JP2006096798A - Epoxy resin composition for printed wiring board, prepreg for printed wiring board and metal-clad laminate and multilayer printed wiring board each using the same composition - Google Patents
Epoxy resin composition for printed wiring board, prepreg for printed wiring board and metal-clad laminate and multilayer printed wiring board each using the same composition Download PDFInfo
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本発明は、プリント配線板をはじめとする電気絶縁材料に使用するエポキシ樹脂組成物、およびその用途、例えば、プリント配線板用プリプレグおよびそれを用いた金属張積層板，および多層プリント配線板に関するものである。 The present invention relates to an epoxy resin composition used for an electrical insulating material such as a printed wiring board, and its use, for example, a prepreg for a printed wiring board, a metal-clad laminate using the same, and a multilayer printed wiring board. It is.
エポキシ樹脂を用いたプリント配線板用プリプレグは、エポキシ樹脂組成物のワニス溶液をガラス織布またはガラス不織布に含浸し、乾燥してＢステージ化する事により製造されている。エポキシ樹脂組成物としては、エポキシ樹脂に硬化剤および硬化促進剤を配合し、必要により難燃剤や充填剤を配合したものが使用されている。 A prepreg for a printed wiring board using an epoxy resin is manufactured by impregnating a glass woven fabric or glass nonwoven fabric with a varnish solution of an epoxy resin composition, and drying to form a B-stage. As an epoxy resin composition, a compound in which a curing agent and a curing accelerator are blended with an epoxy resin, and a flame retardant and a filler are blended as necessary is used.
従来、産業用電子機器などに使用される高度の特性が要求されるプリント配線板は、上記プリプレグと金属箔とを、加熱加圧することにより、積層一体化してなる金属張積層板に回路加工を施して製造されている。また、多層プリント配線板は、内層回路板および金属箔などを構成材として、構成材相互間を上記プリプレグを介して加熱加圧することにより、積層一体化して製造されている。 Conventionally, printed wiring boards that require advanced characteristics used in industrial electronic equipment, etc., are circuit-processed on metal-clad laminates that are laminated and integrated by heating and pressing the prepreg and metal foil. It is manufactured by applying. The multilayer printed wiring board is manufactured by stacking and integrating by using an inner layer circuit board, metal foil, and the like as components, and heating and pressing the components through the prepreg.
近年、電子機器の小型化，高性能化に伴い、その中に搭載されるプリント配線板は、高多層化、薄物化、スルーホールの小型化および穴間隔の狭小等による高密度化が進んでいる。さらに、携帯電話やモバイルコンピュータ等の携帯情報端末機器に搭載されるプリント配線板には、マイクロプロセッシングユニット（ＭＰＵ）をプリント配線板上に直接搭載するプラスチックパッケージや各種モジュール用のプリント配線板をはじめとして、大容量の情報を高速に処理することが求められている。そのため、プリント配線板には信号処理の高速化や低伝送損失化、更なるダウンサイジングが必要となってきており、プリント配線板は、より一層の高密度化が進み、これまで以上の微細配線が要求されている。 In recent years, along with the downsizing and high performance of electronic devices, the printed wiring boards mounted in them have been increasing in density due to higher multilayers, thinner materials, smaller through holes, and narrower hole spacing. Yes. Furthermore, printed wiring boards mounted on portable information terminal devices such as mobile phones and mobile computers include plastic packages in which a microprocessing unit (MPU) is directly mounted on a printed wiring board and printed wiring boards for various modules. Therefore, it is required to process a large amount of information at high speed. For this reason, printed circuit boards are required to have higher signal processing speed, lower transmission loss, and further downsizing. Printed circuit boards are becoming more dense and have finer wiring than ever before. Is required.
そこで、このようにＭＰＵを搭載するプリント配線板やモジュール用プリント配線板には、これまで以上の接続信頼性を確保するために、耐熱性に優れた高ガラス転移温度（以下，Ｔｇと略す）材料が開発されている（特開平８−１２７４４号公報参照）。また，高周波特性が要求される通信機器や測定機器の普及に伴い，低誘電特性が必要となってきており、それに適した材料が開発されている（特開２００２−３１７０８５号公報参照）。 Therefore, in such a printed wiring board or module printed wiring board on which an MPU is mounted, a high glass transition temperature (hereinafter abbreviated as Tg) excellent in heat resistance in order to ensure connection reliability higher than ever. Materials have been developed (see JP-A-8-12744). In addition, with the widespread use of communication devices and measuring devices that require high-frequency characteristics, low dielectric characteristics have become necessary, and materials suitable for these have been developed (see JP 2002-317085 A).
本発明は，従来以上の高いＴｇを有し，かつ低誘電特性を有するのに適したプリント配線板を得る為に成されたものである。本発明の目的は、プリント配線板のＴｇを高くし、低誘電特性を有するのに適したエポキシ樹脂組成物、ならびに、それを用いたプリント配線板用プリプレグ，金属張積層板及び多層プリント配線板を提供することにある。 The present invention has been made in order to obtain a printed wiring board having a higher Tg than conventional and suitable for having a low dielectric property. An object of the present invention is to provide an epoxy resin composition suitable for increasing the Tg of a printed wiring board and having low dielectric properties, and a prepreg for a printed wiring board, a metal-clad laminate, and a multilayer printed wiring board using the same. Is to provide.
本発明は、次のものに関する。
（１）（ａ）フェノール類とヒドロキシベンズアルデヒドとの縮合物をエポキシ化して得られるエポキシ樹脂、（ｂ）フェノール類付加ポリブタジエン、（ｃ）１−シアノエチル−２−エチル−イミダゾールの環状縮合物を必須成分として含むプリント配線板用エポキシ樹脂組成物。
（２）項（１）に記載のプリント配線板用エポキシ樹脂組成物をガラス織布又はガラス不織布に含浸し、加熱して、Ｂステージ化してなるプリント配線板用プリプレグ。
（３）項（２）に記載のプリント配線板用プリプレグを少なくとも１枚以上重ね、その片面もしくは両面に金属箔を介して加熱加圧成形して得られる金属張積層板。
（４）項（２）に記載のプリント配線板用プリプレグを、多層プリント配線板の構成材の接着材料として、積層一体化して得られる多層プリント配線板。
The present invention relates to the following.
(1) (a) an epoxy resin obtained by epoxidizing a condensate of phenols and hydroxybenzaldehyde, (b) a phenol-added polybutadiene, and (c) a cyclic condensate of 1-cyanoethyl-2-ethyl-imidazole are essential. An epoxy resin composition for printed wiring boards, which is included as a component.
(2) A prepreg for a printed wiring board obtained by impregnating a glass woven fabric or glass nonwoven fabric with the epoxy resin composition for a printed wiring board according to item (1) and heating to form a B stage.
(3) A metal-clad laminate obtained by stacking at least one prepreg for a printed wiring board according to item (2) and heat-pressing one or both sides thereof with a metal foil.
(4) A multilayer printed wiring board obtained by stacking and integrating the prepreg for printed wiring board according to item (2) as an adhesive material for a constituent material of the multilayer printed wiring board.
本発明によれば、プリント配線板のＴｇを高くし、かつ低誘電特性を有するのに適したエポキシ樹脂組成物を得ることができる。また、本発明のエポキシ樹脂組成物を用いてＴｇが高く低誘電特性を有するプリント配線板用プリプレグ，金属張積層板および多層プリント配線板を得ることができる。 According to the present invention, an epoxy resin composition suitable for increasing the Tg of a printed wiring board and having low dielectric properties can be obtained. In addition, a printed wiring board prepreg, a metal-clad laminate, and a multilayer printed wiring board having high Tg and low dielectric properties can be obtained using the epoxy resin composition of the present invention.
以下，本発明を詳細に説明する。
（ａ）フェノール類とヒドロキシベンズアルデヒドとの縮合物をエポキシ化して得られるエポキシ樹脂としては，フェノール類、ヒドロキシベンズアルデヒドの種類については特に限定するものではなく、縮合及びエポキシ化の方法についても特に限定するものではない。例えば、フェノール類としては、フェノール、クレゾールをはじめ、プロピル基、ｔｅｒｔ−ブチル基などのアルキル基を有する一価フェノール類と、ヒドロキシベンズアルデヒドとしては、サリチルアルデヒド、ｍ−ヒドロキシベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、バニリン、シリンガアルデヒド、β−レゾルシアルデヒド、プロトカテキュアルデヒドなどのヒドロキシベンズアルデヒドとを、酸触媒下における縮合物を原料とし、エピクロルヒドリンなどによりエポキシ化した化合物が挙げられる。そして、酸触媒下において、フェノール類とヒドロキシベンズアルデヒドとを縮合させ、その縮合物を原料とし、エピクロルヒドリンなどによりエポキシ化し、本発明で使用するエポキシ樹脂としても良い。
The present invention will be described in detail below.
(A) As an epoxy resin obtained by epoxidizing a condensate of phenols and hydroxybenzaldehyde, the types of phenols and hydroxybenzaldehyde are not particularly limited, and the methods of condensation and epoxidation are also particularly limited. It is not a thing. For example, as phenols, monohydric phenols having an alkyl group such as propyl group and tert-butyl group as well as phenol and cresol, and as hydroxybenzaldehyde, salicylaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, Examples thereof include compounds obtained by epoxidation with epichlorohydrin or the like using a condensate in the presence of an acid catalyst and hydroxybenzaldehyde such as vanillin, syringaldehyde, β-resorcaldehyde, or protocatecaldehyde. Then, in the presence of an acid catalyst, phenols and hydroxybenzaldehyde are condensed, the condensate is used as a raw material, and epoxidized with epichlorohydrin or the like, and may be used as an epoxy resin used in the present invention.
また、（ａ）フェノール類とヒドロキシベンズアルデヒドとを縮合して得られるエポキシ樹脂としては，市販品であるフェノールサリチルアルデヒドノボラック型エポキシ樹脂（ジャパンエポキシレジン株式会社製商品名ＹＬ６７８１，エポキシ当量１７０）などが使用できる。また、本発明においては、（ａ）フェノール類とヒドロキシベンズアルデヒドとを縮合して得られるエポキシ樹脂以外のエポキシ樹脂を併用してもよい。本発明の目的に鑑みて、用いるエポキシ樹脂は、低誘電率化されたエポキシ樹脂が好ましい。また、プリント配線板用エポキシ樹脂組成物の性能を補うため、本発明の効果を損なわない程度に二官能エポキシ樹脂、多官能エポキシ樹脂、他の熱硬化性樹脂あるいは官能基を有する熱可塑性樹脂を併用することもできる。 Moreover, (a) As an epoxy resin obtained by condensing phenols and hydroxybenzaldehyde, a commercially available phenol salicylaldehyde novolac type epoxy resin (trade name YL6781, epoxy equivalent 170 by Japan Epoxy Resin Co., Ltd.) and the like are available. Can be used. Moreover, in this invention, you may use together epoxy resins other than the epoxy resin obtained by condensing (a) phenols and hydroxybenzaldehyde. In view of the object of the present invention, the epoxy resin used is preferably an epoxy resin having a low dielectric constant. In addition, in order to supplement the performance of the epoxy resin composition for printed wiring boards, a bifunctional epoxy resin, a polyfunctional epoxy resin, another thermosetting resin or a thermoplastic resin having a functional group is added to the extent that the effects of the present invention are not impaired. It can also be used together.
本発明において使用される熱硬化性樹脂又は熱可塑性樹脂としては、特に制限されないが、ポリイミド樹脂、トリアジン樹脂、メラミン樹脂、フェノール樹脂、シアネート類化合物等が挙げられ、これらを単独で、または、２種以上併用することができる。 Although it does not restrict | limit especially as a thermosetting resin or a thermoplastic resin used in this invention, A polyimide resin, a triazine resin, a melamine resin, a phenol resin, cyanate compounds, etc. are mentioned, These are individual or 2 More than one species can be used in combination.
本発明で使用する（ｂ）フェノール類付加ポリブタジエンは、ブタジエン単独重合体あるいはブタジエンとスチレン等のビニルモノマーやイソプレン等のジオレフィンとを共重合させたブタジエン共重合体を、硫酸、過塩素酸、塩化アルミニウム、３フッ化ホウ素、３フッ化ホウ素・エーテル錯体、３フッ化ホウ素・フェノール錯体等のいずれかを触媒として、フェノール類と反応させて製造することが好ましい。フェノール類の付加量は、好ましくは生成付加重合体（フェノール類付加ポリブタジエン）１００ｇ中に含まれるヒドロキシル基が０．１〜１モルとなるように調整することが好ましい。フェノール類付加ポリブタジエンは、エポキシ樹脂と架橋するが、前記ヒドロキシル基の量が０．１モルより少ないとエポキシ樹脂硬化物の架橋密度が小さくなり耐熱性が低下する。一方、前記ヒドロキシル基の量が１モルより多いと組成物の流動性が悪くなり成形が難しくなる。ここで使用されるフェノール類とは、一価フェノール、多価フェノールあるいはこれらのアルキル置換体から選ばれたものが挙げられる。 (B) Phenol-added polybutadiene used in the present invention is a butadiene homopolymer or a butadiene copolymer obtained by copolymerizing butadiene with a vinyl monomer such as styrene or a diolefin such as isoprene, sulfuric acid, perchloric acid, It is preferable to produce by reacting with phenols using any one of aluminum chloride, boron trifluoride, boron fluoride / ether complex, boron fluoride / phenol complex and the like as a catalyst. The addition amount of phenols is preferably adjusted so that the hydroxyl group contained in 100 g of the resulting addition polymer (phenol addition polybutadiene) is 0.1 to 1 mol. The phenol-added polybutadiene crosslinks with the epoxy resin. However, if the amount of the hydroxyl group is less than 0.1 mol, the crosslink density of the cured epoxy resin is reduced and the heat resistance is lowered. On the other hand, when the amount of the hydroxyl group is more than 1 mol, the fluidity of the composition is deteriorated and molding becomes difficult. The phenols used here include those selected from monohydric phenols, polyhydric phenols, and alkyl-substituted products thereof.
また、本発明で使用する（ｂ）フェノール類付加ポリブタジエンとしては、ＰＰ−７００−３００（日本石油化学株式会社製商品名，ＯＨ当量３１５）が市販品として例示できる。 Moreover, as (b) phenol addition polybutadiene used by this invention, PP-700-300 (The Nippon Petrochemical Co., Ltd. brand name, OH equivalent 315) can be illustrated as a commercial item.
（ｃ）１−シアノエチル−２−エチルイミダゾールの環状縮合物は，硬化促進剤として用いられ、市販品としては：キュアゾール２ＥＺ−ＣＹ（四国化成工業株式会社製製品名）が例示できる。（ｃ）１−シアノエチル−２−エチルイミダゾールの環状縮合物の配合量は、エポキシ樹脂（（ａ）フェノール類とヒドロキシベンズアルデヒドとの縮合物をエポキシ化して得られるエポキシ樹脂及びそれ以外の必要に応じて用いられるエポキシ樹脂の合計量）１００重量部に対して、０．０１〜５重量部が好ましい。０．０１重量部より少ないと硬化促進効果が小さくなる傾向があり、５重量部より多いとプリント配線板用エポキシ樹脂組成物の保存安定性が低下する傾向がある。 (C) The cyclic condensate of 1-cyanoethyl-2-ethylimidazole is used as a curing accelerator, and examples of commercially available products include: Curazole 2EZ-CY (product name, manufactured by Shikoku Kasei Kogyo Co., Ltd.). (C) The amount of the cyclic condensate of 1-cyanoethyl-2-ethylimidazole is determined depending on the epoxy resin ((a) an epoxy resin obtained by epoxidizing a condensate of phenols and hydroxybenzaldehyde, and other needs. The total amount of the epoxy resin used is preferably from 0.01 to 5 parts by weight per 100 parts by weight. When the amount is less than 0.01 part by weight, the curing acceleration effect tends to be small, and when the amount is more than 5 parts by weight, the storage stability of the epoxy resin composition for a printed wiring board tends to decrease.
上記（ａ）、（ｂ）、および（ｃ）は、必須成分である。プリント配線板用エポキシ樹脂組成物には、必要に応じて熱可塑性樹脂、着色材、紫外線不透過剤、酸化防止剤、（ｃ）１−シアノエチル−２−エチルイミダゾールの環状縮合物以外の硬化促進剤、硬化剤、還元剤、充填剤、触媒、可とう剤等を配合することもできる。硬化剤としては、特に制限されないが、エポキシ樹脂を使用する場合の硬化剤を例に挙げると、アミン化合物、多官能性フェノール化合物、酸無水物化合物等が挙げられ、これらから単独または２種以上選択される。硬化促進剤としては、特に制限されないが、例えばイミダゾール系化合物、有機リン系化合物、第２級アミン、第３級アミン、第４級アンモニウム塩等が用いられ、これらから単独または２種以上選択される。 The above (a), (b), and (c) are essential components. Epoxy resin composition for printed wiring board includes, if necessary, curing acceleration other than thermoplastic resin, coloring material, UV opaque agent, antioxidant, and (c) 1-cyanoethyl-2-ethylimidazole cyclic condensate An agent, a curing agent, a reducing agent, a filler, a catalyst, a flexible agent, and the like can also be blended. Although it does not restrict | limit especially as a hardening | curing agent, When a hardening | curing agent in the case of using an epoxy resin is mentioned as an example, an amine compound, a polyfunctional phenol compound, an acid anhydride compound, etc. will be mentioned, From these alone or 2 or more types Selected. Although it does not restrict | limit especially as a hardening accelerator, For example, an imidazole type compound, an organophosphorus compound, a secondary amine, a tertiary amine, a quaternary ammonium salt etc. are used, and these are individual or 2 or more types are selected from these. The
プリント配線板用エポキシ樹脂組成物のワニスは、上記（ａ）、（ｂ）、および（ｃ）を必須成分として得た本発明のプリント配線板用エポキシ樹脂組成物に、必要に応じて有機溶剤を加え、混合することにより得られる。本発明に用いられる有機溶剤としては、特に制限されないが、メタノール、エタノール、イソプロピルアルコール、ｎ−ブタノール等のアルコール系溶剤、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン系溶剤、トルエン、キシレン等の芳香族炭化水素系溶剤、ジメチルスルホキシド等の硫黄化合物系溶剤、Ｎ−メチルピロリドン、Ｎ−メチルホルムアルデヒド、Ｎ，Ｎ−ジメチルホルムアミド等のアミド系溶剤、メチルセロソルブ、エチルセロソルブ、セロソルブアセテート等のセロソルブ系溶剤等が使用可能であり、これらから単独または２種以上選択される。 The varnish of the epoxy resin composition for a printed wiring board is obtained by adding an organic solvent as necessary to the epoxy resin composition for a printed wiring board of the present invention obtained by using the above (a), (b), and (c) as essential components. Is added and mixed. The organic solvent used in the present invention is not particularly limited, but alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-butanol, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, and aromatic carbonization such as toluene and xylene. Hydrogen solvents, sulfur compound solvents such as dimethyl sulfoxide, amide solvents such as N-methylpyrrolidone, N-methylformaldehyde, N, N-dimethylformamide, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, cellosolve acetate, etc. They can be used and are selected from these alone or in combination.
本発明のプリント配線板用プリプレグは、上記（ａ）、（ｂ）、および（ｃ）を必須成分として有機溶剤中で配合して得たプリント配線板用エポキシ樹脂組成物のワニスを、ガラス織布またはガラス不織布に含浸させて、乾燥することによりＢステージ化して得ることができる。ここで使用するガラス織布またはガラス不織布の種類や厚さには特に指定はなく、目的のプリント配線板用プリプレグまたは金属張積層板の用途や厚さに合わせて選択することができる。またプリント配線板用プリプレグを製造する時の乾燥条件は、例えば乾燥温度６０〜２００℃、乾燥時間１〜３０分間の間で、目的のプリント配線板用プリプレグの特性に合わせて自由に選択することができる。 The prepreg for a printed wiring board of the present invention is a glass woven varnish of an epoxy resin composition for a printed wiring board obtained by blending the above (a), (b), and (c) as essential components in an organic solvent. It can be obtained by impregnating a cloth or a glass nonwoven fabric and drying to form a B-stage. The type and thickness of the glass woven fabric or glass nonwoven fabric used here are not particularly specified, and can be selected according to the intended use and thickness of the prepreg for the printed wiring board or the metal-clad laminate. The drying conditions for producing the printed wiring board prepreg can be freely selected according to the characteristics of the target printed wiring board prepreg, for example, within a drying temperature of 60 to 200 ° C. and a drying time of 1 to 30 minutes. Can do.
本発明の金属張積層板は、目的とする金属張積層板の厚みに合わせて得られた本発明のプリント配線板用プリプレグを少なくとも１枚以上重ね、その片側または両側に金属箔を重ね、加熱加圧して製造する。同様に、目的とする多層プリント配線板に合わせて、多層プリント配線板の構成材の間に、接着材料となる本発明のプリント配線板用プリプレグを所定枚数配し、加熱加圧成形して多層プリント配線板を製造することができる。なお本発明の多層プリント配線板の構成材としては、電機絶縁材料として使用される樹脂積層板、金属張積層板、金属箔、プリント配線板などが挙げられる。金属箔としては主に銅箔やアルミ箔を用いるが、他の金属箔を用いてもよい。金属箔の厚みは３〜２００μｍが好ましい。 The metal-clad laminate of the present invention is obtained by stacking at least one prepreg for a printed wiring board of the present invention obtained in accordance with the thickness of the target metal-clad laminate, laminating metal foil on one side or both sides, and heating Manufacture under pressure. Similarly, according to the target multilayer printed wiring board, a predetermined number of prepregs for the printed wiring board of the present invention, which will be an adhesive material, are arranged between the constituent materials of the multilayer printed wiring board, and multilayered by heating and pressing. A printed wiring board can be manufactured. In addition, as a structural material of the multilayer printed wiring board of this invention, the resin laminated board used as an electrical insulation material, a metal tension laminated board, metal foil, a printed wiring board, etc. are mentioned. Although copper foil and aluminum foil are mainly used as the metal foil, other metal foils may be used. The thickness of the metal foil is preferably 3 to 200 μm.
金属張積層板製造時の加熱温度は１３０〜２１０℃、より好ましくは１６０〜１９０℃で、圧力は０．５〜１０ＭＰａ、より好ましくは１〜４ＭＰａであり、プリント配線板用プリプレグ特性や、プリント配線板用エポキシ樹脂組成物の反応性，プレス機の能力、目的の金属張積層板の厚み等により適宜決定することができる。また、多層プリント配線板の製造時の条件も、上記金属張積層板製造時の条件と同様にして適宜決定することができる。 The heating temperature at the time of producing the metal-clad laminate is 130 to 210 ° C., more preferably 160 to 190 ° C., and the pressure is 0.5 to 10 MPa, more preferably 1 to 4 MPa. It can be appropriately determined depending on the reactivity of the epoxy resin composition for wiring boards, the capability of the press, the thickness of the target metal-clad laminate, and the like. Moreover, the conditions at the time of manufacturing the multilayer printed wiring board can be appropriately determined in the same manner as the conditions at the time of manufacturing the metal-clad laminate.
以下に、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。
（実施例１）
（ａ）フェノール類とヒドロキシベンズアルデヒドとの縮合物をエポキシ化して得られるエポキシ樹脂として、フェノールサリチルアルデヒドノボラック型エポキシ樹脂（ジャパンエポキシレジン株式会社製商品名ＹＬ６７８１，エポキシ当量１７０）１０重量部と，（ｂ）フェノール類付加ポリブタジエンとして、ＰＰ−７００−３００（日本石油化学株式会社製商品名，ＯＨ当量３１５）４０重量部と、低誘電率化されたエポキシ樹脂（住友化学工業株式会社製スミエポキシＬＤＸ−４１２７，エポキシ当量３８５）４０重量部と、テトラブロモビスフェノールＡ（ＯＨ当量２７０）１０重量部を混合した。さらに，硬化促進剤として，（ｃ）１−シアノエチル−２−エチル−イミダゾールの環状縮合物（製品名：キュアゾール２ＥＺ−ＣＹ；四国化成工業株式会社製）を１重量部加えプリント配線板用エポキシ樹脂組成物を作製した。これらをジメチルホルムアミド，メチルエチルケトンおよびエチレングリコールモノメチルエーテルの混合有機溶剤に溶解して、樹脂固形分６０重量％のプリント配線板用エポキシ樹脂組成物ワニスを得た。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Example 1
(A) As an epoxy resin obtained by epoxidizing a condensate of phenols and hydroxybenzaldehyde, 10 parts by weight of a phenol salicylaldehyde novolac type epoxy resin (Japan Epoxy Resin Co., Ltd., trade name YL6781, epoxy equivalent 170), b) 40 parts by weight of PP-700-300 (trade name, manufactured by Nippon Petrochemical Co., Ltd., OH equivalent 315) as a phenol-added polybutadiene, and an epoxy resin having a low dielectric constant (Sumiepoxy LDX- manufactured by Sumitomo Chemical Co., Ltd.) 4127, epoxy equivalent 385) 40 parts by weight and tetrabromobisphenol A (OH equivalent 270) 10 parts by weight were mixed. Furthermore, as a curing accelerator, 1 part by weight of a cyclic condensate of (c) 1-cyanoethyl-2-ethyl-imidazole (product name: Curesol 2EZ-CY; manufactured by Shikoku Kasei Kogyo Co., Ltd.) is added and an epoxy resin for printed wiring boards. A composition was prepared. These were dissolved in a mixed organic solvent of dimethylformamide, methyl ethyl ketone and ethylene glycol monomethyl ether to obtain an epoxy resin composition varnish for a printed wiring board having a resin solid content of 60% by weight.
（実施例２）
（ｂ）フェノール類付加ポリブタジエン（ＰＰ−７００−３００）を５５重量部に，低誘電率エポキシ樹脂（スミエポキシＬＤＸ−４１２７）を２５重量部に変更した他は、実施例１と同様にして，プリント配線板用エポキシ樹脂組成物ワニスを得た。
(Example 2)
(B) Printing was performed in the same manner as in Example 1 except that 55 parts by weight of phenol-added polybutadiene (PP-700-300) and 25 parts by weight of low dielectric constant epoxy resin (Sumiepoxy LDX-4127) were changed. An epoxy resin composition varnish for wiring boards was obtained.
（実施例３）
（ｂ）フェノール類付加ポリブタジエン（ＰＰ−７００−３００）を３０重量部に，低誘電率エポキシ樹脂（スミエポキシＬＤＸ−４１２７）を５０重量部に変更した他は、実施例１と同様にして，プリント配線板用エポキシ樹脂組成物ワニスを得た。
(Example 3)
(B) Printing was performed in the same manner as in Example 1 except that 30 parts by weight of phenol-added polybutadiene (PP-700-300) and 50 parts by weight of low dielectric constant epoxy resin (Sumiepoxy LDX-4127) were changed. An epoxy resin composition varnish for wiring boards was obtained.
（比較例１）
実施例１に使用した硬化促進剤を、（ｃ）１−シアノエチル−２−エチル−イミダゾールの環状縮合物から２−エチル−４−メチルイミダゾール１重量部に変更した以外は，実施例１と同様にして樹脂固形分６０重量％のプリント配線板用エポキシ樹脂組成物ワニスを得た。
(Comparative Example 1)
The curing accelerator used in Example 1 was the same as in Example 1 except that (c) 1-cyanoethyl-2-ethyl-imidazole cyclic condensate was changed to 1 part by weight of 2-ethyl-4-methylimidazole. Thus, an epoxy resin composition varnish for a printed wiring board having a resin solid content of 60% by weight was obtained.
（比較例２）
実施例１に使用したエポキシ樹脂（ＹＬ６７８１及びスミエポキシＬＤＸ−４１２７）をビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン株式会社製、商品名エピコート１００４）に変更し，配合量を３００重量部に変更した以外は，実施例１と同様にして樹脂固形分６０重量％のプリント配線板用エポキシ樹脂組成物ワニスを得た。
(Comparative Example 2)
Except for changing the epoxy resin used in Example 1 (YL6781 and Sumiepoxy LDX-4127) to a bisphenol A type epoxy resin (product name Epicoat 1004, manufactured by Japan Epoxy Resin Co., Ltd.) and changing the blending amount to 300 parts by weight. In the same manner as in Example 1, an epoxy resin composition varnish for a printed wiring board having a resin solid content of 60% by weight was obtained.
（プリント配線板用プリプレグの作製）
実施例１〜３および比較例１〜２のプリント配線板用エポキシ樹脂組成物ワニスを、厚さ１００μｍのガラス織布（ＭＩＬ品番２１１６タイプ）に含浸し、１５０℃の乾燥器中で５分間乾燥し、樹脂分５０重量％のＢ−ステージ状態のプリント配線板用プリプレグを得た。
(Preparation of printed circuit board prepreg)
The epoxy resin composition varnish for printed wiring boards of Examples 1 to 3 and Comparative Examples 1 to 2 was impregnated into a glass woven fabric (MIL part number 2116 type) having a thickness of 100 μm and dried in a dryer at 150 ° C. for 5 minutes. Thus, a prepreg for a printed wiring board in a B-stage state having a resin content of 50% by weight was obtained.
（金属張積層板の作製）
得られたプリント配線板用プリプレグをそれぞれ４枚ずつ重ねて、その両側に厚み３５μｍの銅箔を配し、圧力２．５ＭＰａ、温度１８０℃で１００分間加熱加圧して両面銅張積層板（金属張積層板）を得た。
(Production of metal-clad laminate)
Four prepregs for the printed wiring board thus obtained were stacked, and a copper foil having a thickness of 35 μm was placed on both sides of the prepreg. Tension laminate).
（Ｔｇの測定）
得られた両面銅箔張積層板を用い、銅箔をエッチング後、Ｔｇの測定を行った。Ｔｇの測定は、Ｄｕ Ｐｏｎｔ製熱機械分析装置（以下ＴＭＡと略す）にて行った。測定した値を表１に示した。
(Measurement of Tg)
Using the obtained double-sided copper foil-clad laminate, the Tg was measured after etching the copper foil. Measurement of Tg was performed with a Du Pont thermomechanical analyzer (hereinafter abbreviated as TMA). The measured values are shown in Table 1.
（誘電率及び誘電正接の測定）
得られた両面銅箔張積層板を用い、ＪＩＳ Ｃ ６４８１に準拠して，常態にて誘電率及び誘電正接の測定を行った。
(Measurement of dielectric constant and dissipation factor)
Using the obtained double-sided copper foil-clad laminate, the dielectric constant and dielectric loss tangent were measured in a normal state in accordance with JIS C 6481.
以上の結果から，実施例１〜３において，従来以上の高いＴｇを得られる事が確認された。また、誘電特性のおいても、比較例１、２と比べ、誘電正接は、低く、また誘電率は、同等程度であり、低誘電特性を得られる事が確認された。
From the above results, in Examples 1 to 3, it was confirmed that a higher Tg than the conventional one can be obtained. Also, in terms of dielectric characteristics, compared to Comparative Examples 1 and 2, the dielectric loss tangent was low and the dielectric constant was comparable, confirming that low dielectric characteristics could be obtained.
Claims (4)
A multilayer printed wiring board obtained by stacking and integrating the prepreg for a printed wiring board according to claim 2 as an adhesive material of a constituent material of the multilayer printed wiring board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004281506A JP2006096798A (en) | 2004-09-28 | 2004-09-28 | Epoxy resin composition for printed wiring board, prepreg for printed wiring board and metal-clad laminate and multilayer printed wiring board each using the same composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004281506A JP2006096798A (en) | 2004-09-28 | 2004-09-28 | Epoxy resin composition for printed wiring board, prepreg for printed wiring board and metal-clad laminate and multilayer printed wiring board each using the same composition |
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| Publication Number | Publication Date |
|---|---|
| JP2006096798A true JP2006096798A (en) | 2006-04-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004281506A Pending JP2006096798A (en) | 2004-09-28 | 2004-09-28 | Epoxy resin composition for printed wiring board, prepreg for printed wiring board and metal-clad laminate and multilayer printed wiring board each using the same composition |
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| JP (1) | JP2006096798A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010006883A (en) * | 2008-06-25 | 2010-01-14 | Sumitomo Bakelite Co Ltd | Resin composition for circuit board, prepreg, and laminate |
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2004
- 2004-09-28 JP JP2004281506A patent/JP2006096798A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010006883A (en) * | 2008-06-25 | 2010-01-14 | Sumitomo Bakelite Co Ltd | Resin composition for circuit board, prepreg, and laminate |
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