JP2003137971A - Epoxy resin composition, prepreg, laminate and printed wiring board - Google Patents
Epoxy resin composition, prepreg, laminate and printed wiring boardInfo
- Publication number
- JP2003137971A JP2003137971A JP2001337254A JP2001337254A JP2003137971A JP 2003137971 A JP2003137971 A JP 2003137971A JP 2001337254 A JP2001337254 A JP 2001337254A JP 2001337254 A JP2001337254 A JP 2001337254A JP 2003137971 A JP2003137971 A JP 2003137971A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- prepreg
- formula
- printed wiring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明は、その硬化物が放熱
性に優れるエポキシ樹脂組成物、当該エポキシ樹脂組成
物を用いるプリプレグ、さらには、当該プリプレグを用
いる積層板ないしはプリント配線板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition whose cured product has excellent heat dissipation properties, a prepreg using the epoxy resin composition, and a laminated board or printed wiring board using the prepreg.
【０００２】[0002]
【従来の技術】近年、携帯電話や各種モバイル機器に見
られるように、電子機器の小型軽量化または薄型化が顕
著である。これにより、電子機器内部のプリント配線板
に搭載されたＩＣやＬＳＩ等の電子部品は高密度化して
おり、それに伴って電子機器内部の発熱密度も大きくな
っている。電子機器内の発熱密度が大きくなると、電子
機器内部の発熱に伴う温度上昇は顕著になる。電子機器
内部の温度上昇が著しくなると、電子部品の動作信頼性
は低下する。よって、電子部品や導体から発生した熱を
速やかに外部に放出するために、プリント配線基板（絶
縁層）の放熱性を向上させる必要がある。2. Description of the Related Art In recent years, electronic devices have been remarkably reduced in size, weight and thickness as seen in mobile phones and various mobile devices. As a result, the density of electronic components such as ICs and LSIs mounted on a printed wiring board inside an electronic device has increased, and the heat generation density inside the electronic device has increased accordingly. When the heat generation density inside the electronic device increases, the temperature rise due to the heat generation inside the electronic device becomes remarkable. When the temperature inside the electronic device rises significantly, the operational reliability of the electronic component decreases. Therefore, it is necessary to improve the heat dissipation of the printed wiring board (insulating layer) in order to quickly radiate the heat generated from the electronic component or the conductor to the outside.
【０００３】上記問題の解決手段として、次のような積
層板をプリント配線基板に採用する提案がある。
（１）無機充填剤を添加した樹脂組成物で金属板を絶縁
被覆した金属ベース積層板（特開平６−２１６４８４号
公報）。
（２）金属板にエポキシ樹脂からなる絶縁接着シートを
貼り付けた金属ベース積層板（特開平８−１６７７７５
号公報）。
（３）窒化アルミニウムを漉き込んだシート状繊維基材
にエポキシ樹脂ワニスを含浸し乾燥して得たプリプレグ
の層を加熱加圧成形した積層板（特開２０００−１５７
４６号公報）。
これらの積層板は熱伝導性のよい金属や無機セラミック
スを用いて放熱性を高めたものであり、従来の積層板、
すなわち、シート状繊維基材に熱硬化性樹脂ワニスを含
浸し乾燥して得たプリプレグの層を加熱加圧成形した積
層板に比べて、加工性が劣り、また、絶縁性も低下する
という問題があった。As a means for solving the above problems, there is a proposal to employ the following laminated board for a printed wiring board. (1) A metal base laminated plate in which a metal plate is insulation-coated with a resin composition containing an inorganic filler (JP-A-6-216484). (2) A metal base laminated plate in which an insulating adhesive sheet made of epoxy resin is attached to a metal plate (Japanese Patent Laid-Open No. 8-167775).
Issue). (3) A laminated sheet obtained by heat-press molding a layer of a prepreg obtained by impregnating a sheet-shaped fiber base material into which aluminum nitride has been impregnated with an epoxy resin varnish and drying it (JP-A-2000-157).
No. 46). These laminated plates have improved heat dissipation using a metal or inorganic ceramics having good thermal conductivity.
That is, compared with a laminate obtained by impregnating a sheet-like fiber base material with a thermosetting resin varnish and drying the layer of a prepreg and subjecting it to heat-press molding, the workability is poor, and the insulating property is also deteriorated. was there.
【０００４】[0004]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、その硬化物自体が良好な熱伝導性を保持し
放熱性が優れたものとなるエポキシ樹脂組成物を提供す
ることである。また、このようなエポキシ樹脂組成物を
適用したプリプレグ、このプリプレグを用いた積層板な
いしはプリント配線板を提供することである。The problem to be solved by the present invention is to provide an epoxy resin composition in which the cured product itself has good thermal conductivity and excellent heat dissipation. . Another object of the present invention is to provide a prepreg to which such an epoxy resin composition is applied, and a laminated board or a printed wiring board using the prepreg.
【０００５】[0005]
【課題を解決するための手段】上記課題を達成するため
に、本発明に係るエポキシ樹脂組成物は、次の成分を含
有する。すなわち、ビフェニル基あるいはビフェニル誘
導体を有し下記（式１）で示される分子構造式のエポキ
シ樹脂モノマと、少なくともオルト位に水酸基が配置さ
れた二価以上のフェノール類又はその化合物と、硬化促
進剤とを含有することを特徴とする。In order to achieve the above object, the epoxy resin composition according to the present invention contains the following components. That is, an epoxy resin monomer having a biphenyl group or a biphenyl derivative and having a molecular structural formula represented by the following (formula 1), a divalent or higher phenol having a hydroxyl group at least in the ortho position or a compound thereof, and a curing accelerator. It is characterized by containing and.
【０００６】[0006]
【化５】 [Chemical 5]
【０００７】上記二価以上のフェノール類又はその化合
物は、（式１）のエポキシ樹脂モノマの硬化剤として働
く。上記エポキシ樹脂組成物の硬化物が高熱伝導性とな
る理由は、二価以上のフェノール類又はその化合物のオ
ルト位の水酸基が（式１）のエポキシ樹脂モノマのエポ
キシ基と反応し、エポキシ樹脂硬化物中にビフェニル基
あるいはビフェニル誘導体の配列による高次構造が形成
され、この高次構造が熱伝導に寄与するためと考えられ
る。二価以上のフェノール類又はその化合物として、オ
ルト位に水酸基を有しないものを選択した場合、すなわ
ち、レゾルシン（ｍ−ジヒドロキシベンゼン）、ヒドロ
キノン（ｐ−ジヒドロキシベンゼン）、フロログルシン
（１，３，５−トリヒドロキシベンゼン）やこれらの化
合物を選択した場合には、架橋したエポキシ樹脂モノマ
単位同士の間隔が広がるために、ビフェニル基あるいは
ビフェニル誘導体が配列せず、高次構造の形成が困難に
なる。従って、このような場合には、エポキシ樹脂硬化
物の熱伝導率を高くすることに期待をもてない。硬化剤
として、少なくともオルト位に水酸基が配置された二価
以上のフェノール類又はその化合物を選択することが重
要である。The above-mentioned dihydric or higher phenols or compounds thereof act as a curing agent for the epoxy resin monomer of the formula (1). The reason why the cured product of the epoxy resin composition has high thermal conductivity is that the ortho hydroxyl groups of the divalent or higher phenols or their compounds react with the epoxy groups of the epoxy resin monomer of the formula (1) to cure the epoxy resin. It is considered that a higher-order structure is formed in the product by the arrangement of biphenyl groups or biphenyl derivatives, and this higher-order structure contributes to heat conduction. When dihydric or higher phenols or compounds thereof having no hydroxyl group at the ortho position are selected, that is, resorcin (m-dihydroxybenzene), hydroquinone (p-dihydroxybenzene), phloroglucin (1,3,5- When (trihydroxybenzene) or these compounds are selected, the distance between the crosslinked epoxy resin monomer units is increased, so that the biphenyl group or the biphenyl derivative is not arranged, and it becomes difficult to form a higher-order structure. Therefore, in such a case, it cannot be expected to increase the thermal conductivity of the cured epoxy resin. It is important to select, as the curing agent, a divalent or higher valent phenol or compound having a hydroxyl group at least in the ortho position.
【０００８】上記のエポキシ樹脂組成物において、二価
以上のフェノール類の化合物として、好ましくは、当該
フェノール類の二量体以上の重合体を選択する。オルト
位の水酸基が多くなるため、エポキシ樹脂硬化物中にビ
フェニル基あるいはビフェニル誘導体の配列によって形
成される高次構造がより緻密になり、熱伝導率をさらに
高くすることができる。In the above epoxy resin composition, as the compound of divalent or higher phenols, preferably, a dimer or higher polymer of the phenols is selected. Since the number of hydroxyl groups in the ortho position increases, the higher-order structure formed by the arrangement of biphenyl groups or biphenyl derivatives in the cured epoxy resin becomes more dense, and the thermal conductivity can be further increased.
【０００９】また、上記のエポキシ樹脂組成物におい
て、（式１）で示される分子構造式のエポキシ樹脂モノ
マとして、好ましくは、下記（式２）で示される分子構
造式のものを選択する。ビフェニル基がより配列しやす
いため、熱伝導率をより高くすることができる。In the above epoxy resin composition, the epoxy resin monomer having the molecular structural formula represented by (Formula 1) is preferably selected from the molecular structural formula represented by the following (Formula 2). Since the biphenyl groups are more easily arranged, the thermal conductivity can be increased.
【００１０】[0010]
【化６】 [Chemical 6]
【００１１】本発明に係るプリプレグは、上記のような
エポキシ樹脂組成物をシート状の繊維基材に含浸し半硬
化状態としてなるものである。当該エポキシ樹脂組成物
を含浸したシート状の繊維基材を加熱乾燥することによ
り、半硬化の状態まで硬化反応を進める。The prepreg according to the present invention is obtained by impregnating the above-mentioned epoxy resin composition into a sheet-like fiber base material to be in a semi-cured state. By heating and drying the sheet-shaped fiber base material impregnated with the epoxy resin composition, the curing reaction proceeds to a semi-cured state.
【００１２】本発明に係る別のプリプレグは、上記の
（式１）好ましくは（式２）で示される分子構造式のエ
ポキシ樹脂モノマと、イオン重合性の硬化触媒とを含有
するエポキシ樹脂組成物をシート状の繊維基材に含浸し
半硬化状態としてなるものである。このエポキシ樹脂組
成物も、その硬化物中にビフェニル基あるいはビフェニ
ル誘導体の配列による高次構造が形成され、この高次構
造が熱伝導に寄与すると考えられる。（式２）で示され
る分子構造式のエポキシ樹脂モノマを選択すると、ビフ
ェニル基がより配列しやすいため、熱伝導率をより高く
することができる。Another prepreg according to the present invention is an epoxy resin composition containing an epoxy resin monomer having a molecular structural formula represented by the above (formula 1), preferably (formula 2), and an ionically polymerizable curing catalyst. Is impregnated into a sheet-shaped fiber base material to be in a semi-cured state. It is considered that this epoxy resin composition also has a higher-order structure formed by the arrangement of biphenyl groups or biphenyl derivatives in the cured product, and this higher-order structure contributes to heat conduction. When the epoxy resin monomer having the molecular structural formula represented by (Equation 2) is selected, the biphenyl groups are more easily arranged, so that the thermal conductivity can be further increased.
【００１３】上述した二種類のエポキシ樹脂組成物、す
なわち、硬化剤として、少なくともオルト位に水酸基が
配置された二価以上のフェノール類またはその化合物を
選択したエポキシ樹脂組成物と、イオン重合性の硬化触
媒を選択したエポキシ樹脂組成物とを比較すると、前者
のエポキシ組成物は、融点が低下して有機溶剤への溶解
性が良い。従って、プリプレグ製造工程において、シー
ト状繊維基材に含浸するためのエポキシ樹脂組成物ワニ
スの調製が容易になる。The above-mentioned two kinds of epoxy resin compositions, that is, an epoxy resin composition in which a dihydric or higher phenol having at least a hydroxyl group at the ortho position or a compound thereof is selected as a curing agent, and an ionic polymerizable compound. When compared with an epoxy resin composition in which a curing catalyst is selected, the former epoxy composition has a lower melting point and better solubility in an organic solvent. Therefore, in the prepreg manufacturing process, it becomes easy to prepare the epoxy resin composition varnish for impregnating the sheet-shaped fiber base material.
【００１４】本発明に係る積層板は、上述したプリプレ
グの層を、一体に成形するプリプレグ層の全層ないしは
一部の層として加熱加圧成形してなるものである。ま
た、本発明に係るプリント配線板は、上述したプリプレ
グの層を加熱加圧成形してなる絶縁層を備えたものであ
る。The laminated plate according to the present invention is formed by heating and pressing the above-mentioned prepreg layers as all or a part of the prepreg layers integrally formed. A printed wiring board according to the present invention includes an insulating layer formed by heating and pressing the above-mentioned prepreg layer.
【００１５】[0015]
【発明の実施の形態】本発明に係るエポキシ樹脂組成物
は、ビフェニル基あるいはビフェニル誘導体を有するエ
ポキシ樹脂モノマを主剤として用いることが重要であ
る。ビフェニル基あるいはビフェニル誘導体を有するエ
ポキシ樹脂モノマとは、ビフェニル骨格あるいはビフェ
ニル誘導体の骨格をもち、一分子中に二個以上のエポキ
シ基をもつエポキシ樹脂モノマ全般であり、上述した分
子構造式（式１）で表される。その中でも、上述した分
子構造式（式２）で表されるエポキシ樹脂モノマを用い
ると、硬化物の熱伝導性はさらに高くなり、これを適用
したプリント配線板の放熱性がさらに向上するので好ま
しい。BEST MODE FOR CARRYING OUT THE INVENTION It is important for the epoxy resin composition according to the present invention to use an epoxy resin monomer having a biphenyl group or a biphenyl derivative as a main component. The epoxy resin monomer having a biphenyl group or a biphenyl derivative is a general epoxy resin monomer having a biphenyl skeleton or a biphenyl derivative skeleton and having two or more epoxy groups in one molecule, and the above-mentioned molecular structural formula (formula 1 ). Among them, it is preferable to use the epoxy resin monomer represented by the above-described molecular structural formula (Formula 2) because the cured product has higher thermal conductivity and the printed wiring board to which it is applied has further improved heat dissipation. .
【００１６】また、本発明に係るエポキシ樹脂組成物に
おいては、少なくともオルト位に水酸基が配置された二
価以上のフェノール類またはその化合物が用いられる。
例えば、カテコール（ｏ−ジヒドロキシベンゼン）、ピ
ロガロール（１，２，３−トリヒドロキシベンゼン）、
ヒドロキシヒドロキノン（１，２，４−トリヒドロキシ
ベンゼン）のようなモノマ型フェノール類やその化合物
である。その化合物は、例えば、前記モノマ型フェノー
ル類の誘導体、カテコールノボラックのようなオリゴマ
型フェノール化合物やその誘導体、すなわち、前記モノ
マ型フェノール類やその誘導体の二量体以上の重合体が
挙げられる。その中でも、前記二量体以上の重合体を用
いることで、硬化物の熱伝導性はさらに高くなり、これ
を適用したプリント配線板の放熱性がさらに向上するの
で好ましい。In the epoxy resin composition according to the present invention, a divalent or higher phenol having a hydroxyl group at least in the ortho position or a compound thereof is used.
For example, catechol (o-dihydroxybenzene), pyrogallol (1,2,3-trihydroxybenzene),
Monomeric phenols such as hydroxyhydroquinone (1,2,4-trihydroxybenzene) and their compounds. Examples of the compound include oligomeric phenolic compounds such as derivatives of the above-mentioned monomeric phenols and catechol novolac, and derivatives thereof, that is, dimer or higher polymers of the above-mentioned monomeric phenols and their derivatives. Among them, it is preferable to use the above-mentioned dimer or higher polymer, because the thermal conductivity of the cured product is further increased and the heat dissipation of the printed wiring board to which this is applied is further improved.
【００１７】本発明に係るエポキシ樹脂組成物におい
て、硬化促進剤は、エポキシ樹脂モノマとフェノール類
又はその化合物との重縮合反応を進行させるために従来
用いられている硬化促進剤を使用することができる。例
えば、トリフェニルホスフィン、イミダゾールやその誘
導体、三級アミン化合物やその誘導体などが挙げられ
る。In the epoxy resin composition according to the present invention, as the curing accelerator, it is possible to use a curing accelerator which has been conventionally used for promoting the polycondensation reaction between the epoxy resin monomer and the phenol or its compound. it can. Examples thereof include triphenylphosphine, imidazole and its derivatives, and tertiary amine compounds and their derivatives.
【００１８】本発明に係るプリプレグにおいて、硬化剤
としてフェノール類又はその化合物を配合しない場合、
硬化触媒としては、エポキシ樹脂モノマを単独で硬化さ
せることができるイオン重合性の硬化触媒を用いること
ができる。例えば、アミン化合物やその誘導体、イミダ
ゾール誘導体、ハロゲン化ホウ素やそのアミン錯体など
を用いることができる。In the prepreg according to the present invention, when a phenol or its compound is not blended as a curing agent,
As the curing catalyst, an ionically polymerizable curing catalyst that can cure the epoxy resin monomer alone can be used. For example, an amine compound or a derivative thereof, an imidazole derivative, a boron halide or an amine complex thereof can be used.
【００１９】本発明に係るエポキシ樹脂組成物は、必要
に応じて難燃剤や希釈剤、可塑剤、カップリング剤等を
含むことができる。また、エポキシ樹脂組成物をシート
状繊維基材に含浸し乾燥してプリプレグを作製する際、
必要に応じて溶剤を使用することができる。これらの使
用によって、硬化物の熱伝導性には影響を与えない。さ
らに、本発明に係るエポキシ樹脂組成物には、金属ある
いは無機セラミックス、その他の充填剤を含むことがで
きる。例えば、アルミナ、シリカ、酸化マグネシウム、
水酸化アルミニウム等の無機粉末充填剤、ガラス繊維、
パルプ繊維、合成繊維、セラミックス繊維等の繊維質充
填剤、着色剤等を添加することができる。充填剤の形状
は、粉末（塊状、球状）、単繊維、長繊維等いずれであ
ってもよい。The epoxy resin composition according to the present invention may contain a flame retardant, a diluent, a plasticizer, a coupling agent, etc., if necessary. Further, when a sheet-shaped fiber base material is impregnated with an epoxy resin composition and dried to prepare a prepreg,
A solvent can be used if necessary. The use thereof does not affect the thermal conductivity of the cured product. Furthermore, the epoxy resin composition according to the present invention may contain a metal or an inorganic ceramic, or other filler. For example, alumina, silica, magnesium oxide,
Inorganic powder filler such as aluminum hydroxide, glass fiber,
Fibrous fillers such as pulp fibers, synthetic fibers and ceramic fibers, colorants and the like can be added. The shape of the filler may be powder (lump, spherical), single fiber, long fiber, or the like.
【００２０】本発明に係るプリプレグは、上記のエポキ
シ樹脂組成物を、ガラス繊維や有機繊維で構成されたシ
ート状繊維基材（織布や不織布）に含浸し加熱乾燥し
て、エポキシ樹脂を半硬化状態としたものである。そし
て、積層板は、前記プリプレグの層を、プリプレグ層の
全層ないしは一部の層として加熱加圧成形してなるもの
であり、必要に応じて前記加熱加圧成形により片面ある
いは両面に銅箔等の金属箔を一体に貼り合せる。さら
に、プリント配線板は、前記のプリプレグ層を加熱加圧
成形してなる絶縁層を備えたものであり、片面プリント
配線板、両面プリント配線板、さらには、内層にプリン
ト配線を有する多層プリント配線板である。以上のよう
な構成のプリント配線板は、絶縁層の熱伝導性が良好で
優れた放熱性を有する。自動車機器用のプリント配線
板、パソコン等の高密度実装プリント配線板に好適であ
る。In the prepreg according to the present invention, the above epoxy resin composition is impregnated into a sheet-like fiber base material (woven cloth or non-woven cloth) made of glass fiber or organic fiber, and the epoxy resin composition is semi-dried by heating and drying. It is in a cured state. The laminated plate is formed by heat-pressing the prepreg layer as a whole layer or a part of the prepreg layer, and if necessary, copper foil on one side or both sides by the heat-pressure forming. The metal foils such as the above are stuck together. Further, the printed wiring board is provided with an insulating layer formed by heating and pressing the prepreg layer described above, and a single-sided printed wiring board, a double-sided printed wiring board, and further a multilayer printed wiring board having a printed wiring as an inner layer. It is a plate. The printed wiring board having the above-described configuration has excellent heat dissipation because the insulating layer has good thermal conductivity. Suitable for printed wiring boards for automobile equipment and high-density printed wiring boards for personal computers.
【００２１】[0021]
【実施例】以下、本発明に係る実施例を示し、本発明に
ついて詳細に説明する。尚、以下の実施例及び比較例に
おいて、「部」とは「重量部」を意味するものとする。ま
た、本発明は、その要旨を逸脱しない限り、本実施例に
限定されるものではない。EXAMPLES The present invention will be described in detail below by showing Examples according to the present invention. In the following Examples and Comparative Examples, "part" means "part by weight". Further, the present invention is not limited to this embodiment without departing from the gist thereof.
【００２２】実施例１
エポキシ当量１７９のエポキシ樹脂モノマ（ジャパンエ
ポキシレジン製「ＹＸ４０００Ｈ」）１００部を１２０
℃に加熱し融解させた。尚、「ＹＸ４０００Ｈ」は、上
記分子構造式（式１）において、Ｒ＝−ＣＨ３、ｎ＝
０．１のエポキシ樹脂モノマである。次に、フェノール
類として水酸基当量４２のヒドロキシヒドロキノン（和
光純薬製「ＨＨＱ」）２３部、硬化促進剤２−エチル−
４−メチルイミダゾール（和光純薬製「２Ｅ４ＭＺ」）
０．３部、メチルイソブチルケトン（和光純薬製）１７
５部を添加しワニス中の樹脂固形分含有量が３０質にな
るようにして１００℃で攪拌した。このエポキシ樹脂組
成物を、厚さ０．２mmのガラス繊維織布に含浸し加熱乾
燥してプリプレグを得た。このプリプレグ８枚を重ね、
温度１７５℃、圧力４MPaの条件で９０分間加熱加圧形
成して一体化し、厚さ１．６mmの積層板を得た。Example 1 120 parts of 100 parts of an epoxy resin monomer having an epoxy equivalent of 179 (“YX4000H” manufactured by Japan Epoxy Resin)
It was heated to ℃ and melted. In addition, “YX4000H” means R = —CH 3 , n = in the above molecular structural formula (Formula 1).
It is an epoxy resin monomer of 0.1. Next, 23 parts of hydroxyhydroquinone having a hydroxyl equivalent of 42 as phenols (“HHQ” manufactured by Wako Pure Chemical Industries, Ltd.), a curing accelerator 2-ethyl-
4-Methylimidazole ("2E4MZ" manufactured by Wako Pure Chemical Industries)
0.3 parts, methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries) 17
5 parts were added and the varnish was stirred at 100 ° C. so that the resin solid content was 30. A 0.2 mm thick glass fiber woven fabric was impregnated with this epoxy resin composition and dried by heating to obtain a prepreg. 8 pieces of this prepreg are piled up,
It was heated and pressed for 90 minutes under the conditions of a temperature of 175 ° C. and a pressure of 4 MPa to be integrated, and a 1.6 mm thick laminated plate was obtained.
【００２３】比較例１
「ＨＨＱ」の代わりに、フェノール類の化合物として、
水酸基当量１１７のｐ−クレゾールノボラック（ジャパ
ンエポキシレジン製「ＹＬＨ９８７」）を用いた以外は
実施例１と同様にして積層板を得た。尚、ｐ−クレゾー
ルノボラックは、二価以上のフェノール類化合物である
が、オルト位に水酸基を有しない。Comparative Example 1 Instead of “HHQ”, as a phenol compound,
A laminated board was obtained in the same manner as in Example 1 except that p-cresol novolac having a hydroxyl equivalent of 117 (“YLH987” manufactured by Japan Epoxy Resin) was used. Although p-cresol novolac is a divalent or higher valent phenol compound, it does not have a hydroxyl group at the ortho position.
【００２４】実施例２
「ＨＨＱ」の代わりに、フェノール類の化合物として、
水酸基当量５９のカテコールノボラック（ジャパンエポ
キシレジン製「ＹＬＨ６００」）を用いた以外は実施例
１と同様にして積層板を得た。Example 2 Instead of "HHQ", as a phenol compound,
A laminated sheet was obtained in the same manner as in Example 1 except that catechol novolak having a hydroxyl equivalent of 59 (“YLH600” manufactured by Japan Epoxy Resin) was used.
【００２５】実施例３
上記分子構造式（式１）において、Ｒ＝−ＣＨ３，ｎ＝
０．１であるエポキシ樹脂モノマとＲ＝−Ｈ，ｎ＝０．
１であるエポキシ樹脂モノマを等モルで含有するエポキ
シ樹脂モノマ（ジャパンエポキシレジン製「ＹＬ６１２
１Ｈ」）を２−ブタノンに溶解し、７０℃で温めた後に
室温で放置し、ろ過・乾燥してエポキシ当量１７０のエ
ポキシ樹脂モノマ（ＢＧＥ）を抽出した。これは、上記
分子構造式（式２）で表されるエポキシ樹脂モノマ（ｎ
＝０．１）である。ＢＧＥ１００部を１５０℃に加熱し
て融解し、水酸基当量４２の「ＨＨＱ」２５部、硬化促
進剤「２Ｅ４ＭＺ」０．３部を添加し攪拌した。このエ
ポキシ樹脂組成物を、厚さ０．２mmのガラス繊維織布に
含浸し加熱乾燥してプリプレグを得た。このプリプレグ
８枚を重ね、温度１７５℃、圧力４MPaの条件で９０分
間加熱加圧形成して一体化し、厚さ１．６mmの積層板を
得た。Example 3 In the above molecular structural formula (Formula 1), R = -CH 3 , n =
0.1 epoxy resin monomer and R = -H, n = 0.
Epoxy resin monomer containing the epoxy resin monomer of No. 1 in an equimolar amount (“YL612 manufactured by Japan Epoxy Resin”)
1H ”) was dissolved in 2-butanone, warmed at 70 ° C., allowed to stand at room temperature, filtered and dried to extract an epoxy resin monomer (BGE) having an epoxy equivalent of 170. This is the epoxy resin monomer (n represented by the above-mentioned molecular structural formula (Formula 2).
= 0.1). 100 parts of BGE was heated to 150 ° C. and melted, 25 parts of “HHQ” having a hydroxyl equivalent of 42 and 0.3 part of a curing accelerator “2E4MZ” were added and stirred. A 0.2 mm thick glass fiber woven fabric was impregnated with this epoxy resin composition and dried by heating to obtain a prepreg. Eight sheets of this prepreg were stacked, heated and pressed for 90 minutes under the conditions of a temperature of 175 ° C. and a pressure of 4 MPa to be integrated, and a laminate having a thickness of 1.6 mm was obtained.
【００２６】実施例４
「ＨＨＱ」の代わりに、フェノール類の化合物として、
「ＹＬＨ６００」を用いた以外は実施例３と同様と同様
にして積層板を得た。Example 4 Instead of "HHQ", as a compound of phenols,
A laminated board was obtained in the same manner as in Example 3 except that "YLH600" was used.
【００２７】実施例５
エポキシ当量１７９のエポキシ樹脂モノマ（ジャパンエ
ポキシレジン製「ＹＸ４０００Ｈ」）１００部を１２０
℃に加熱し融解させた。尚、「ＹＸ４０００Ｈ」は、上
記分子構造式（式１）において、Ｒ＝−ＣＨ３、ｎ＝
０．１のエポキシ樹脂モノマである。次に、イオン重合
性の硬化触媒として２−エチル−４−メチルイミダゾー
ル（和光純薬製「２Ｅ４ＭＺ」）１．５部を添加して攪
拌した。このエポキシ樹脂組成物を、厚さ０．２mmのガ
ラス繊維織布に含浸し加熱乾燥してプリプレグを得た。
このプリプレグ８枚を重ね、温度１７５℃、圧力４MPa
の条件で９０分間加熱加圧形成して一体化し、厚さ１．
６mmの積層板を得た。Example 5 120 parts of 100 parts of an epoxy resin monomer (“YX4000H” manufactured by Japan Epoxy Resin) having an epoxy equivalent of 179 was used.
It was heated to ℃ and melted. In addition, “YX4000H” means R = —CH 3 , n = in the above molecular structural formula (Formula 1).
It is an epoxy resin monomer of 0.1. Next, 1.5 parts of 2-ethyl-4-methylimidazole (“2E4MZ” manufactured by Wako Pure Chemical Industries, Ltd.) as an ion-polymerizable curing catalyst was added and stirred. A 0.2 mm thick glass fiber woven fabric was impregnated with this epoxy resin composition and dried by heating to obtain a prepreg.
8 sheets of this prepreg are piled up, temperature 175 ℃, pressure 4MPa
Under conditions of 90 minutes under heating and pressurizing, they are integrated, and the thickness is 1.
A 6 mm laminated plate was obtained.
【００２８】比較例２
エポキシ樹脂モノマとして、「ＹＸ４０００Ｈ」の代わ
りに、エポキシ当量１８５のビスフェノールＡ型エポキ
シ樹脂モノマ（ジャパンエポキシレジン製「ＥＰ８２
８」）を用いた以外は実施例５と同様にして積層板を得
た。尚、「ＥＰ８２８は」は、ビフェニル基あるいはビ
フェニル誘導体をその分子骨格にもたないエポキシ樹脂
モノマである。Comparative Example 2 Instead of "YX4000H" as an epoxy resin monomer, a bisphenol A type epoxy resin monomer having an epoxy equivalent of 185 ("EP82" manufactured by Japan Epoxy Resin) is used.
8 ”) was used, and a laminated plate was obtained in the same manner as in Example 5. Incidentally, "EP828" is an epoxy resin monomer having no biphenyl group or biphenyl derivative in its molecular skeleton.
【００２９】実施例６
エポキシ樹脂モノマとして、「ＹＸ４０００Ｈ」の代わ
りに、実施例３で用いたＢＧＥを用いた以外は、実施例
５と同様にして積層板を得た。Example 6 A laminated board was obtained in the same manner as in Example 5 except that BGE used in Example 3 was used as the epoxy resin monomer instead of “YX4000H”.
【００３０】上記各例の積層板から５０mmφの円盤状試
料を切り出し、熱伝導率を測定した。熱伝導率の測定
は、定常比較法であるＡＳＴＭ−Ｅ１２２５に準拠して
約８０℃で行なった。各例の熱伝導率の測定結果を、エ
ポキシ樹脂組成物の配合組成と共に表１にまとめて示
す。A disc-shaped sample having a diameter of 50 mm was cut out from the laminated plate of each of the above examples, and the thermal conductivity was measured. The thermal conductivity was measured at about 80 ° C. according to ASTM-E1225 which is a steady comparison method. The measurement results of the thermal conductivity of each example are collectively shown in Table 1 together with the composition of the epoxy resin composition.
【００３１】表１から明らかなように、本発明に係る実
施例はいずれも熱伝導率が高く、放熱性に優れる。一
方、（式１）で表されるエポキシ樹脂モノマを用いて
も、二価以上のフェノール類あるいはその化合物として
オルト位に水酸基を有しないものを用いると熱伝導率を
高くすることはできず（比較例１）、また、（式１）で
表されるエポキシ樹脂モノマを用いないと、熱伝導率を
高くすることができないこと（比較例２）を理解でき
る。As is clear from Table 1, all the examples according to the present invention have high thermal conductivity and excellent heat dissipation. On the other hand, even if the epoxy resin monomer represented by (Formula 1) is used, the thermal conductivity cannot be increased if a divalent or higher-valent phenol or a compound thereof having no hydroxyl group at the ortho position is used ( It can be understood that the thermal conductivity cannot be increased (Comparative Example 1) unless the epoxy resin monomer represented by (Formula 1) is used.
【００３２】実施例２は、少なくともオルト位に水酸基
が配置された二価以上のフェノール類の化合物として、
当該フェノール類の二量体以上の重合体を選択すると、
熱伝導率をより高くできることを示している。実施例３
は、（式２）で表されるエポキシ樹脂モノマを選択する
と、熱伝導率をより高くできることを示している。そし
て、実施例４は、（式２）で表されるエポキシ樹脂モノ
マと、少なくともオルト位に水酸基が配置された二価以
上のフェノール類の化合物として当該フェノール類の二
量体以上の重合体とを選択すると、さらに熱伝導率を高
くできることを示している。Example 2 is a compound of a divalent or higher phenol having a hydroxyl group at least in the ortho position.
When a polymer of a dimer or more of the phenol is selected,
It shows that the thermal conductivity can be made higher. Example 3
Shows that the thermal conductivity can be further increased by selecting the epoxy resin monomer represented by (Equation 2). Then, in Example 4, an epoxy resin monomer represented by (Formula 2) and a polymer of a dimer or more of the phenol as a compound of a divalent or higher phenol having a hydroxyl group arranged at least in the ortho position. Shows that the thermal conductivity can be further increased by selecting.
【００３３】また、実施例５は、硬化剤として、二価以
上のフェノール類の代わりにイオン重合性の硬化触媒を
用いた場合にも、（式１）で表されるエポキシ樹脂モノ
マを選択することにより、熱伝導率を高くできることを
示している。この場合にも、（式２）で表されるエポキ
シ樹脂モノマを選択すると、熱伝導率をより高くするこ
とができる（実施例６）。In Example 5, the epoxy resin monomer represented by the formula (1) is selected as the curing agent even when the ionically polymerizable curing catalyst is used instead of the divalent or higher phenols. This indicates that the thermal conductivity can be increased. Also in this case, if the epoxy resin monomer represented by (Equation 2) is selected, the thermal conductivity can be further increased (Example 6).
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【発明の効果】以上詳述したように、本発明係るエポキ
シ樹脂組成物ならびにプリプレグは、熱伝導率の高い硬
化物を与えることができ、これを適用したプリント配線
板は、優れた放熱性を有することになる。As described in detail above, the epoxy resin composition and the prepreg of the present invention can give a cured product having a high thermal conductivity, and a printed wiring board to which this is applied has excellent heat dissipation. Will have.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 竹澤 由高 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 赤塚 正樹 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 Ｆターム(参考） 4F072 AA04 AA07 AB09 AB28 AD27 AD29 AE02 AF27 AG03 AG17 AH02 AH22 AJ04 AL09 AL13 4J036 AA02 AD07 DB05 DC40 JA07 JA11 KA01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Yutaka Takezawa 7-1-1, Omika-cho, Hitachi-shi, Ibaraki Prefecture Inside the Hitachi Research Laboratory, Hitachi Ltd. (72) Inventor Masaki Akatsuka 7-1-1, Omika-cho, Hitachi-shi, Ibaraki Prefecture Inside the Hitachi Research Laboratory, Hitachi Ltd. F-term (reference) 4F072 AA04 AA07 AB09 AB28 AD27 AD29 AE02 AF27 AG03 AG17 AH02 AH22 AJ04 AL09 AL13 4J036 AA02 AD07 DB05 DC40 JA07 JA11 KA01
Claims (8)
有し下記（式１）で示される分子構造式のエポキシ樹脂
モノマと、少なくともオルト位に水酸基が配置された二
価以上のフェノール類又はその化合物と、硬化促進剤と
を含有することを特徴とするエポキシ樹脂組成物。 【化１】 1. An epoxy resin monomer having a biphenyl group or a biphenyl derivative and having a molecular structural formula represented by the following (formula 1), and a divalent or higher phenol having a hydroxyl group at least in the ortho position or a compound thereof: An epoxy resin composition comprising a curing accelerator. [Chemical 1]
二価以上のフェノール類の化合物が、当該フェノール類
の二量体以上の重合体であることを特徴とする請求項１
記載のエポキシ樹脂組成物。2. The compound of a divalent or higher phenol compound in which a hydroxyl group is arranged at least in the ortho position is a polymer of a dimer or higher of the phenol compound.
The epoxy resin composition described.
樹脂モノマが、下記（式２）で示される分子構造式であ
ることを特徴とする請求項１又は２記載のエポキシ樹脂
組成物。 【化２】 3. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin monomer having a molecular structural formula represented by (Formula 1) is a molecular structural formula represented by the following (Formula 2). . [Chemical 2]
樹脂組成物をシート状の繊維基材に含浸し半硬化状態と
してなるプリプレグ。4. A prepreg obtained by impregnating a sheet-shaped fiber base material with the epoxy resin composition according to any one of claims 1 to 3 to be in a semi-cured state.
に含浸し半硬化状態としてなるプリプレグにおいて、前
記エポキシ樹脂組成物が、ビフェニル基あるいはビフェ
ニル誘導体を有し下記（式１）で示される分子構造式の
エポキシ樹脂モノマと、イオン重合性の硬化触媒とを含
有するエポキシ樹脂組成物であることを特徴とするプリ
プレグ。 【化３】 5. A prepreg obtained by impregnating a sheet-shaped fiber base material with an epoxy resin composition to be in a semi-cured state, wherein the epoxy resin composition has a biphenyl group or a biphenyl derivative and is represented by the following (formula 1). A prepreg, which is an epoxy resin composition containing an epoxy resin monomer having a molecular structural formula and an ionically polymerizable curing catalyst. [Chemical 3]
樹脂モノマが、下記（式２）で示される分子構造式であ
ることを特徴とする請求項５記載のプリプレグ。 【化４】 6. The prepreg according to claim 5, wherein the epoxy resin monomer having a molecular structural formula represented by (Formula 1) is a molecular structural formula represented by the following (Formula 2). [Chemical 4]
グの層をプリプレグ層の全層ないしは一部の層として加
熱加圧成形してなる積層板。7. A laminate obtained by heat-press molding the layers of the prepreg according to claim 4 as all or part of the prepreg layer.
グの層を加熱加圧成形してなる絶縁層を備えることを特
徴とするプリント配線板。8. A printed wiring board comprising an insulating layer formed by heating and pressing the layer of the prepreg according to any one of claims 4 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001337254A JP2003137971A (en) | 2001-11-02 | 2001-11-02 | Epoxy resin composition, prepreg, laminate and printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001337254A JP2003137971A (en) | 2001-11-02 | 2001-11-02 | Epoxy resin composition, prepreg, laminate and printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003137971A true JP2003137971A (en) | 2003-05-14 |
Family
ID=19151926
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001337254A Abandoned JP2003137971A (en) | 2001-11-02 | 2001-11-02 | Epoxy resin composition, prepreg, laminate and printed wiring board |
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| Country | Link |
|---|---|
| JP (1) | JP2003137971A (en) |
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