偶因異丁醚等苯偶因類、過氧化苯甲醯、過氧化月桂醯、過氧化乙醯、對氯過氧化苯甲醯、二過氧化鄰苯二甲酸二第三丁酯等有機過氧化物、苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、2-羥基-2-甲基-苯基丙烷-1-酮、二乙氧基苯乙酮、1-羥基環己基苯酮、2-甲基-1-[4-(甲硫基)苯基]-2-??啉代-丙烷-1-酮等苯乙酮類、2-乙基蒽醌、2-第三丁基蒽醌、2-氯蒽醌、2-戊基蒽醌等蒽醌類、2,4-二乙基噻吨酮、2-異丙基噻吨酮、2-氯噻吨酮等噻吨酮類、苯乙酮二甲基縮酮、苄基二甲基縮酮等縮酮類、二苯酮、4-苯甲醯基-4’-甲基二苯基硫醚、4,4’-雙甲胺基二苯酮等二苯酮類、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等氧化膦類、1,2-辛烷二酮,1-[4-(苯硫基) -,2-(O-苯甲醯肟)]等肟酯類等自由基型光硬化起始劑、氟膦酸對甲氧基苯基重氮鹽、六氟膦酸N,N-二乙胺基苯基重氮鹽等路易士酸之重氮鹽、二苯基錪六氟膦酸鹽、六氟銻酸二苯基錪鹽等路易士酸之錪鹽、六氟膦酸三苯基鋶鹽、六氟銻酸三苯基鋶鹽等路易士酸的鋶鹽、六氟銻酸三苯基鏻鹽等路易士酸之鏻鹽、其他的鹵化物、三??系起始劑、硼酸鹽系起始劑、及其他之光酸產生劑等陽離子系光聚合起始劑。For example: benzoin, benzoin methyl ether, benzoin ether, benzoin propyl ether, benzoin isobutyl ether and other benzoin, benzammonium peroxide, laurel, ruthenium peroxide , organic peroxides such as benzyl peroxide, benzoic acid dibutyl phthalate, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, Acetophenones such as 1-hydroxycyclohexyl benzophenone and 2-methyl-1-[4-(methylthio)phenyl]-2-?-morpholino-propan-1-one, 2-ethylhydrazine Anthraquinone, 2-tert-butylhydrazine, 2-chloroindole, 2-pentylhydrazine, etc., 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2- a ketoxime such as thioxanthone, a ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal, a benzophenone or a 4-benzylidene-4'-methyldiphenyl group Dibenzophenones such as thioethers, 4,4'-bismethylaminobenzophenone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethyl) Phosphine oxides such as benzyl benzhydryl)-phenylphosphine oxide, 1,2-octanedione, 1-[4 a radical photohardening initiator such as -(phenylthio)-,2-(O-benzhydrazide)], an oxime ester such as p-methoxyphenyldiazonium fluorophosphonate or hexafluorophosphonic acid a diazonium salt of Lewis acid such as N,N-diethylaminophenyldiazonium salt, diphenylsulfonium hexafluorophosphonate, diphenylphosphonium hexafluoroantimonate or the like, and a salt of Lewis acid, six Barium salts of Lewis acid such as triphenylsulfonium fluorophosphonate and triphenylsulfonium hexafluoroantimonate, barium salts of Lewis acid such as triphenylsulfonium hexafluoroantimonate, other halides, and three? A cationic photopolymerization initiator such as a starter, a borate initiator, and other photoacid generators.

其中,考量有適於多層印刷電路板用途之反應性,對於金屬導體之可靠性高之觀點,2-苄基-2-二甲胺基-1-(4-??啉代苯基)-丁-1酮(BASF Japan(股)製,Irgacu re(註冊商標)369)等苯乙酮類之自由基型光硬化起始劑為較佳。Among them, consideration is given to the reactivity suitable for the use of multilayer printed circuit boards, and the viewpoint of high reliability of metal conductors, 2-benzyl-2-dimethylamino-1-(4-?-morpholinophenyl)- A radically-type photohardening initiator of acetophenone such as butan-1 ketone (manufactured by BASF Japan Co., Ltd., Irgacu re (registered trademark) 369) is preferred.

該等光硬化起始劑(E)可以單獨使用1種或將2種以上適當混用,也可以併用自由基系與陽離子系之兩者的起始劑。These photohardening initiators (E) may be used singly or in combination of two or more kinds thereof, or a combination of a radical and a cationic one.

本實施形態之樹脂組成物中,光硬化起始劑(E)之含量不特別限定,考量使樹脂組成物以活性能量射線充分硬化,使耐熱性增進之觀點,相對於樹脂組成物中之樹脂固體成分100質量份為0.1質量份以上較佳,0.2質量份以上更佳,0.3質量份以上又更佳,1質量份以上更理想。又,考量抑制光硬化後之熱硬化並降低耐熱性之觀點,相對於樹脂組成物中之樹脂固體成分100質量份為30質量份以下較佳,25質量份以下更佳,20質量份以下又更佳,10質量份以下更理想。In the resin composition of the present embodiment, the content of the photo-curing initiator (E) is not particularly limited, and the resin composition is sufficiently cured by active energy rays to improve heat resistance, and the resin in the resin composition is considered. 100 parts by mass of the solid component is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and still more preferably 1 part by mass or more. In addition, it is preferable that it is 30 parts by mass or less, more preferably 25 parts by mass or less, and more preferably 20 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of suppressing heat hardening after photohardening and lowering heat resistance. More preferably, 10 parts by mass or less is more desirable.

<熱硬化促進劑> 本實施形態之樹脂組成物中,在無損本實施形態之特性之範圍內,也可以併用熱硬化促進劑。熱硬化促進劑不特別限定,例如:過氧化苯甲醯、過氧化月桂醯、過氧化乙醯、對氯過氧化苯甲醯、二過氧化鄰苯二甲酸二第三丁酯等例示之有機過氧化物;偶氮雙腈等偶氮化合物;N,N-二甲基苄胺、N,N-二甲基苯胺、N,N-二甲基甲苯胺、2-N-乙基苯胺基乙醇、三正丁胺、吡啶、喹啉、N-甲基??啉、三乙醇胺、三乙二胺、四甲基丁烷二胺、N-甲基哌啶等三級胺類;苯酚、二甲酚、甲酚、間苯二酚、兒茶酚等苯酚類;環烷酸鉛、硬脂酸鉛、環烷酸鋅、辛酸鋅、油酸錫、蘋果酸二丁基錫、環烷酸錳、環烷酸鈷、乙醯基丙酮鐵等有機金屬鹽;此等有機金屬鹽溶於苯酚、雙酚等含有羥基之化合物而成者;氯化錫、氯化鋅、氯化鋁等無機金屬鹽;二辛基氧化錫、其他之烷基錫、烷基氧化錫等有機錫化合物;1,2-二甲基咪唑、1-苄基-2-苯基咪唑、2,4,5-三苯基咪唑等咪唑化合物等。<Thermal hardening accelerator> In the resin composition of the present embodiment, a thermosetting accelerator may be used in combination insofar as the properties of the embodiment are not impaired. The thermosetting accelerator is not particularly limited, and examples thereof include: benzamidine peroxide, lauric acid peroxide, ethidium peroxide, p-cyanoguanidine chloroformate, di-tert-butyl diperoxyphthalate, and the like. Anion; azo compound such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilino a tertiary amine such as ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine or N-methylpiperidine; phenol, Phenols such as xylenol, cresol, resorcinol, catechol; lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate An organic metal salt such as cobalt naphthenate or iron acetonate; the organic metal salt is soluble in a compound containing a hydroxyl group such as phenol or bisphenol; and an inorganic metal such as tin chloride, zinc chloride or aluminum chloride. Salt; an organic tin compound such as dioctyltin oxide, other alkyl tin, alkyl tin oxide; 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-three Imidazole Compounds, etc.

此等熱硬化促進劑可單獨使用1種或將2種以上適當混用。 本實施形態之樹脂組成物中,熱硬化促進劑之含量不特別限定,通常相對於樹脂組成物中之樹脂組成物100質量份為0.1~10質量份。These thermosetting accelerators may be used alone or in combination of two or more. In the resin composition of the present embodiment, the content of the thermosetting accelerator is not particularly limited, and is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition in the resin composition.

<有機溶劑> 本實施形態之樹脂組成物中,視需要也可以含有溶劑。例如若使用有機溶劑,樹脂組成物之製備時可調整黏度。溶劑之種類只要是樹脂組成物中之樹脂之一部分或全部可溶解者即可,無特殊限制。其具體例不特別限定,例如:丙酮、甲乙酮、甲基賽珞蘇等酮類;甲苯、二甲苯等芳香族烴類;二甲基甲醯胺等醯胺類;丙二醇單甲醚及其乙酸酯。 此等有機溶劑可以單獨使用1種或將2種以上適當混用。<Organic solvent> The resin composition of the present embodiment may contain a solvent as needed. For example, if an organic solvent is used, the viscosity of the resin composition can be adjusted. The type of the solvent is not particularly limited as long as it is partially or wholly soluble in the resin composition. Specific examples thereof are not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl cedar; aromatic hydrocarbons such as toluene and xylene; guanamines such as dimethylformamide; propylene glycol monomethyl ether and its B. Acid ester. These organic solvents may be used alone or in combination of two or more.

<其他成分> 本實施形態之樹脂組成物中,在無損本實施形態之特性之範圍內,也可併用至今未列舉之熱硬化性樹脂、熱塑性樹脂及其寡聚物、彈性體類等各種高分子化合物;至今未列舉之阻燃性之化合物;添加劑等。它們只要是一般使用者即可,無特殊限制。例如:阻燃性化合物可列舉三聚氰胺、苯胍胺等含氮化合物、含㗁??環之化合物、及磷系化合物之磷酸酯化合物、芳香族縮合磷酸酯、含鹵素縮合磷酸酯等。添加劑可以列舉紫外線吸收劑、抗氧化劑、螢光增白劑、光增感劑、染料、顏料、增黏劑、潤滑劑、消泡劑、表面調整劑、光澤劑、聚合抑制劑等。該等成分可單獨使用1種或將2種以上適當混用。 本實施形態之樹脂組成物中,其他成分之含量不特別限定,通常相對於樹脂組成物100質量份各為0.1~10質量份。<Other components> In the resin composition of the present embodiment, various thermosetting resins, thermoplastic resins, oligomers thereof, and elastomers which have not been enumerated so far may be used in combination with the properties of the present embodiment. Molecular compounds; flame retardant compounds not listed so far; additives, and the like. They are as long as they are general users, and there are no special restrictions. For example, examples of the flame retardant compound include a nitrogen-containing compound such as melamine or benzoguanamine, a compound containing a ruthenium ring, a phosphate compound of a phosphorus compound, an aromatic condensed phosphate, and a halogen-containing condensed phosphate. Examples of the additives include ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, tackifiers, lubricants, antifoaming agents, surface conditioners, glossing agents, polymerization inhibitors, and the like. These components may be used alone or in combination of two or more. In the resin composition of the present embodiment, the content of the other components is not particularly limited, and is usually 0.1 to 10 parts by mass per 100 parts by mass of the resin composition.

本實施形態之樹脂組成物,係藉由將被覆有二氧化矽之氟樹脂粒子(A)、樹脂成分(B)及因應所望的上述其他任意成分予以適當混合而製備。本實施形態之樹脂組成物適合使用在製作後述本實施形態之預浸體、及樹脂片時之清漆。 <樹脂組成物之製造方法> 本實施形態之樹脂組成物之製造方法不特別限定,例如將上述各成分按順序摻合在溶劑並充分攪拌之方法。The resin composition of the present embodiment is prepared by appropriately mixing fluororesin particles (A) coated with cerium oxide, a resin component (B), and other optional components as described above. In the resin composition of the present embodiment, a varnish for producing a prepreg according to the present embodiment and a resin sheet described later is suitably used. <Method for Producing Resin Composition> The method for producing the resin composition of the present embodiment is not particularly limited. For example, the above components are blended in a solvent in a stepwise manner and sufficiently stirred.

樹脂組成物製造時,可視需要實施為了使各成分均勻地溶解或分散之公知之處理(攪拌、混合、混練處理等)。具體而言,使用附設有適當攪拌能力之攪拌機之攪拌槽進行攪拌分散處理,能使被覆有二氧化矽之氟樹脂粒子(A)對樹脂組成物之分散性增進。上述攪拌、混合、混練處理可使用例如超音波均質機等以分散為目的之攪拌裝置、三輥、球磨機、珠磨機、砂磨等以混合為目的之裝置、或公轉或自轉型之混合裝置等公知之裝置適當進行。又,本實施形態之樹脂組成物製備時,視需要可以使用有機溶劑。有機溶劑之種類,只要是樹脂組成物中之樹脂可溶解者即可,不特別限定,其具體例如上所述。 <用途>In the production of the resin composition, a known treatment (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component may be carried out as needed. Specifically, the stirring and dispersing treatment is carried out using a stirring tank equipped with a stirrer having an appropriate stirring ability, whereby the dispersibility of the resin composition coated with the cerium oxide-containing fluororesin particles (A) can be improved. For the agitation, mixing, and kneading treatment, for example, a stirring device for dispersing, a three-roller, a ball mill, a bead mill, a sanding machine, or the like, or a mixing device for revolving or self-transforming may be used. The known device is suitably carried out. Further, in the preparation of the resin composition of the present embodiment, an organic solvent may be used as needed. The type of the organic solvent is not particularly limited as long as it is soluble in the resin composition, and is specifically described above. <Use>

本實施形態之樹脂組成物可使用在需要絕緣性之樹脂組成物的用途,不特別限定,可使用在感光性薄膜、附設支持體感光性薄膜、預浸體等絕緣樹脂片、電路基板(疊層板用途、多層印刷電路板用途等)、阻焊劑、底層填充(underfill)材、黏晶材、半導體密封材、孔填埋樹脂、零件填埋樹脂等用途。其中,適合作為多層印刷電路板之絕緣層用樹脂組成物、阻焊劑。The resin composition of the present embodiment can be used for a resin composition requiring an insulating property, and is not particularly limited, and can be used for a photosensitive film, an insulating film such as a support photosensitive film, a prepreg, or a circuit board. Laminate use, multilayer printed circuit board use, etc.), solder resist, underfill material, adhesive crystal, semiconductor sealing material, hole filling resin, part filling resin, etc. Among them, it is suitable as a resin composition for an insulating layer of a multilayer printed wiring board, and a solder resist.

<預浸體> 本實施形態之預浸體,係使上述本實施形態之樹脂組成物含浸或塗佈於基材而成者。預浸體之製造方法,只要是將本實施形態之樹脂組成物與基材組合而製造預浸體之方法即可,並無特殊限制。具體而言,使本實施形態之樹脂組成物含浸或塗佈於基材後,於120~220℃進行約2~15分鐘乾燥之方法等使其半硬化,以製造本實施形態之預浸體。此時,樹脂組成物對於基材之附著量,亦即樹脂組成物量相對於半硬化後之預浸體之總量(包括填充材)為20~99質量%之範圍較佳。<Prepreg> The prepreg according to the present embodiment is obtained by impregnating or coating the resin composition of the present embodiment on a substrate. The method for producing the prepreg is not particularly limited as long as it is a method in which the resin composition of the present embodiment is combined with a substrate to produce a prepreg. Specifically, the resin composition of the present embodiment is impregnated or applied to a substrate, and then semi-cured by drying at 120 to 220 ° C for about 2 to 15 minutes to produce a prepreg according to the present embodiment. . At this time, the amount of the resin composition attached to the substrate, that is, the amount of the resin composition is preferably in the range of 20 to 99% by mass based on the total amount (including the filler) of the prepreg after the semi-curing.

製造本實施形態之預浸體時使用之基材,可以使用在各種印刷電路板材料使用之公知者。例如:E玻璃、D玻璃、L玻璃、S玻璃、T玻璃、Q玻璃、UN玻璃、NE玻璃、球狀玻璃等玻璃纖維、石英等玻璃以外之無機纖維、聚醯亞胺、聚醯胺、聚酯等有機纖維、液晶聚酯等織布,但不特別限於此等。基材之形狀已知有織布、不織布、粗紗、切股氈、表面氈等,皆可以使用。基材可單獨使用1種或將2種以上組合使用。又,基材之厚度不特別限定,若為疊層板用途,為0.01~0.2mm之範圍較理想,尤其施有超開纖處理、孔目堵塞處理之織布,考量尺寸安定性之觀點為較理想。再者,經環氧矽烷處理、胺基矽烷處理等矽烷偶聯劑等進行了表面處理的玻璃織布,從吸濕耐熱性之觀點較理想。又,液晶聚酯織布,從電特性方面較理想。The substrate used in the production of the prepreg of the present embodiment can be used by any of various printed circuit board materials. For example: glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, inorganic fibers other than glass such as quartz, polyimine, polyamine, A woven fabric such as an organic fiber such as polyester or a liquid crystal polyester is not particularly limited thereto. The shape of the substrate is known as woven fabric, non-woven fabric, roving, stranded felt, surface felt, etc., and can be used. The base material may be used alone or in combination of two or more. Further, the thickness of the substrate is not particularly limited, and it is preferably in the range of 0.01 to 0.2 mm for laminated board applications, and in particular, a fabric having a super-opening treatment and a hole-blocking treatment, and the viewpoint of dimensional stability is considered. More ideal. Further, a glass woven fabric surface-treated with a decane coupling agent such as an epoxy decane treatment or an amino decane treatment is preferable from the viewpoint of moisture absorption and heat resistance. Further, the liquid crystal polyester woven fabric is preferable in terms of electrical characteristics.

<覆金屬箔疊層板> 本實施形態之覆金屬箔疊層板,係將至少1片以上之疊層在一起之上述預浸體,及配置在該預浸體之單面或兩面之金屬箔予以疊層成形而成。具體而言,可藉由重疊1或多片前述預浸體,於其單面或兩面配置銅、鋁等金屬箔並疊層成形而製作。在此使用之金屬箔,只要是使用在印刷電路板材料者即可,不特別限定,壓延銅箔、電解銅箔等銅箔為較佳。又,金屬箔之厚度不特別限定,2~70μm較理想,3~35μm更理想。成形條件可採用通常之印刷電路板用疊層板及多層板的方法。例如可使用多段壓製機、多段真空壓製機、連續成形機、高壓釜成形機等,於溫度180~350℃、加熱時間100~300分鐘、面壓20~100kg/cm2 之條件進行疊層成形,以製造本發明之覆金屬箔疊層板。又,也可將上述預浸體與另外製作的內層用之配線板組合並疊層成形以製成多層板。多層板之製造方法,例如在上述預浸體1片之兩面配置35μm之銅箔,以上述條件進行疊層形成後,形成內層電路,對於此電路實施黑化處理而形成內層電路板,之後將此內層電路板與上述預浸體交替地一片一片逐片配置,再於最外層配置銅箔,以上述條件較佳為於真空下進行疊層成形,以製作多層板。<Metal-clad laminate> The metal foil-clad laminate of the present embodiment is a prepreg in which at least one or more sheets are laminated, and a metal disposed on one or both sides of the prepreg The foil is laminated and formed. Specifically, it is possible to form a metal foil such as copper or aluminum on one or both sides by laminating one or more sheets of the prepreg and laminating them. The metal foil to be used here is not particularly limited as long as it is used for a printed circuit board material, and a copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. Further, the thickness of the metal foil is not particularly limited, and 2 to 70 μm is preferable, and 3 to 35 μm is more preferable. As the molding conditions, a usual method for laminating sheets and multilayer sheets for printed circuit boards can be employed. For example, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, or the like can be used for lamination forming at a temperature of 180 to 350 ° C, a heating time of 100 to 300 minutes, and a surface pressure of 20 to 100 kg/cm 2 . To produce the metal foil-clad laminate of the present invention. Further, the prepreg may be combined with a separately prepared wiring board for the inner layer to form a multilayer board. In the method for producing a multilayer board, for example, a copper foil of 35 μm is placed on both surfaces of the prepreg, and after lamination is formed under the above conditions, an inner layer circuit is formed, and the circuit is subjected to a blackening treatment to form an inner layer circuit board. Thereafter, the inner layer circuit board and the prepreg are alternately arranged one by one, and the copper foil is disposed on the outermost layer, and the laminate is preferably formed under vacuum under the above conditions to produce a multilayer board.

<樹脂片> 另外,本實施形態之樹脂片可藉由將把上述本實施形態之樹脂組成物溶於溶劑而得的溶液塗佈於支持體並乾燥以獲得。在此使用之支持體,例如:聚乙烯薄膜、聚丙烯薄膜、聚碳酸酯薄膜、聚對苯二甲酸乙二醇酯薄膜、乙烯四氟乙烯共聚物薄膜、及在該等薄膜之表面塗佈了脫模劑而得之脫模薄膜、聚醯亞胺薄膜等有機系之薄膜基材、銅箔、鋁箔等導體箔、玻璃板、SUS板、FRP等板狀者,無特殊限制。<Resin Sheet> The resin sheet of the present embodiment can be obtained by applying a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a support and drying it. Supports for use herein, for example, polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and coating on the surface of such films The organic film substrate such as a release film or a polyimide film, a conductive foil such as a copper foil or an aluminum foil, a glass plate, a SUS plate, or an FRP plate is not particularly limited.

再者,本實施形態中之樹脂片之樹脂組成物層可以經保護薄膜保護。 藉由將樹脂組成物層側以保護薄膜保護,能防止髒污等附著於樹脂組成物層表面等或是防止受傷。保護薄膜可使用以和上述樹脂薄膜同樣的材料構成的薄膜。保護薄膜之厚度不特別限定,1μm~50μm之範圍較佳,5μm~40μm之範圍更佳。厚度若未達1μm,保護薄膜之操作性有降低的傾向,若超過50μm,有廉價性差的傾向。又,保護薄膜,宜為樹脂組成物層與保護薄膜之黏著力比起樹脂組成物層與支持體之黏著力為小者較佳。Further, the resin composition layer of the resin sheet in the present embodiment can be protected by a protective film. By protecting the film on the side of the resin composition layer, it is possible to prevent dirt or the like from adhering to the surface of the resin composition layer or the like or to prevent injury. As the protective film, a film composed of the same material as the above resin film can be used. The thickness of the protective film is not particularly limited, and a range of 1 μm to 50 μm is preferable, and a range of 5 μm to 40 μm is more preferable. When the thickness is less than 1 μm, the handleability of the protective film tends to decrease, and if it exceeds 50 μm, the inexpensiveness tends to be inferior. Further, the protective film is preferably one in which the adhesion between the resin composition layer and the protective film is smaller than the adhesion between the resin composition layer and the support.

塗佈方法,例如把使本實施形態之樹脂組成物溶於溶劑而得之溶液以桿塗機、模塗機、刮刀、貝克塗抹器等塗佈在支持體上而製得支持體與樹脂片成為一體之疊層片之方法。又,亦可於乾燥後從疊層片將支持體剝離或蝕刻,製成樹脂片為單獨的單層片。又,藉由將使上述本實施形態之樹脂組成物溶於溶劑而得之溶液對於有片狀之模穴的模具內供給並乾燥等而成形為片狀,則不使用支持體亦可獲得單層片。In the coating method, for example, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied to a support by a bar coater, a die coater, a doctor blade, a Baker applicator or the like to obtain a support and a resin sheet. A method of becoming a one-piece laminate. Further, after the drying, the support may be peeled off or etched from the laminate to form a single sheet of the resin sheet. In addition, when the solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried, or formed into a sheet shape, a single sheet can be obtained without using a support. Layer.

又,本實施形態之樹脂片(單層或疊層片)製作時,去除溶劑時之乾燥條件不特別限定,考量若為低溫則樹脂組成物中易殘留溶劑,若為高溫則樹脂組成物之硬化會進行的觀點,宜於20℃~200℃之溫度進行1~90分鐘較佳。又,本實施形態之樹脂片(單層或疊層片)之樹脂層之厚度可藉由本實施形態之樹脂組成物之溶液之濃度與塗佈厚度調整,不特別限定,一般而言,塗佈厚度若增厚,乾燥時易殘留溶劑,故為0.1~500μm較佳。Further, in the production of the resin sheet (single layer or laminated sheet) of the present embodiment, the drying conditions in the case of removing the solvent are not particularly limited, and if the temperature is low, the solvent tends to remain in the resin composition, and if it is high, the resin composition is high. The viewpoint that the hardening will proceed is preferably from 1 to 90 minutes at a temperature of from 20 ° C to 200 ° C. In addition, the thickness of the resin layer of the resin sheet (single layer or laminated sheet) of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited. Generally, coating is applied. If the thickness is increased, the solvent tends to remain during drying, so that it is preferably 0.1 to 500 μm.

<印刷電路板> 本實施形態之覆金屬箔疊層板及樹脂片可理想地作為印刷電路板使用。印刷電路板可依常法製造,其製造方法無特殊限制。以下顯示使用了覆金屬箔疊層板之印刷電路板之製造方法之一例。首先準備上述覆銅疊層板等覆金屬箔疊層板。然後對於覆金屬箔疊層板之表面實施蝕刻處理,實施內層電路之形成,製作內層基板。對於此內層基板之內層電路表面視需要實施用以提高黏著強度之表面處理,然後在此內層電路表面重疊所需片數之上述預浸體再於其外側疊層外層電路用之金屬箔,加熱加壓而一體成體成形。依此方式,製作在內層電路與外層電路用之金屬箔之間形成了基材及由熱硬化性樹脂組成物之硬化物構成之絕緣層的多層疊層板。其次,於此多層疊層板施以通孔、介層孔用之開孔加工後,於其孔之壁面形成用以使內層電路與外層電路用之金屬箔導通之鍍敷金屬皮膜,再對於外層電路用之金屬箔實施蝕刻處理而形成外層電路,製成印刷電路板。<Printed Circuit Board> The metal foil-clad laminate and the resin sheet of the present embodiment are preferably used as a printed circuit board. The printed circuit board can be manufactured in accordance with a conventional method, and the manufacturing method thereof is not particularly limited. An example of a method of manufacturing a printed circuit board using a metal foil-clad laminate is shown below. First, a metal foil-clad laminate such as the above-mentioned copper-clad laminate is prepared. Then, the surface of the metal foil-clad laminate is subjected to an etching treatment to form an inner layer circuit, and an inner layer substrate is produced. The surface of the inner layer of the inner substrate is subjected to a surface treatment for improving the adhesion strength, and then the surface of the inner layer is overlapped with the required number of sheets of the prepreg and the metal for the outer layer is laminated on the outer side. The foil is heated and pressurized to be integrally formed. In this manner, a multilayer laminated plate in which an insulating layer composed of a base material and a cured product of a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit is formed. Next, after the multilayer laminated board is subjected to the opening for the through hole and the via hole, a plated metal film for conducting the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the hole, and then The metal foil for the outer layer circuit is etched to form an outer layer circuit to form a printed circuit board.

上述製造例獲得之印刷電路板,具有絕緣層及在此絕緣層之表面形成之導體層,絕緣層為含有上述本實施形態之樹脂組成物之構成。亦即,上述本實施形態之預浸體(基材及含浸或塗佈於此基材之本實施形態之樹脂組成物)、上述本實施形態之覆金屬箔疊層板之樹脂組成物之層(由本發明之樹脂組成物構成之層),係由含有本實施形態之樹脂組成物之絕緣層構成。The printed circuit board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer is composed of the resin composition of the above-described embodiment. In other words, the prepreg of the present embodiment (the substrate and the resin composition of the present embodiment impregnated or coated on the substrate) and the layer of the resin composition of the metal foil-clad laminate of the present embodiment. (Layer composed of the resin composition of the present invention) is composed of an insulating layer containing the resin composition of the present embodiment.

以下顯示使用了樹脂片之印刷電路板之製造方法之一例。本實施形態之樹脂片適合使用於作為印刷電路板之層間絕緣層,可將上述樹脂片1片以上重疊並硬化而得。具體而言可依以下之方法製造。An example of a method of manufacturing a printed circuit board using a resin sheet is shown below. The resin sheet of the present embodiment is suitably used as an interlayer insulating layer of a printed circuit board, and one or more sheets of the above resin sheet can be laminated and cured. Specifically, it can be produced by the following method.

將本實施形態之樹脂片之樹脂組成物層側成形於電路基板之單面或兩面。成型條件可採用通常之印刷電路板用疊層板及多層板的方法,也可以利用真空層合成形。電路基板,可列舉例如:玻璃環氧基板、金屬基板、陶瓷基板、矽基板、半導體密封樹脂基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚伸苯醚基板等。又,在此,電路基板係指在如上述基板之單面或兩面形成了進行圖案加工而得的導體層(電路)之基板。又,導體層與絕緣層交替疊層而成之多層印刷電路板中,該多層印刷電路板之最外層之單面或兩面成為經圖案加工之導體層(電路)的基板,也包括於在此所指之電路基板。又,也可以對於導體層表面預先實施黑化處理、利用銅蝕刻等的粗糙化處理。成型步驟中,樹脂片有保護薄膜時,係將該保護薄膜剝離除去後,視需要將樹脂片及電路基板預熱,並邊將樹脂組成物層加壓及加熱邊壓接在電路基板。本實施形態之樹脂片,宜採行利用真空層合法於減壓下層合在電路基板的方法。The resin composition layer side of the resin sheet of the present embodiment is formed on one surface or both surfaces of a circuit board. The molding conditions may be a conventional method for laminating sheets and multilayer sheets for printed circuit boards, or a vacuum layer may be used for forming. Examples of the circuit board include a glass epoxy substrate, a metal substrate, a ceramic substrate, a tantalum substrate, a semiconductor sealing resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the circuit board refers to a substrate on which a conductor layer (circuit) obtained by patterning is formed on one surface or both surfaces of the substrate. Further, in a multilayer printed circuit board in which a conductor layer and an insulating layer are alternately laminated, a single-sided or both surfaces of an outermost layer of the multilayer printed circuit board are substrates of a patterned conductor layer (circuit), and are also included herein. The circuit board referred to. Further, the surface of the conductor layer may be subjected to a blackening treatment or a roughening treatment such as copper etching. In the molding step, when the protective film is peeled off, the resin sheet and the circuit board are preheated as necessary, and the resin composition layer is pressed against the circuit board while being heated and heated. In the resin sheet of the present embodiment, a method of laminating the circuit board under reduced pressure by vacuum lamination is preferred.

層合步驟之條件無特殊限制,例如:壓接溫度(層合溫度)較佳為50℃~140℃,壓接壓力較佳為1kgf/cm2 ~15kgf/cm2 ,壓接時間較佳為5秒~300秒,且空氣壓為20mmHg以下之減壓下進行層合較佳。又,層合步驟,可為批式也可為使用輥之連續式。真空層合法可以使用市售之真空層合機進行。市售真空層合機,例如:Nikko Materials(股)製2階段增建層合機等。The conditions of the laminating step are not particularly limited. For example, the crimping temperature (laminating temperature) is preferably from 50 ° C to 140 ° C, the crimping pressure is preferably from 1 kgf / cm 2 to 15 kgf / cm 2 , and the crimping time is preferably The lamination is preferably carried out under reduced pressure of 5 seconds to 300 seconds and an air pressure of 20 mmHg or less. Further, the laminating step may be a batch type or a continuous type using a roll. Vacuum lamination can be carried out using a commercially available vacuum laminator. A commercially available vacuum laminator, for example, a two-stage addition laminator manufactured by Nikko Materials Co., Ltd., or the like.

孔加工處理係為了形成介層孔、通孔等而實施。孔加工處理可使用NC鑽機、二氧化碳氣體雷射、UV雷射、YAG雷射、電漿等公知之方法中的任1種,或若有必要可將2種以上組合進行。樹脂片為光硬化性樹脂組成物時,也可以利用曝光、顯影實施孔加工處理。The hole processing is performed to form via holes, via holes, and the like. For the hole processing, any one of known methods such as an NC drill, a carbon dioxide gas laser, a UV laser, a YAG laser, and a plasma may be used, or two or more types may be combined if necessary. When the resin sheet is a photocurable resin composition, the hole processing may be performed by exposure and development.

孔加工處理前或處理後,視需要實施後烘烤步驟,形成絕緣層(硬化物)。後烘烤步驟可列舉利用高壓水銀燈所為之紫外線照射步驟、使用潔淨烘箱之加熱步驟等。照射紫外線時,視需要可以調整其照射量,可以於例如約0.05J/cm2 ~10J/ cm2 之照射量進行照射。又,加熱之條件可因應樹脂組成物中之樹脂成分之種類、 含量等而適當選擇,較佳為150℃~220℃20分鐘~180分鐘之範圍,更佳為160℃~200℃30分鐘~150分鐘之範圍中選擇。Before or after the hole processing, a post-baking step is performed as needed to form an insulating layer (hardened material). The post-baking step may be an ultraviolet irradiation step using a high-pressure mercury lamp, a heating step using a clean oven, or the like. When the ultraviolet ray is irradiated, the amount of irradiation can be adjusted as needed, and irradiation can be performed, for example, at an irradiation amount of about 0.05 J/cm 2 to 10 J/cm 2 . Further, the heating condition can be appropriately selected depending on the kind and content of the resin component in the resin composition, and is preferably in the range of from 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably from 160 ° C to 200 ° C for 30 minutes. Choose from a range of 150 minutes.

絕緣層表面有導體層時,可藉由於孔的壁面形成使內層電路與外層電路用之金屬箔導通之鍍敷金屬皮膜,再對於外層電路用之金屬箔實施蝕刻處理而形成外層電路,以製造印刷電路板。When the surface of the insulating layer has a conductive layer, a metallized film for conducting the inner layer circuit and the metal foil for the outer layer circuit is formed by the wall surface of the hole, and then the metal foil for the outer layer circuit is etched to form an outer layer circuit. Manufacturing printed circuit boards.

絕緣層表面沒有導體層時,接著係利用乾式鍍敷或濕式鍍敷在絕緣層表面形成導體層。乾式鍍敷可使用蒸鍍法、濺鍍法、離子鍍法等公知之方法。蒸鍍法(真空蒸鍍法),例如可將支持體放入到真空容器內,使金屬加熱蒸發以在絕緣層上形成金屬膜。濺鍍法亦為例如將支持體放入到真空容器內,導入氬氣等鈍性氣體,施加直流電壓,使游離的鈍性氣體碰撞靶金屬,並利用被擊出的金屬在絕緣層上形成金屬膜。When there is no conductor layer on the surface of the insulating layer, a conductor layer is formed on the surface of the insulating layer by dry plating or wet plating. A known method such as a vapor deposition method, a sputtering method, or an ion plating method can be used for the dry plating. In the vapor deposition method (vacuum evaporation method), for example, a support can be placed in a vacuum container, and the metal can be heated and evaporated to form a metal film on the insulating layer. The sputtering method is, for example, putting a support into a vacuum container, introducing a passive gas such as argon gas, applying a direct current voltage, causing a free passive gas to collide with the target metal, and forming a metal on the insulating layer by the struck metal. Metal film.

濕式鍍敷的情形,對於已形成之絕緣層之表面按順序實施利用膨潤液所為之膨潤處理、利用氧化劑所為之粗糙化處理及利用中和液所為之中和處理,以將絕緣層表面進行粗糙化。利用膨潤液所為之膨潤處理,係藉由使絕緣層於50℃~80℃浸於膨潤液1分鐘~20分鐘以進行。膨潤液可列舉鹼溶液,該鹼溶液可列舉氫氧化鈉溶液、氫氧化鉀溶液等。市售的膨潤液,例如上村工業(股)製之APPDE S(註冊商標)MDS-37等。 利用氧化劑所為之粗糙化處理,係藉由使絕緣層於60℃~80℃浸於氧化劑溶液5分鐘~30分鐘以進行行。氧化劑,例如:氫氧化鈉之水溶液溶有過錳酸鉀、過錳酸鈉之鹼性過錳酸溶液、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸等。又,鹼性過錳酸溶液中之過錳酸鹽之濃度宜為5質量%~10質量%較佳。市售之氧化劑,例如:上村工業(股)製APPDES(註冊商標)MDE-40、APPDES(註冊商標)ELC- SH等鹼性過錳酸溶液。利用中和液所為之中和處理,係藉由於30℃~50℃浸於中和液1分鐘~10分鐘以進行。中和液宜為酸性水溶液較理想,市售品可列舉上村工業(股)製之APPDES(註冊商標)MDN-62。In the case of wet plating, the surface of the formed insulating layer is sequentially subjected to a swelling treatment by a swelling liquid, a roughening treatment by an oxidizing agent, and a neutralization treatment using a neutralizing liquid to carry out the surface of the insulating layer. Roughening. The swelling treatment by the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 ° C to 80 ° C for 1 minute to 20 minutes. The swelling solution may, for example, be an alkali solution, and examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. A commercially available swelling liquid, for example, APPDE S (registered trademark) MDS-37 manufactured by Uemura Industrial Co., Ltd., and the like. The roughening treatment by the oxidizing agent is carried out by immersing the insulating layer in an oxidizing agent solution at 60 ° C to 80 ° C for 5 minutes to 30 minutes. The oxidizing agent, for example, an aqueous solution of sodium hydroxide is dissolved in potassium permanganate, an alkaline permanganic acid solution of sodium permanganate, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, or the like. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably from 5% by mass to 10% by mass. Commercially available oxidizing agents, for example, an alkaline permanganic acid solution such as APPDES (registered trademark) MDE-40, APPDES (registered trademark) ELC-SH manufactured by Uemura Industrial Co., Ltd. The neutralization treatment by the neutralization solution is carried out by immersing the neutralization solution at 30 ° C to 50 ° C for 1 minute to 10 minutes. The neutralizing liquid is preferably an acidic aqueous solution, and the commercial product may be APPDES (registered trademark) MDN-62 manufactured by Uemura Industrial Co., Ltd.

其次,將無電解鍍敷與電解鍍敷組合而形成導體層。也可形成和導體層為相反圖案的鍍敷光阻,僅以無電解鍍敷形成導體層。之後之圖案形成的方法例如:減去法、半加成法等。Next, electroless plating is combined with electrolytic plating to form a conductor layer. It is also possible to form a plating resist having an opposite pattern to the conductor layer, and to form the conductor layer only by electroless plating. Subsequent pattern formation methods are, for example, subtractive methods, semi-additive methods, and the like.

<半導體裝置> 本實施形態之半導體裝置具備包括本實施形態之樹脂組成物之層間絕緣層,具體而言可依以下之方法製造。藉由在本實施形態之多層印刷電路板的導通處安裝半導體晶片,可製造半導體裝置。在此,導通處係多層印刷電路板中傳達電訊號之處,此處可在表面也可在埋入之處。又,半導體晶片只要是以半導體作為材料之電氣電路元件即可,並無特殊限制。<Semiconductor device> The semiconductor device of the present embodiment includes an interlayer insulating layer including the resin composition of the present embodiment, and specifically, it can be produced by the following method. A semiconductor device can be manufactured by mounting a semiconductor wafer on the conduction portion of the multilayer printed wiring board of the present embodiment. Here, the conduction point is where the electrical signal is transmitted in the multilayer printed circuit board, where it can be buried on the surface or in the place where it is buried. Further, the semiconductor wafer is not particularly limited as long as it is an electrical circuit component made of a semiconductor.

製造本實施形態之半導體裝置時之半導體晶片之安裝方法,只要是能使半導體晶片作用的即可,不特別限定,具體而言可列舉接線安裝方法、覆晶晶片安裝方法、利用無凸塊之增建層(BBUL)所為之安裝方法、利用異向性導電薄膜(ACF)所為之安裝方法、利用非導電性薄膜(NCF)所為之安裝方法等。The method of mounting the semiconductor wafer in the case of manufacturing the semiconductor device of the present embodiment is not particularly limited as long as it can function as a semiconductor wafer, and specifically, a wiring mounting method, a flip chip mounting method, and a bump-free method are used. The mounting method for the build-up layer (BBUL), the mounting method using an anisotropic conductive film (ACF), and the mounting method using a non-conductive film (NCF).

又,藉由將本實施形態之樹脂片層合在半導體晶片,也可以製造半導體裝置。層合後,可以使用和前述多層印刷電路板同樣的方法製造。 [實施例]Further, a semiconductor device can be manufactured by laminating the resin sheet of the present embodiment on a semiconductor wafer. After lamination, it can be produced in the same manner as the above multilayer printed circuit board. [Examples]

以下依合成例、實施例對於本發明更具體説明,但是本發明不限於該等實施例。Hereinafter, the present invention will be more specifically described by way of Synthesis Examples and Examples, but the present invention is not limited to the Examples.

[合成例1] (氰酸酯化合物之合成) 使1-萘酚芳烷基樹脂(新日鐵住金化學(股)公司製)300g(OH基換算1.28mol)及三乙胺194.6g(1.92mol)(相對於羥基1mol為1.5mol)溶於二氯甲烷1800g,命名為溶液1。[Synthesis Example 1] (Synthesis of a cyanate compound) 300 g of a 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) (1.28 mol in terms of OH group) and 194.6 g (1.92 in triethylamine) Mol) (1.5 mol relative to 1 mol of the hydroxyl group) was dissolved in 1800 g of dichloromethane and designated as Solution 1.

將氯化氰125.9g(2.05mol)(相對於羥基1mol為1.6mol)、二氯甲烷293.8g、36%鹽酸194.5g(1.92mol)(相對於羥基1mol為1.5莫耳)、水1205.9g於攪拌下保持在液溫-2~-0.5℃的狀態,費時30分鐘加注溶液1。溶液1加注結束後,於同溫攪拌30分鐘,之後費時10分鐘加注使三乙胺65g(0.64mol)(相對於羥基1mol為0.5mol)溶於二氯甲烷65g而得之溶液(溶液2)。溶液2加注結束後,於同溫攪拌30分鐘,使反應完結。 之後將反應液靜置,將有機相與水相分離。獲得之有機相以水1300g清洗5次。水洗第5次的廢水的電傳導度為5μS/cm,確認以水洗淨能夠將可除去之離子性化合物充分除去。 將水洗後之有機相於減壓下濃縮,最終於90℃進行1小時濃縮乾固,獲得目的之萘酚芳烷基型之氰酸酯化合物(SNCN)(橙色黏性物)331g。獲得之SNCN之質量平均分子量Mw為600。又,SNCN之IR光譜顯示2250cm-1 (氰酸酯基)之吸收且未顯示羥基之吸收。125.9 g (2.05 mol) of cyanogen chloride (1.6 mol with respect to 1 mol of hydroxyl group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol with respect to 1 mol of hydroxyl group), and 1205.9 g of water were used. The solution was kept at a liquid temperature of -2 to -0.5 ° C under stirring, and the solution 1 was added over a period of 30 minutes. After the completion of the filling of the solution 1, the mixture was stirred at the same temperature for 30 minutes, and then a solution of 35 g of triethylamine (0.64 mol) (0.5 mol relative to 1 mol of the hydroxyl group) dissolved in dichloromethane was added for 10 minutes. 2). After the completion of the filling of the solution 2, the mixture was stirred at the same temperature for 30 minutes to complete the reaction. Thereafter, the reaction solution was allowed to stand, and the organic phase was separated from the aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the fifth-time wastewater was 5 μS/cm, and it was confirmed that the removable ionic compound can be sufficiently removed by washing with water. The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated and dried at 90 ° C for one hour to obtain 331 g of the desired naphthol aralkyl type cyanate compound (SNCN) (orange viscous). The mass average molecular weight Mw of the obtained SNCN was 600. Further, the IR spectrum of SNCN showed absorption of 2250 cm -1 (cyanate group) and showed no absorption of a hydroxyl group.

[合成例2] (具乙烯基之2官能性伸苯醚寡聚物體之合成) 於配備攪拌裝置、溫度計、空氣導入管、擋板的12L的縱長反應器中加入CuBr 23.88g(17.4mmol)、N,N’-二第三丁基乙二胺0.75g(4.4mmol)、正丁基二甲胺28.04g (277.6mmol)、甲苯2600g,於反應溫度40℃攪拌,並將預先溶於2300g之甲醇之2,2’,3,3’,5,5’-六甲基-(1,1’-聯苯酚)-4,4’-二醇129.3g(0.48mol)、2,6-二甲基苯酚233. 7g(1.92mol)、2,3,6-三甲基苯酚64.9g(0.48mol)、N,N’-二第三丁基乙二胺0.51g(2.9 mmol)、正丁基二甲胺10.90g(108.0mmol)之混合溶液,於邊將氮氣與空氣混合成氧濃度8%之混合氣體以5.2L/min的流速邊鼓泡的狀態,邊費時230分鐘滴加,並進行攪拌。滴加結束後加入溶有乙二胺四乙酸四鈉19.89g(52.3mmol)之水1500g, 並將反應停止。將水層與有機層分液,將有機層以1N鹽酸水溶液清洗,再以純水清洗。獲得之溶液以蒸發器濃縮成50wt%,獲得2官能性伸苯醚寡聚物之甲苯溶液836.5g。2官能性伸苯醚寡聚物體之數量平均分子量為986、重量平均分子量為1530、羥基當量為471。[Synthesis Example 2] (Synthesis of a bifunctional phenylene ether oligomer having a vinyl group) CuBr 23.88 g (17.4 mmol) was added to a 12 L lengthwise reactor equipped with a stirring device, a thermometer, an air introduction tube, and a baffle. ), N,N'-di-t-butylethylenediamine 0.75g (4.4mmol), n-butyldimethylamine 28.04g (277.6mmol), toluene 2600g, stirred at a reaction temperature of 40 ° C, and pre-dissolved 2300 g of methanol 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'-diol 129.3 g (0.48 mol), 2,6 - dimethylphenol 233.7 g (1.92 mol), 2,3,6-trimethylphenol 64.9 g (0.48 mol), N,N'-di-t-butylethylenediamine 0.51 g (2.9 mmol), a mixed solution of n-butyldimethylamine 10.90 g (108.0 mmol), which was mixed with nitrogen and air to form a mixed gas having an oxygen concentration of 8%, and was bubbled at a flow rate of 5.2 L/min, and it took 230 minutes to drip. And stir. After the completion of the dropwise addition, 1500 g of water in which 19.89 g (52.3 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added, and the reaction was stopped. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N aqueous hydrochloric acid solution and then washed with purified water. The obtained solution was concentrated to 50% by weight with an evaporator to obtain 836.5 g of a toluene solution of a bifunctional phenylene ether oligomer. The bifunctional phenylene ether oligomer had a number average molecular weight of 986, a weight average molecular weight of 1530, and a hydroxyl equivalent of 471.

(乙烯基化合物之合成) 於配備攪拌裝置、溫度計、回流管之反應器中裝入2官能性伸苯醚寡聚物之甲苯溶液836.5g、乙烯基苄基氯(商品名CMS-P、AGC Seimichemical(股)製)162.6 g、二氯甲烷1600g、苄基二甲胺12.95g、純水420g、30.5wt% NaOH水溶液178.0g,於反應溫度40℃進行攪拌。實施24小時攪拌後,將有機層以1N鹽酸水溶液清洗,然後以純水清洗。將獲得之溶液以蒸發器濃縮,滴加到甲醇中進行固化,以過濾回收固體,真空乾燥而獲得乙烯基化合物503.5g。乙烯基化合物之數量平均分子量為1187、重量平均分子量為1675,乙烯基當量為590g/乙烯基。(Synthesis of Vinyl Compound) 836.5 g of a toluene solution of a bifunctional phenylene ether oligomer was charged into a reactor equipped with a stirring device, a thermometer, and a reflux tube, and vinyl benzyl chloride (trade name CMS-P, AGC) 162.6 g of Seimichemical Co., Ltd., 1600 g of dichloromethane, 12.95 g of benzyldimethylamine, 420 g of pure water, and 178.0 g of a 30.5 wt% aqueous NaOH solution were stirred at a reaction temperature of 40 °C. After stirring for 24 hours, the organic layer was washed with a 1N aqueous solution of hydrochloric acid and then washed with purified water. The obtained solution was concentrated by an evaporator, added dropwise to methanol to be solidified, and the solid was collected by filtration, and dried under vacuum to obtain 503.5 g of a vinyl compound. The vinyl compound had a number average molecular weight of 1,187, a weight average molecular weight of 1,675, and a vinyl equivalent of 590 g/vinyl.

[實施例1] (樹脂組成物及預浸體之製作) 將作為被覆有二氧化矽之氟樹脂粒子(A)之被覆有二氧化矽之PTFE填料之甲乙酮(以下有時簡稱MEK)漿液(0.5μmPTFE-YA(商品名)、一次粒子之體積平均粒徑0.5μm、不揮發成分20質量%、Admatechs(股)製)250質量份(按不揮發成分換算,為50質量份)、作為氰酸酯化合物之合成例1獲得之SNCN2.1質量份、2,2-雙(4-氰氧基苯基)丙烷之預聚物(CA210(商品名)、氰酸酯當量139、三菱瓦斯化學(股)製)6.6質量份、作為環氧樹脂之溴化雙酚A型環氧樹脂(E153(商品名)、環氧當量400、2級羥基量0.3meq/g、DIC(股)製)10.6質量份、作為具乙烯性不飽和基之化合物之合成例2獲得之乙烯基化合物(數量平均分子量為1187、乙烯基當量為590g/乙烯基)77.5質量份、α-甲基苯乙烯寡聚物(KA3085(商品名)、質量平均分子量:664、美國Eastman Chemical Company製)3.2質量份、作為其他填充材(C)之乙烯基矽烷處理二氧化矽之MEK漿液(SC2050MNU(商品名)、中位徑0.5μm、不揮發成分70質量%、(股)Admatechs製)71.4質量份(按不揮發成分換算,為50質量份)混合,獲得清漆(樹脂組成物之溶液)。將此清漆以甲乙酮稀釋,含浸塗佈於厚度0.1mm之E玻璃織布,於160℃進行5分鐘加熱乾燥,獲得樹脂含量50質量%之預浸體。[Example 1] (Preparation of a resin composition and a prepreg) A methyl ethyl ketone (hereinafter sometimes referred to as MEK) slurry of a PTFE filler coated with cerium oxide as a fluororesin particle (A) coated with cerium oxide (hereinafter referred to as MEK) 0.5 μm PTFE-YA (trade name), a volume average particle diameter of primary particles of 0.5 μm, a nonvolatile content of 20% by mass, and an amount of 250 parts by mass of Admatechs Co., Ltd. (50 parts by mass in terms of nonvolatile content), and Synthetic Example 1 of the acid ester compound: 2.1 parts by mass of SNCN, 2,2-bis(4-cyanooxyphenyl)propane prepolymer (CA210 (trade name), cyanate equivalent 139, Mitsubishi Gas Chemical (Stock) 6.6 parts by mass of brominated bisphenol A type epoxy resin (E153 (trade name), epoxy equivalent 400, 2-stage hydroxyl group 0.3 meq/g, DIC (manufactured by DIC)) 10.6 parts by mass of a vinyl compound (quantitative average molecular weight: 1187, vinyl equivalent of 590 g/vinyl group) obtained in Synthesis Example 2, which is an ethylenically unsaturated group, 77.5 parts by mass, α-methylstyrene oligomerization (KA3085 (trade name), mass average molecular weight: 664, manufactured by Eastman Chemical Company, USA) 3.2 parts by mass, as other fillers (C) MEK slurry (SC2050MNU (trade name), median diameter: 0.5 μm, nonvolatile content: 70% by mass, manufactured by Admatechs) of vinyl decane-treated cerium oxide, 71.4 parts by mass (50 parts by mass in terms of nonvolatile content) Mixing to obtain a varnish (a solution of a resin composition). The varnish was diluted with methyl ethyl ketone, impregnated and coated on an E glass woven fabric having a thickness of 0.1 mm, and dried by heating at 160 ° C for 5 minutes to obtain a prepreg having a resin content of 50% by mass.

(內層電路基板之製作) 對於形成了最小配線節距為10μm之內層電路之玻璃布基材BT樹脂兩面覆銅疊層板(銅箔厚度12μm、厚度0.2mm、三菱瓦斯化學(股)製CCL(註冊商標)-HL83 2NS(商品名))之兩面,以MEC(股)製CZ8100(商品名)實施銅表面之粗糙化處理,獲得內層電路基板。(Production of inner layer circuit board) A copper-clad laminate of BT resin having a minimum wiring pitch of 10 μm inner layer circuit (copper foil thickness 12 μm, thickness 0.2 mm, Mitsubishi Gas Chemical Co., Ltd.) On both sides of the CCL (registered trademark)-HL83 2NS (trade name), the copper surface was roughened by a CZ8100 (trade name) manufactured by MEC Co., Ltd. to obtain an inner layer circuit board.

(覆金屬箔疊層體之製作) 將前述預浸體配置在內層電路基板上下,12μm厚之電解銅箔(3EC-M3-VLP (商品名)、三井金屬(股)製)配置在上下,以壓力30kgf/cm2 、溫度220℃的條件實施120分鐘之疊層成型,獲得將內層電路基板與樹脂組成物層與銅箔疊層而得的覆金屬箔疊層體。(Preparation of a metal foil-clad laminate) The prepreg is placed on the inner layer of the inner layer circuit board, and an electrolytic copper foil (3EC-M3-VLP (trade name) or Mitsui Metals Co., Ltd.) having a thickness of 12 μm is placed on the upper and lower sides. The laminate was molded by a pressure of 30 kgf/cm 2 and a temperature of 220 ° C for 120 minutes to obtain a metal foil-clad laminate in which an inner layer circuit board and a resin composition layer were laminated with a copper foil.

(評價用硬化物之製作) 將4片前述預浸體重疊,並將12μm厚之電解銅箔(3EC-M3-VLP(商品名)、三井金屬(股)製)配置在上下,以壓力30kgf/cm2 、溫度220℃的條件進行120分鐘的疊層成型,獲得絕緣層厚度0.4mm之覆金屬箔疊層板。將獲得之覆金屬箔疊層板之全部金屬箔蝕刻除去,獲得評價用硬化物。(Preparation of cured product for evaluation) Four sheets of the above-mentioned prepreg were superposed, and 12 μm thick electrolytic copper foil (3EC-M3-VLP (trade name), manufactured by Mitsui Metals Co., Ltd.) was placed up and down at a pressure of 30 kgf. /cm 2 and a temperature of 220 ° C were subjected to lamination molding for 120 minutes to obtain a metal foil-clad laminate having an insulating layer thickness of 0.4 mm. All the metal foils of the obtained metal foil-clad laminate were etched away to obtain a cured product for evaluation.

[實施例2] 將作為被覆有二氧化矽之氟樹脂粒子(A)之一次粒子之體積平均粒徑為3.0 μm之被覆有二氧化矽之PTFE填料之MEK漿液(PTFE-YA4(商品名)、一次粒子之體積平均粒徑3.0μm、不揮發成分40質量%、Admatechs(股)製)改為使用125質量份(按不揮發成分換算,為50質量份),除此以外和實施例1同樣製備清漆,獲得預浸體、覆金屬箔疊層體、評價用硬化物。[Example 2] A MEK slurry (PTFE-YA4 (trade name)) of a PTFE filler coated with cerium oxide as a primary particle having a size of 3.0 μm as a primary particle of fluororesin particles (A) coated with cerium oxide In addition, the volume average particle diameter of the primary particles is 3.0 μm, the nonvolatile content is 40% by mass, and the product of Admatechs is used in an amount of 125 parts by mass (50 parts by mass in terms of nonvolatile content), and Example 1 is used. A varnish was prepared in the same manner, and a prepreg, a metal foil-clad laminate, and a cured product for evaluation were obtained.

[實施例3] 將作為被覆有二氧化矽之氟樹脂粒子(A)之被覆有二氧化矽之PTFE填料之MEK漿液(0.5μm PTFE-YA(商品名)、一次粒子之體積平均粒徑0.5μm、不揮發成分20質量%、Admatechs(股)製)250質量份(按不揮發成分換算,為50質量份)、作為氰酸酯化合物之合成例1獲得之SNCN2.0質量份、2,2-雙(4-氰氧基苯基)丙烷之預聚物(CA210(商品名)、氰酸酯當量139、三菱瓦斯化學(股)製)6.2質量份、作為環氧樹脂之溴化雙酚A型環氧樹脂(E153(商品名)、環氧當量400、2級羥基量0.3 meq/g、DIC(股)製)10.0質量份、作為具乙烯性不飽和基之化合物之合成例2獲得之乙烯基化合物(數量平均分子量為1187、乙烯基當量為590g/乙烯基)72.8質量份、α-甲基苯乙烯寡聚物(KA3085(商品名)、質量平均分子量:664、美國Eastman Chemical Company製)3.0質量份、作為其他填充材(C)之乙烯基矽烷處理二氧化矽之MEK漿液(SC2050MNU(商品名)、中位徑0.5μm、不揮發成分70質量%、Admatec hs(股)製)71.4質量份(按不揮發成分換算,為50質量份)、作為阻燃劑(D)之溴化聚碳酸酯(FG8500(商品名)、帝人(股)製,溴含量58重量%)6質量份混合,獲得清漆。之後和實施例1同樣進行,獲得預浸體、覆金屬箔疊層體、評價用硬化物。[Example 3] MEK slurry (0.5 μm PTFE-YA (trade name), volume average particle diameter of primary particles) of PTFE filler coated with cerium oxide coated with cerium oxide-containing fluororesin particles (A) 250 parts by mass of the non-volatile component (manufactured by Admatechs Co., Ltd.), 50 parts by mass (50 parts by mass in terms of nonvolatile content), and 2.0 parts by mass of SNCN obtained as the synthesis example 1 of the cyanate compound, 2, Prepolymer of 2-bis(4-cyanooxyphenyl)propane (CA210 (trade name), cyanate equivalent 139, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 6.2 parts by mass, brominated double as epoxy resin Phenol A-type epoxy resin (E153 (trade name), epoxy equivalent 400, 2-stage hydroxyl group 0.3 meq/g, manufactured by DIC), 10.0 parts by mass, and Synthesis Example 2 as a compound having an ethylenically unsaturated group The obtained vinyl compound (number average molecular weight: 1187, vinyl equivalent weight: 590 g / vinyl group) 72.8 parts by mass, α-methylstyrene oligomer (KA3085 (trade name), mass average molecular weight: 664,, Eastman Chemical, USA) 3.0 parts by mass of MEK slurry treated with vinyl decane as a filler (C) (SC2050MNU (trade name) ), a median diameter of 0.5 μm, a nonvolatile content of 70% by mass, and 71.4 parts by mass of Admatec hs (manufactured by the company) (50 parts by mass in terms of nonvolatile content), and a brominated polycarbonate as a flame retardant (D) Ester (FG8500 (trade name), manufactured by Teijin Co., Ltd., bromine content: 58% by weight) was mixed in an amount of 6 parts by mass to obtain a varnish. Thereafter, in the same manner as in Example 1, a prepreg, a metal foil-clad laminate, and a cured product for evaluation were obtained.

[實施例4] (樹脂組成物及樹脂片之製作) 將作為被覆有二氧化矽之氟樹脂粒子(A)之被覆有二氧化矽之PTFE填料之MEK漿液(0.5μmPTFE-YA(商品名)、一次粒子之體積平均粒徑0.5μm、不揮發成分20質量%、Admatechs(股)製)250質量份(按不揮發成分換算,為50質量份)、作為氰酸酯化合物之合成例1獲得之SNCN2.1質量份、2,2-雙(4-氰氧基苯基)丙烷之預聚物(CA210(商品名)、氰酸酯當量139、三菱瓦斯化學(股)製)6.6質量份、作為環氧樹脂之溴化雙酚A型環氧樹脂(E153(商品名)、環氧當量400、2級羥基量0.3 meq/g,DIC(股)製)10.6質量份、作為具乙烯性不飽和基之化合物之合成例2獲得之乙烯基化合物(數量平均分子量為1187、乙烯基當量為590g/乙烯基)77.5質量份、α-甲基苯乙烯寡聚物(KA3085(商品名)、質量平均分子量:664、美國Eastman Chemical Company製)3.2質量份、作為其他填充材(C)之乙烯基矽烷處理二氧化矽之MEK漿液(SC2050MNU(商品名)、中位徑0.5μm、不揮發成分70質量%、Admatec hs(股)製)71.4質量份(按不揮發成分換算,為50質量份)混合,獲得清漆。將該等清漆塗佈在厚度12μm的電解銅箔(3EC-M2S-VLP(商品名)、三井金屬(股)製)上,於120℃進行5分鐘加熱乾燥,獲得以銅箔作為支持體且樹脂組成物層之厚度為40μm之樹脂片。[Example 4] (Preparation of resin composition and resin sheet) MEK slurry (0.5 μm PTFE-YA (trade name)) as a PTFE filler coated with cerium oxide coated with cerium oxide-containing fluororesin particles (A) , the volume average particle diameter of the primary particles is 0.5 μm, the nonvolatile content is 20% by mass, and 250 parts by mass of Admatechs Co., Ltd. (50 parts by mass in terms of nonvolatile content), and the synthesis example 1 of the cyanate compound is obtained. 2.1 parts by mass of SNCN and a prepolymer of 2,2-bis(4-cyanooxyphenyl)propane (CA210 (trade name), cyanate equivalent 139, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 6.6 parts by mass A brominated bisphenol A type epoxy resin (E153 (trade name), an epoxy equivalent of 400, a 2-stage hydroxyl group of 0.3 meq/g, DIC (manufactured by DIC)) as an epoxy resin, and having an ethylene property as 10.6 parts by mass. Synthesis Example 2 The vinyl compound (number average molecular weight: 1187, vinyl equivalent weight: 590 g/vinyl group) of 77.5 parts by mass, α-methylstyrene oligomer (KA3085 (trade name), Mass average molecular weight: 664, manufactured by Eastman Chemical Company, USA, 3.2 parts by mass, treated with vinyl decane as other filler (C) The MEK slurry (SC2050MNU (trade name), median diameter 0.5 μm, nonvolatile matter 70 mass%, manufactured by Admatec hs) was mixed with 71.4 parts by mass (50 parts by mass in terms of nonvolatile content). Varnish. The varnish was applied onto an electrolytic copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metals Co., Ltd.) having a thickness of 12 μm, and dried by heating at 120 ° C for 5 minutes to obtain a copper foil as a support. A resin sheet having a thickness of 40 μm was used as the resin composition layer.

(覆金屬箔疊層體之製作) 將前述以銅箔作為支持體之樹脂片之樹脂面配置在實施例1使用的內層電路基板上,於壓力30kgf/cm2 、溫度220℃進行120分鐘的疊層成型,獲得內層電路基板與樹脂組成物層與銅箔疊層而成的覆金屬箔疊層體。(Production of the metal foil-clad laminate) The resin surface of the resin sheet having the copper foil as a support was placed on the inner layer circuit board used in Example 1, and the pressure was 30 kgf/cm 2 and the temperature was 220 ° C for 120 minutes. In the multilayer molding, a metal foil-clad laminate in which an inner layer circuit board, a resin composition layer, and a copper foil are laminated is obtained.

(評價用硬化物之製作) 將獲得之覆金屬箔疊層體之全部金屬箔蝕刻除去,獲得評價用硬化物。(Production of cured product for evaluation) All the metal foils of the obtained metal foil-clad laminate were removed by etching to obtain a cured product for evaluation.

[比較例1] 將被覆有二氧化矽之氟樹脂粒子(A)替換為使用PTFE分散液(EXP. FD-030 (商品名)、中位徑0.5μm、不揮發成分40質量%、DIC(股)製)125質量份(按不揮發成分換算,為50質量份),除此以外和實施例3同樣進行,製備清漆,獲得預浸體、覆金屬箔疊層體、評價用硬化物。[Comparative Example 1] The fluororesin particles (A) coated with cerium oxide were replaced with a PTFE dispersion (EXP. FD-030 (trade name), a median diameter of 0.5 μm, a nonvolatile content of 40% by mass, and DIC ( A varnish was prepared in the same manner as in Example 3 except that 125 parts by mass (50 parts by mass in terms of a nonvolatile content) was obtained, and a prepreg, a metal foil-clad laminate, and a cured product for evaluation were obtained.

[比較例2] 不使用被覆有二氧化矽之氟樹脂粒子(A),並就其他填充材(C)而言使用乙烯基矽烷處理二氧化矽之MEK漿液(SC2050MNU(商品名)、中位徑0.5μm、不揮發成分70質量%、Admatechs(股)製)142.9質量份(按不揮發成分換算,為100質量份),除此以外和實施例1同樣進行,製備清漆,獲得預浸體、覆金屬箔疊層體、評價用硬化物。[Comparative Example 2] MEK slurry (SC2050MNU (trade name), median) in which cerium oxide coated with cerium oxide (A) was not used, and cerium oxide was treated with vinyl decane for other fillers (C) A varnish was prepared in the same manner as in Example 1 except that the diameter was 0.5 μm, the nonvolatile content was 70% by mass, and 142.9 parts by mass of Admatechs (manufactured by Admatechs Co., Ltd.), and a prepreg was obtained. A metal foil-clad laminate and a cured product for evaluation.

[實施例5] 將作為被覆有二氧化矽之氟樹脂粒子(A)之被覆有二氧化矽之PTFE填料之MEK漿液(0.5μm PTFE-YA(商品名)、一次粒子之體積平均粒徑0.5μm、不揮發成分20質量%、Admatechs(股)製)250質量份(按不揮發成分換算,為50質量份)、作為馬來醯亞胺化合物之馬來醯亞胺化合物(BMI-2300(商品名)、大和化成工業(股)製)3.5質量份、作為環氧樹脂之聯苯芳烷基型環氧樹脂(NC3000H(商品名)、日本化藥(股)製)19.8質量份、作為具乙烯性不飽和基之化合物之酸改性雙酚F型環氧丙烯酸酯化合物之丙二醇單甲醚乙酸酯(以下有時簡稱PMA)溶液(KAYARAD (註冊商標)ZFR-1553H(商品名)、不揮發成分68質量%、酸價:70mgKOH/g、日本化藥(股)製)77.6質量份(按不揮發成分換算,為52.8質量份)、六丙烯酸二新戊四醇酯(KAYARAD(註冊商標)DPHA(商品名)、日本化藥(股)製)18.9質量份、作為光硬化起始劑(E)之2-苄基-2-二甲胺基-1-(4-??啉代苯基)-丁-1-酮(Irgacure(註冊商標)369(商品名)、BASF Japan(股)製)5質量份摻合,以超音波均質機攪拌,獲得清漆(樹脂組成物之溶液)。將該等清漆塗佈在厚度38μm的PET薄膜(Unipeel (註冊商標)TR1-38、Unitika(股)製,商品名)上,於80℃進行7分鐘加熱乾燥,獲得以PET薄膜作為支持體且樹脂組成物層之厚度為40μm之樹脂片。[Example 5] MEK slurry (0.5 μm PTFE-YA (trade name), volume average particle diameter of primary particles) of PTFE filler coated with cerium oxide coated with cerium oxide-containing fluororesin particles (A) Mm, a nonvolatile component (20% by mass, manufactured by Admatechs Co., Ltd.), 250 parts by mass (50 parts by mass in terms of nonvolatile content), and a maleic imine compound (BMI-2300 (as a maleimide compound) 3.5 parts by mass of a biphenyl aralkyl type epoxy resin (NC3000H (trade name), manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, as a product name) A solution of an acid-modified bisphenol F-type epoxy acrylate compound having an ethylenically unsaturated group, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PMA) (KAYARAD (registered trademark) ZFR-1553H (trade name) 68% by mass of nonvolatile matter, acid value: 70 mgKOH/g, manufactured by Nippon Chemical Co., Ltd., 77.6 parts by mass (52.8 parts by mass in terms of nonvolatile content), and dipentaerythritol hexaacrylate (KAYARAD ( Registered trademark) DPHA (trade name), Nippon Chemical Co., Ltd.) 18.9 parts by mass, 2-benzyl-2-dimethyl group as photohardening initiator (E) 5-(4-?-morpholinophenyl)-butan-1-one (Irgacure (registered trademark) 369 (trade name), manufactured by BASF Japan Co., Ltd.) blended with 5 parts by mass, with ultrasonic homogenizer Stirring to obtain a varnish (a solution of a resin composition). The varnish was applied to a PET film (Unipeel (registered trademark) TR1-38, manufactured by Unitika Co., Ltd., trade name) having a thickness of 38 μm, and dried by heating at 80 ° C for 7 minutes to obtain a PET film as a support. A resin sheet having a thickness of 40 μm was used as the resin composition layer.

(評價用疊層體之製作) 將前述以PET薄膜作為支持體之樹脂片之樹脂面配置在實施例1使用的內層電路基板上,使用真空層合機(Nikko materials(股)製)進行30秒真空抽吸(5.0MPa以下)後,於壓力10kgf/cm2 、溫度70℃進行30秒疊層成形。再於壓力10kgf/cm2 、溫度70℃進行60秒疊層成形,獲得內層電路基板與樹脂組成物層與支持體疊層而得的疊層體。對於獲得之疊層體實施照射200mJ/cm2 之紫外線之曝光步驟,將支持體剝下,以1質量%之碳酸鈉水溶液顯影,製成評價用疊層體。(Production of the laminate for evaluation) The resin surface of the resin sheet having the PET film as a support was placed on the inner layer circuit board used in Example 1, and vacuum laminator (manufactured by Nikko Materials Co., Ltd.) was used. After 30 seconds of vacuum suction (5.0 MPa or less), lamination molding was carried out for 30 seconds at a pressure of 10 kgf/cm 2 and a temperature of 70 °C. Further, lamination molding was carried out for 60 seconds at a pressure of 10 kgf/cm 2 and a temperature of 70 ° C to obtain a laminate in which an inner layer circuit board, a resin composition layer and a support were laminated. The obtained laminate was subjected to an exposure step of irradiating ultraviolet rays of 200 mJ/cm 2 , and the support was peeled off and developed with a 1% by mass aqueous solution of sodium carbonate to prepare a laminate for evaluation.

(評價用硬化物之製作) 對於前述樹脂片照射200mJ/cm2 之紫外線,再實施於180℃進行120分鐘加熱處理之後烘烤步驟後,將支持體剝下,作為評價用硬化物。(Preparation of cured product for evaluation) The resin sheet was irradiated with ultraviolet rays of 200 mJ/cm 2 , and further subjected to a heat treatment at 180 ° C for 120 minutes, followed by a baking step, and then the support was peeled off to obtain a cured product for evaluation.

[實施例6] 將作為被覆有二氧化矽之氟樹脂粒子(A)之被覆有二氧化矽之PTFE填料之MEK漿液(0.5μmPTFE-YA(商品名)、一次粒子之體積平均粒徑0.5μm、不揮發成分20質量%、Admatechs(股)製)100質量份(不揮發成分換算20質量份)、馬來醯亞胺化合物(BMI-2300(商品名)、大和化成工業(股)製)3.5質量份、作為環氧樹脂之聯苯芳烷基型環氧樹脂(KAYARAD(註冊商標)NC3000H(商品名)、日本化藥(股)製)19.8質量份、作為具乙烯性不飽和基之化合物之酸改性雙酚F型環氧丙烯酸酯化合物之PMA溶液(KAYARAD(註冊商標)ZFR-1553H(商品名)、不揮發成分68質量%、酸價:70mgKOH/g、日本化藥(股)製)77.6質量份(按不揮發成分換算,為52.8質量份)、六丙烯酸二新戊四醇酯(KAYARAD(註冊商標)DPHA(商品名)、日本化藥(股)製)18.9質量份、作為其他填充材(C)之環氧矽烷處理二氧化矽之ME K漿液(SC2050MB(商品名)、中位徑0.5μm、不揮發成分70質量%、Admatechs(股)製)42.9質量份(按不揮發成分換算,為30質量份)、作為光硬化起始劑(E)之2-苄基-2-二甲胺基-1-(4-??啉代苯基)-丁-1-酮(Irgacure(註冊商標)369(商品名)、BASF Japan(股)製)5質量份摻合,以超音波均質機攪拌,獲得清漆。之後和實施例5同樣進行,獲得樹脂片、評價用疊層體、評價用硬化物。[Example 6] A MEK slurry (0.5 μm PTFE-YA (trade name), a primary particle having a volume average particle diameter of 0.5 μm as a PTFE filler coated with cerium oxide-coated fluororesin particles (A) 100 parts by mass of non-volatile components, 100 parts by weight of Admatechs (20 parts by mass of non-volatile components), and maleic imine compounds (BMI-2300 (trade name), Daiwa Kasei Kogyo Co., Ltd.) 3.5 parts by mass of a biphenyl aralkyl type epoxy resin (KAYARAD (registered trademark) NC3000H (trade name), manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, as an ethylenically unsaturated group PMA solution of acid-modified bisphenol F-type epoxy acrylate compound of compound (KAYARAD (registered trademark) ZFR-1553H (trade name), non-volatile content 68% by mass, acid value: 70 mgKOH/g, Nippon Chemical Co., Ltd. 77.6 parts by mass (52.8 parts by mass in terms of non-volatile content), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd.) 18.9 parts by mass MEK slurry (SC2050MB (trade name), median diameter 0.5 μm, no wave) of cerium oxide treated with epoxy decane as another filler (C) 70% by mass of the component, 42.9 parts by mass of Admatechs Co., Ltd. (30 parts by mass in terms of nonvolatile content), 2-benzyl-2-dimethylamino-1 as photohardening initiator (E) 5 parts by mass of -(4-?-morpholinophenyl)-butan-1-one (Irgacure (registered trademark) 369 (trade name), manufactured by BASF Japan Co., Ltd.) was mixed with a sonic homogenizer to obtain Varnish. Thereafter, in the same manner as in Example 5, a resin sheet, a laminate for evaluation, and a cured product for evaluation were obtained.

[實施例7] 使用作為被覆有二氧化矽之氟樹脂粒子(A)之一次粒子之體積平均粒徑為3.0μm之被覆有二氧化矽之PTFE填料之MEK漿液(PTFE-YA4(商品名)、一次粒子之體積平均粒徑3.0μm、不揮發成分40質量%、Admatechs(股)製)125質量份(按不揮發成分換算,為50質量份),除此以外和實施例5同樣製備清漆,獲得樹脂片、評價用疊層體、評價用硬化物。[Example 7] A MEK slurry (PTFE-YA4 (trade name)) of a PTFE filler coated with cerium oxide having a volume average particle diameter of 3.0 μm as a primary particle of urethane resin particles (A) coated with cerium oxide was used. A varnish was prepared in the same manner as in Example 5 except that the volume average particle diameter of the primary particles was 3.0 μm, the nonvolatile content was 40% by mass, and 125 parts by mass of Admatechs Co., Ltd. (50 parts by mass in terms of nonvolatile content). A resin sheet, a laminate for evaluation, and a cured product for evaluation were obtained.

[實施例8] 將作為具乙烯性不飽和基之化合物之酸改性雙酚F型環氧丙烯酸酯化合物之PMA溶液(KAYARAD(註冊商標)ZFR-1553H(商品名)、不揮發成分68質量%、酸價:70mgKOH/g、日本化藥(股)製)替換為使用式(4)表示之TrisP-PA環氧丙烯酸酯化合物之PMA溶液(KAYARAD(註冊商標)ZCR-6007H(商品名)、不揮發成分65質量%、酸價:70mgKOH/g、日本化藥(股)製)81.2質量份(按不揮發成分換算,為52.8質量份),除此以外和實施例5同樣進行,製備清漆,獲得樹脂片、評價用疊層體、評價用硬化物。 又,前述KAYARAD(註冊商標)ZCR-6007H係含有上述化合物(A1)及上述化合物(A2)~(A5)中任一種以上之混合物。[Example 8] A PMA solution (KAYARAD (registered trademark) ZFR-1553H (trade name), non-volatile content 68 mass of an acid-modified bisphenol F-type epoxy acrylate compound as a compound having an ethylenically unsaturated group %, acid value: 70 mg KOH/g, manufactured by Nippon Kayaku Co., Ltd., replaced with PMA solution of TrisP-PA epoxy acrylate compound represented by formula (4) (KAYARAD (registered trademark) ZCR-6007H (trade name) In the same manner as in Example 5, except that the amount of the nonvolatile component was 65 mass%, the acid value was 70 mg KOH/g, and the amount of the acid (manufactured by Nippon Chemical Co., Ltd.) was 81.2 parts by mass (52.8 parts by mass in terms of nonvolatile content). The varnish was obtained as a resin sheet, a laminate for evaluation, and a cured product for evaluation. Further, KAYARAD (registered trademark) ZCR-6007H contains a mixture of any one or more of the above compound (A1) and the above compounds (A2) to (A5).

[比較例3] 將被覆有二氧化矽之氟樹脂粒子(A)替換為使用PTFE分散液(EXP. FD-030 (商品名)、中位徑0.5μm、不揮發成分40質量%、DIC(股)製)125質量份(按不揮發成分換算,為50質量份),除此以外和實施例5同樣製備清漆,獲得樹脂片、評價用疊層體、評價用硬化物。[Comparative Example 3] The fluororesin particles (A) coated with ceria were replaced with a PTFE dispersion (EXP. FD-030 (trade name), a median diameter of 0.5 μm, a nonvolatile component of 40% by mass, and DIC ( A varnish was prepared in the same manner as in Example 5 except that 125 parts by mass (50 parts by mass in terms of non-volatile content) was obtained, and a resin sheet, a laminate for evaluation, and a cured product for evaluation were obtained.

[比較例4] 不使用被覆有二氧化矽之氟樹脂粒子(A),並就其他填充材(C)而言使用環氧矽烷處理二氧化矽之MEK漿液(SC2050MB(商品名)、中位徑0.5μm、不揮發成分70質量%、Admatechs(股)製)71.4質量份(按不揮發成分換算,為50質量份),除此以外和實施例5同樣製備清漆,獲得樹脂片、評價用疊層體、評價用硬化物。[Comparative Example 4] MEK slurry (SC2050MB (trade name), median) in which cerium oxide coated with cerium oxide (A) was not used, and cerium oxide was treated with epoxy decane for other fillers (C) A varnish was prepared in the same manner as in Example 5 except that the diameter was 0.5 μm, the nonvolatile content was 70% by mass, and 71.4 parts by mass of Admatechs (manufactured by Admatechs Co., Ltd.), and the resin sheet was obtained for evaluation. A laminate and a cured product for evaluation.

[物性測定評價] 依以下之方法測定覆金屬箔疊層體、評價用疊層體及評價用硬化物並評價。 它們的結果彙整於表1~3。[Evaluation of Physical Property Measurement] The metal foil-clad laminate, the evaluation laminate, and the evaluation cured product were measured and evaluated by the following methods. Their results are summarized in Tables 1-3.

<配線填埋性> 將覆金屬箔疊層體50mm×50mm之樣本之單面之一半以外之全部銅箔已蝕刻除去之試驗片、或評價用疊層體50mm×50mm之試驗片,以壓力鍋試驗機(平山製作所製,PC-3型)於121℃、2大氣壓進行5小時處理後,於260℃之焊料中浸漬60秒後,以目視觀察外觀變化,並依以下之基準評價。 ◎:5個試驗片皆未發生隆起。 ○:5個試驗片中有1個發生隆起。 ×:5個試驗片中有2個以上發生隆起。<Wiring and filling property> A test piece in which all the copper foils other than one half of the one-sided half of the sample of the metal foil-clad laminate 50 mm × 50 mm have been etched away, or a test piece of 50 mm × 50 mm for the evaluation laminated body is used as a pressure cooker The test machine (manufactured by Hirayama Seisakusho Co., Ltd., PC-3 type) was subjected to a treatment at 121 ° C for 2 hours at 2 atm, and then immersed in a solder at 260 ° C for 60 seconds, and visually observed the change in appearance, and evaluated according to the following criteria. ◎: None of the five test pieces had a bulge. ○: One of the five test pieces was bulged. ×: Two or more of the five test pieces were embossed.

<焊料耐熱性> 使覆金屬箔疊層體50mm×50mm之試驗片、或評價用疊層體50mm×50mm之試驗片浮於280℃之焊料30分鐘,以目視觀察外觀是否有異常,並依以下之基準評價。 ○:試驗片5個皆未發生隆起。 ×:試驗片5個中有1個以上發生隆起。<Solder heat resistance> The test piece of the metal foil-clad laminate 50 mm × 50 mm or the test piece of the evaluation laminate 50 mm × 50 mm was floated on the solder at 280 ° C for 30 minutes, and the appearance was visually observed for abnormality. The following benchmark evaluation. ○: No bulging occurred in all of the test pieces. ×: One or more of the five test pieces were embossed.

<介電常數、介電正切> 將評價用硬化物之試驗片以空洞共振器擾動法(Agilent(註冊商標)8722ES、安捷倫科技公司製)測定10GHz之介電常數、及介電正切。<Dielectric Constant, Dielectric Tangent> The dielectric constant of the 10 GHz and the dielectric tangent were measured by a cavity resonator perturbation method (Agilent (registered trademark) 8722ES, manufactured by Agilent Technologies Co., Ltd.).

<顯影性> 以目視觀察評價用疊層體之顯影面後,以SEM觀察(倍率1000倍),依下列基準評價是否有殘渣。 ○:在30mm四方之範圍無顯影殘渣,顯影性優良。 ×:在30mm四方之範圍有顯影殘渣,顯影性不佳。<Developability> After visual observation of the development surface of the laminate for evaluation, it was observed by SEM (magnification: 1000 times), and whether or not there was residue was evaluated according to the following criteria. ○: There was no development residue in the range of 30 mm square, and the developability was excellent. X: There is a development residue in the range of 30 mm square, and the developability is not good.

<耐熱性(玻璃轉移溫度)> 使用DMA裝置(TA INSTRUMENT公司製動態黏彈性測定裝置DMAQ800 (商品名))將評價用硬化物以10℃/分升溫,定義LossModulus之峰部位置為玻璃轉移溫度(Tg)。<Heat resistance (glass transition temperature)> Using a DMA apparatus (dynamic viscoelasticity measuring apparatus DMAQ800 (trade name) manufactured by TA INSTRUMENT Co., Ltd.), the cured product for evaluation was heated at 10 ° C /min, and the peak position of LossModulus was defined as the glass transition temperature. (Tg).

【表1】 【Table 1】

【表2】 【Table 2】

【表3】 【table 3】

從表1、表2及表3可以明白,實施例1~8的配線填埋性、及耐熱性優異、介電常數、介電正切良好。其中,實施例1、實施例4及實施例5的配線填埋性、介電常數良好。實施例8,耐熱性(Tg)更高,為良好。反觀比較例1~4,配線填埋性、耐熱性及介電常數皆不理想。因此依照本發明,可獲得介電常數、介電正切、微細配線填埋性、耐熱性、顯影性優良的樹脂組成物、使用此組成物之預浸體、覆金屬箔疊層板、樹脂片、印刷電路板及半導體裝置。As can be understood from Tables 1, 2 and 3, the wirings of Examples 1 to 8 were excellent in landfill property and heat resistance, and the dielectric constant and dielectric tangent were good. Among them, the wiring filling property and the dielectric constant of Example 1, Example 4, and Example 5 were good. In Example 8, the heat resistance (Tg) was higher and was good. In contrast, in Comparative Examples 1 to 4, wiring landfill properties, heat resistance, and dielectric constant were not satisfactory. Therefore, according to the present invention, a resin composition excellent in dielectric constant, dielectric tangent, fine wiring filling property, heat resistance, and developability, a prepreg using the composition, a metal foil-clad laminate, and a resin sheet can be obtained. , printed circuit boards and semiconductor devices.

no

Claims (15)

一種樹脂組成物,含有被覆有二氧化矽之氟樹脂粒子(A)及樹脂成分(B)。A resin composition comprising fluororesin particles (A) coated with cerium oxide and a resin component (B). 如申請專利範圍第1項之樹脂組成物,其中,該被覆有二氧化矽之氟樹脂粒子(A)之一次粒子之體積平均粒徑為5μm以下。The resin composition of the first aspect of the invention, wherein the primary particles of the fluororesin particles (A) coated with cerium oxide have a volume average particle diameter of 5 μm or less. 如申請專利範圍第1項之樹脂組成物,其中,該被覆有二氧化矽之氟樹脂粒子(A)在樹脂組成物中之含量,係相對於樹脂組成物中之樹脂固體成分100質量份為3~ 400質量份。The resin composition of the first aspect of the invention, wherein the content of the cerium oxide-coated fluororesin particles (A) in the resin composition is 100 parts by mass based on the resin solid content in the resin composition. 3 to 400 parts by mass. 如申請專利範圍第1項之樹脂組成物,其中,該樹脂成分(B)含有選自於由馬來醯亞胺化合物、氰酸酯化合物、環氧樹脂、苯酚樹脂、氧雜環丁烷樹脂、苯并㗁??化合物及具乙烯性不飽和基之化合物構成之群組中之任一種以上。The resin composition of claim 1, wherein the resin component (B) is selected from the group consisting of a maleimide compound, a cyanate compound, an epoxy resin, a phenol resin, and an oxetane resin. Any one or more of the group consisting of a benzoxanthene compound and a compound having an ethylenically unsaturated group. 如申請專利範圍第1項之樹脂組成物,更含有該被覆有二氧化矽之氟樹脂粒子(A)以外之填充材(C)。The resin composition of the first aspect of the patent application further contains a filler (C) other than the fluororesin particles (A) coated with cerium oxide. 如申請專利範圍第1項之樹脂組成物,更含有阻燃劑(D)。For example, the resin composition of claim 1 of the patent scope further contains a flame retardant (D). 如申請專利範圍第1項之樹脂組成物,更含有光硬化起始劑(E)。The resin composition of claim 1 of the patent application further contains a photohardening initiator (E). 如申請專利範圍第4項之樹脂組成物,其中,該具有乙烯性不飽和基之化合物包括選自於由具乙烯基之2官能性伸苯醚寡聚物及α-甲基苯乙烯之寡聚物構成之群組中之至少一種以上。The resin composition of claim 4, wherein the compound having an ethylenically unsaturated group is selected from the group consisting of a bifunctional phenylene ether oligomer having a vinyl group and an α-methyl styrene. At least one or more of the group consisting of the polymers. 如申請專利範圍第4項之樹脂組成物,其中,該具有乙烯性不飽和基之化合物包括選自於由酸改性雙酚F型環氧(甲基)丙烯酸酯、下列通式(1)表示之化合物及二新戊四醇六(甲基)丙烯酸酯構成之群組中之至少一種以上; [化1]式(1)中,多數個R1 各自獨立地表示氫原子或甲基,且多數個R2 各自獨立地表示氫原子或甲基,多數個R3 各自獨立地表示下式(2)表示之取代基、下式(3)表示之取代基或羥基; [化2][化3]式(3)中,R4 表示氫原子或甲基。The resin composition of claim 4, wherein the compound having an ethylenically unsaturated group is selected from the group consisting of an acid modified bisphenol F type epoxy (meth) acrylate, the following general formula (1) At least one or more of the group consisting of the compound and dipentaerythritol hexa(meth) acrylate; [Chemical Formula 1] In the formula (1), a plurality of R 1 each independently represent a hydrogen atom or a methyl group, and a plurality of R 2 each independently represent a hydrogen atom or a methyl group, and a plurality of R 3 each independently represent a formula (2). a substituent, a substituent represented by the following formula (3) or a hydroxyl group; [Chemical 2] [Chemical 3] In the formula (3), R 4 represents a hydrogen atom or a methyl group. 如申請專利範圍第9項之樹脂組成物,其中,該具有乙烯性不飽和基之化合物至少包括該通式(1)表示之化合物。The resin composition of claim 9, wherein the compound having an ethylenically unsaturated group includes at least the compound represented by the formula (1). 一種預浸體,具有:基材,及含浸或塗佈於該基材之如申請專利範圍第1至10項中任一項之樹脂組成物。A prepreg comprising: a substrate, and a resin composition impregnated or coated on the substrate according to any one of claims 1 to 10. 一種覆金屬箔疊層板,具有:至少1片以上之疊層在一起之如申請專利範圍第11項之預浸體,及配置在該預浸體之單面或兩面之金屬箔。A metal foil-clad laminate comprising: at least one or more prepregs as disclosed in claim 11 and a metal foil disposed on one or both sides of the prepreg. 一種樹脂片,具有:支持體,及配置在該支持體之表面之如申請專利範圍第1至10項中任一項之樹脂組成物。A resin sheet comprising: a support, and a resin composition according to any one of claims 1 to 10, which is disposed on the surface of the support. 一種印刷電路板,具有如申請專利範圍第1至10項中任一項之樹脂組成物。A printed circuit board having the resin composition according to any one of claims 1 to 10. 一種半導體裝置,具有如申請專利範圍第1至10項中任一項之樹脂組成物。A semiconductor device having the resin composition according to any one of claims 1 to 10.
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JP2015209480A (en) * 2014-04-25 2015-11-24 三井・デュポンフロロケミカル株式会社 Fluororesin composition
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TWI816807B (en) * 2018-06-01 2023-10-01 日商三菱瓦斯化學股份有限公司 Resin compositions, prepregs, metal foil-clad laminates, resin sheets, and printed wiring boards
TWI695202B (en) * 2018-09-03 2020-06-01 亞洲電材股份有限公司 High adhesive strength liquid crystal polymer laminate and the preparation method thereof
TWI764075B (en) * 2019-01-11 2022-05-11 日商大金工業股份有限公司 Fluororesin composition, fluororesin sheet, laminate, and circuit board

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CN108603003A (en) 2018-09-28
JP6880510B2 (en) 2021-06-02

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