JP5037760B2 - Epoxy resin varnish for resin substrates - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、樹脂基板用エポキシ樹脂ワニス、詳しくはプリント配線板等樹脂基板の製造に好適なエポキシ樹脂ワニスに関し、熱的特性の改良されたものである。
【０００２】
【従来の技術】
近年、プリント配線板の高密度実装化の進展にともない、樹脂基板の低熱膨張化や高ガラス転移温度化等の諸特性の改良が求めれ、その対応の一例として、熱膨張係数が樹脂に比べて小さいシリカの配合されたエポキシ樹脂ワニスをガラス不織布に含浸する方法がある。しかしながら、低熱膨張化と高ガラス転移温度化を同時に発現させるためにシリカ充填量を多くすると、樹脂組成物の粘度が上昇して流動性が低下しガラス不織布への含浸作業が困難となるばかりでなく、シリカ粒子が二次凝集して樹脂基板内にボイドなどの欠陥が生じる。この問題を解決するため、例えば平均粒子径Ｄ５０が５〜１０μｍで１００％相当径Ｄ１００が４０μｍ以下のベースシリカと、平均粒子径１μｍ以下の微粉シリカの少量とを併用することが提案（特開平９−２９１１６０号公報）されている。
【０００３】
しかしながら、平均粒子径が５〜１０μｍのシリカは、エポキシ樹脂ワニスの貯蔵中に沈降してシリカ濃度差が発生しやすくなり、再撹拌によってもそれを回復させ難く、ガラス不織布表面のシリカ付着量にばらつきが生じ表面平滑性が損われる。一方、平均粒子が１μｍ以下の微粉シリカは、その形態やシラノール基の極性あるいは水素結合などによって凝集しやすいので、エポキシ樹脂ワニス中で分散不良を起こし、思ったほどにはボイド発生抑止効果を発現せず、むしろ不織布表面での分布が不均一となる。
【０００４】
シリカ表面をカップリング剤で処理してシリカの分散性を高め、熱的特性（熱膨張率やガラス転移温度）を改善する方法が知られているが、更なる向上のためにはシリカ粒子とエポキシ樹脂の複合化が不可欠である。エポキシ樹脂と微紛シリカを複合化する場合、エポキシ樹脂層を拘束する粒子表面構造の形成が必要であるため、微紛シリカを充填したエポキシ樹脂ワニス中にカップリング剤を後添加するインテグラルブレンド法が知られているが、微紛シリカは粒子同士が結合・凝集しているため、後添加したカップリング剤が粒子個々の表面を均一に被覆することは困難である。カップリング剤によって不均一な被覆が起きると、ワニスの粘度が上昇して流動性が低下しガラス不織布への含浸作業が困難となるだけでなく、熱特性向上の効果が低下する。
【０００５】
【発明が解決しようとする課題】
本発明は、上記に鑑みてなされたものであり、その目的はシリカの配合されたエポキシ樹脂ワニスの流動性を高め、ワニス中のシリカ粒子同士の結合・凝集を著しく少なくし、プリント配線板等樹脂基板の低熱膨張化や高ガラス転移温度化等の熱的特性の向上を図ることである。
【０００６】
【課題を解決するための手段】
すなわち、本発明は、平均粒子径Ｄ５０が２．０μｍ以下、１００％相当径Ｄ１００が５．０μｍ以下で、実質的にストラクチャー構造を形成していないシリカ超微粉をエポキシ樹脂中に分散させてなることを特徴とする樹脂基板用エポキシ樹脂ワニスである。本発明においては、シリカ超微紛がシランカップリング剤で表面処理されていることが好ましく、更にはシリカ超微紛が５０〜３５０ＭＰａの加圧下でエポキシ樹脂中に分散させることが好ましい。
【０００７】
【発明の実施の形態】
以下、本発明を更に詳しく説明する。
【０００８】
本発明で用いられるシリカ超微粉は、平均粒子径Ｄ５０が２．０μｍ以下で、１００％相当径Ｄ１００が５．０μｍ以下で、実質的にストラクチャー構造を形成していないことが必要である。平均粒子径Ｄ５０が１．０μｍ超又は１００％相当径Ｄ１００が３．０μｍ超であると、シリカ超微粉表面とエポキシ樹脂の相互作用が低下し、熱的特性の改善効果が不十分となるばかりでなく、エポキシ樹脂ワニスの貯蔵中に沈降してシリカ濃度差が発生しやすくなり、再撹拌によってもそれを回復させ難く、ガラス不織布表面のシリカ付着量にばらつきが生じ表面平滑性が損われる。
【０００９】
本発明において、「実質的にストラクチャー構造を形成していない」とは、以下に従いＴＥＭ観察された粒子の球形度が０.９未満であると定義される。具体的には任意に選ばれた２０個以上の粒子について画像解析装置によって取り込み、表示された値が０.９以上であることが好ましい。画像解析装置としては、例えば日本アビオニクス社製「ＳＰＩＣＣＡ−ＩＩ」が用いられる。
【００１０】
ＴＥＭ（透過型電子顕微鏡）観察は、超微粉シリカを分散させ、所定の倍率（粒子の大きさに応じて１０万倍〜１００万倍）で写真撮影を行い、ストラクチャーの形成観察と画像解析によって行われる。超微粉シリカの分散方法としては、例えばアセトン溶媒に極微量の試料を超音波分散させ、その希薄な溶液をメンブランフィルターで吸引濾過して粉末を分散状態にして乾燥する。その後フィルターに付着したままの粉末をＴＥＭ観察する。
【００１１】
粒子径はレーザー散乱光法によって測定される。その機器の一例は、コールター社製粒度測定器（モデルＬＳ−２３０型）である。平均粒子径Ｄ５０や１００％相当径Ｄ１００を測定する場合、分散媒体には純水やエタノールが用いられ、超音波を付与して試料を分散させる。
【００１２】
シリカ超微粉は、シリコン粒子を化学炎や電気炉等で形成された高温場に投じて酸化反応させながら球状化する方法（例えば特許第１５６８１６８号明細書）、シリコン粒子スラリーを火炎中に噴霧して酸化反応させながら球状化する方法などによって製造することができる。四塩化珪素の気相高温加熱分解法は、製造されたシリカ超微粉がストラクチャー構造を有するため、本発明には適さない。
【００１３】
本発明で用いられるシランカップリング剤としては、特別なものである必要がなく一般品で十分である。それを例示すると、γ−グリシドキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン等である。またこれらの化合物はそのまま、または加水分解して部分縮合物にして用いてもよく、また、２種以上を同時に用いてもよい。シランカップリング剤の使用量は、シリカ超微粉の表面を被覆するのに必要な量あればよよく、具体的にはシリカ超微粉１００質量部に対して、０．０５〜１０質量部である。
【００１４】
シランカップリング剤による処理法としては、慣用手段を採用することができる。たとえば、直接シランカップリング剤を噴霧するスプレー方法、シランカップリング剤を水又は有機溶媒に溶解しておきそれをシリカ超微粉を含浸させる溶液法などである。好ましくは前者であり、特にシリカ超微粉を製造してから捕集するまでの温度５０〜３５０℃の段階で、シランカップリング剤を気流中に噴霧する方法であり、これによって二次凝集の発生を著しく抑止することができる。
【００１５】
本発明で用いられるエポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、クレゾールノボクラック型エポキシ樹脂、脂環式エポキシ樹脂等の１種又は２種以上である。エポキシ樹脂のエポキシ当量は、１００〜５０００、特に１５０〜６００が好適である。
【００１６】
エポキシ樹脂ワニスは、通常、エポキシ樹脂、又はエポキシ樹脂とその硬化剤を必須成分として含有する。必要に応じ、溶剤、エポキシ樹脂と硬化剤との反応等を促進させるための硬化促進剤等を含有してもよい。
【００１７】
硬化剤としては、ジシアンジアミド、ジアミノジフェニルメタン、フェノールノボラックやクレゾールノボラック等の多官能性フェノール等が使用される。また、溶剤としては、メタノール、エ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、メチルイソブチルケトン等のケトン系溶剤などが用いられる。硬化剤又は溶剤は、２種類以上を併用することもできる。
【００１８】
本発明のエポキシ樹脂ワニスの配合組成の一例を示すと、エポキシ樹脂１００質量部あたり、シリカ超微粉５〜６０質量部である。
【００１９】
シリカ超微紛をエポキシ樹脂中に分散させるには、高圧ホモジナイザーと呼ばれている装置を使用することが好ましい。高圧ホモジナイザーの基本的な構成は、エポキシ樹脂ワニスを加圧する高圧発生部と絞り機構よりなる。高圧発生部としては、一般にプランジャーポンプと呼ばれている高圧ポンプが好適に採用される。高圧ポンプには、一連式、二連式、三連式などの形式があり、また動力としては、空圧、電動、油圧などの形式があるが、エポキシ樹脂ワニスを５０〜３５０ＭＰａに加圧できるものが好ましい。このような高圧ホモジナイザーを使用すると、従来のメディア媒体型分散機をはじめとする分散装置を使用して分散した場合に比べて、分散の効率が著しく高められ、短時間処理で極めて安定なエポキシ樹脂ワニスを得ることができる。
【００２０】
高圧ホモジナイザーの商品名を例示すると、スギノマシン社製「アルティマイザー」、ナノマイザー社製「ナノマイザー」、マイクロフルイディクス社製「マイクロフルイダイザー」、ミラクル社製「ナノメーカー」などである。
【００２１】
本発明のエポキシ樹脂ワニスを用いて樹脂基板を製造するには、例えばガラス布基材にエポキシ樹脂ワニスを含浸し、その繊維基材を積層成形して樹脂基板を製造する方法が一般的に用いられる。
【００２２】
【実施例】
以下、本発明の実施例、比較例をあげて更に説明する。
【００２３】
シリカ超微粉の製造炉は、内炎と外炎が形成できるように、二重管構造のＬＰＧ−酸素混合型バーナーが炉頂に設けられており、そのバーナーの中心部には更にスラリー噴射用の二流体ノズルが取り付けられている。そして、二流体ノズルの中心からスラリーが、またその周囲から酸素がそれぞれ火炎に噴射される。火炎の形成は、二重管構造バーナーのそれぞれの噴射口の細孔から、外炎形成用と内炎形成用のＬＰＧ−酸素の混合ガスが噴射されることによって行われ、ＬＰＧと酸素ガス量の制御によって火炎状態が調整される。火炎を通過した熱処理物は、ブロワーで捕集系に送られる。
【００２４】
金属シリコン粉末（平均粒径１０．５μｍ）３０部（質量部、以下同じ）と水７０部とを混合し水系スラリーを調合（固形分濃度２０％）し、二流体ノズルの中心部から火炎中（温度約１９００℃）に１２．０ｋｇ／時間の速度で噴射し、生成したシリカ超微粉をバグフィルターで捕集した。
【００２５】
実施例１
液状エポキシ樹脂（ＹＤ−１２８）８５部、溶剤（メチルエチルケトン）３０部とシリカ超微粉１５部をかき混ぜ予備混合を行った。これを簡易型混練機（シンキー社製商品名「あわとり練太郎ＡＲ−３６０Ｍ」）を用い、自転回転数６００ｒｐｍ、公転回転数２０００ｒｐｍで１０分間混練し、粘度（１ｒｐｍ時）を測定した。また、沈降安定性は１ヶ月間静置後に生じた沈降成分を計量し、初期のシリカ分に対する質量％で示した。混練して得られたエポキシ樹脂ワニスを真空乾燥機で溶媒を除去し、これの２０ｇに硬化剤４，４’−ジアミノジフェニルメタン（ＤＤＭ）を４．８８ｇ（和光純薬特級試薬）を加え、５分間減圧脱法を行い、四フッ化エチレン樹脂製型（５ｍｍ×５ｍｍ×２０ｍｍ）に注入した。その後、１５０℃で１時間、引き続き２００℃で２時間の硬化を行い、硬化物の室温から２５０℃までの熱膨張率を測定した。
【００２６】
実施例２
予備混合物を簡易型混練機で混練する代わりに、高圧ホモジナイザー（スギノマシン社製商品名「アルティマイザー」）を用い、圧力１５０ＭＰａにて５回分散処理（混練）したこと以外は、実施例１と同様にして硬化物を製造し、その熱膨張率を測定した。
【００２７】
実施例３
生成したシリカ超微粉をブロワーで捕集系（バグフィルター）に空気輸送する間の温度約２７０℃の配管部において、シランカップリング剤（信越化学工業社製γ−グリシドキシプロピルトリメトキシシラン「ＫＢＭ−４０３」）を噴霧して、シランカップリング剤で処理されたシリカ超微粉を実施例１に準じて製造し、これを用いたこと以外は、実施例１と同様にして硬化物を製造し、その熱膨張率を測定した。なお、シランカップリング剤は、水１００部に２．５部を混合したものを、シリカ超微粉１００部あたりシランカップリング剤として０．５部の割合となるように噴霧した。
【００２８】
実施例４
実施例３で製造された、シランカップリング剤で処理されたシリカ超微粉を用いたこと以外は、実施例２と同様にして硬化物を製造し、その熱膨張率を測定した。
【００２９】
実施例５
金属シリコン粉末の水系スラリーの固形分濃度が６５％であるものを用いたこと以外は、実施例２と同様にしてシリカ超微粉を製造した。このシリカ超微粉を用いたこと以外は、実施例２と同様にして硬化物を製造し、その熱膨張率を測定した。
【００３０】
実施例６
金属シリコン粉末の水系スラリーの固形分濃度が６５％であるものを用いたこと以外は、実施例４と同様にしてシランカップリング剤で処理されたシリカ超微粉を製造した。このシランカップリング剤で処理されたシリカ超微粉を用いたこと以外は、実施例４と同様にして硬化物を製造し、その熱膨張率を測定した。
【００３１】
比較例１
市販のシリカ超微粉（日本アエロジル社製商品名「アエロジル１３０」）を用いたことは以外は、実施例１と同様にして硬化物を製造し、その熱膨張率を測定した。
【００３２】
比較例２
「アエロジル１３０」を用いたことは以外は、実施例２と同様にして硬化物を製造し、その熱膨張率を測定した。
【００３３】
比較例３
「アエロジル１３０」をミキサーに入れ、２０００ｒｐｍで攪拌し、流動状態に保持し、これにシランカップリング剤（信越化学工業社製γ−グリシドキシプロピルトリメトキシシラン「ＫＢＭ−４０３」）を噴霧、次いで１５０℃で１時間熱処理し、シランカップリング処理されたシリカ超微粉を得た。このシリカ超微紛を用いたことは以外は、実施例１と同様にして硬化物を製造し、その熱膨張率を測定した。
【００３４】
比較例４
比較例３で製造された、シランカップリング処理された「アエロジル１３０」を用いたことは以外は、実施例２と同様にして硬化物を製造し、その熱膨張率を測定した。
【００３５】
以上の結果を表２に、シリカ超微粉の特性を表１に示す。
【００３６】
【表１】
【表２】
実施例１〜６と比較例１〜４との対比から明らかなように、本発明の樹脂基板用エポキシ樹脂ワニスは、シリカ粒子が高度に分散しており、シリカ粒子同士の結合・凝集が極めて起こり難くいため沈降安定性に優れる。その結果、これを用いて製造されたプリント配線板等の樹脂基板は従来品よりも低熱膨張率化等の諸特性の改善が著しく図られている。
【００３９】
【発明の効果】
本発明によれば、エポキシ樹脂ワニス中のシリカ粒子同士の結合・凝集が著しく少なく、これを用いて製造された樹脂基板は、低熱膨張率かつ高ガラス転移温度を有し、熱的特性が極めて向上したものとなる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin varnish for a resin substrate, and more particularly to an epoxy resin varnish suitable for producing a resin substrate such as a printed wiring board, and has improved thermal characteristics.
[0002]
[Prior art]
In recent years, with the progress of high-density mounting of printed wiring boards, improvement of various characteristics such as low thermal expansion and high glass transition temperature of resin substrates is required. As an example of the countermeasure, the thermal expansion coefficient is higher than that of resin. There is a method of impregnating a glass nonwoven fabric with an epoxy resin varnish containing small silica. However, if the silica loading is increased in order to develop low thermal expansion and high glass transition temperature at the same time, the viscosity of the resin composition increases and fluidity decreases, making it difficult to impregnate the glass nonwoven fabric. However, the silica particles are secondarily aggregated to cause defects such as voids in the resin substrate. In order to solve this problem, for example, it is proposed to use in combination a base silica having an average particle diameter D50 of 5 to 10 μm and a 100% equivalent diameter D100 of 40 μm or less and a small amount of finely divided silica having an average particle diameter of 1 μm or less (Japanese Patent Laid-Open 9-291160).
[0003]
However, silica having an average particle size of 5 to 10 μm is likely to settle during storage of the epoxy resin varnish, resulting in a difference in silica concentration, which is difficult to recover even by re-stirring. Variation occurs and surface smoothness is impaired. On the other hand, finely divided silica with an average particle size of 1 μm or less is prone to agglomerate due to its form, silanol group polarity or hydrogen bonds, which causes poor dispersion in the epoxy resin varnish and exhibits a void generation suppression effect as expected. Rather, the distribution on the nonwoven fabric surface is non-uniform.
[0004]
A method for improving the thermal properties (thermal expansion coefficient and glass transition temperature) by treating the silica surface with a coupling agent to improve the dispersibility of silica is known. Composite of epoxy resin is indispensable. When blending epoxy resin and fine powder silica, it is necessary to form a particle surface structure that constrains the epoxy resin layer, so an integral blend in which a coupling agent is added to an epoxy resin varnish filled with fine powder silica. Although the method is known, since fine particles of silica are bonded and agglomerated, it is difficult for the coupling agent added later to uniformly coat the surface of each particle. When non-uniform coating occurs due to the coupling agent, not only does the viscosity of the varnish increase and the fluidity decreases, and the impregnation operation into the glass nonwoven fabric becomes difficult, but the effect of improving the thermal properties decreases.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above, and its purpose is to increase the fluidity of an epoxy resin varnish containing silica, to significantly reduce the bonding / aggregation of silica particles in the varnish, and to a printed wiring board, etc. The purpose is to improve the thermal characteristics of the resin substrate such as low thermal expansion and high glass transition temperature.
[0006]
[Means for Solving the Problems]
That is, in the present invention, an ultrafine silica powder having an average particle diameter D50 of 2.0 μm or less, a 100% equivalent diameter D100 of 5.0 μm or less, and substantially not forming a structure structure is dispersed in an epoxy resin. This is an epoxy resin varnish for a resin substrate. In the present invention, the silica ultrafine powder is preferably surface-treated with a silane coupling agent, and the silica ultrafine powder is preferably dispersed in the epoxy resin under a pressure of 50 to 350 MPa.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0008]
The ultrafine silica powder used in the present invention is required to have an average particle diameter D50 of 2.0 μm or less and a 100% equivalent diameter D100 of 5.0 μm or less and substantially not form a structure structure. When the average particle diameter D50 is more than 1.0 μm or the 100% equivalent diameter D100 is more than 3.0 μm, the interaction between the silica ultrafine powder surface and the epoxy resin is lowered, and the effect of improving the thermal characteristics becomes insufficient. In addition, the silica resin settles during storage of the epoxy resin varnish, and a difference in silica concentration is likely to occur. It is difficult to recover even by re-stirring, and the amount of silica adhered to the surface of the glass nonwoven fabric varies and the surface smoothness is impaired.
[0009]
In the present invention, “substantially no structure is formed” is defined as the sphericity of particles observed by TEM being less than 0.9 according to the following. Specifically, it is preferable that 20 or more particles arbitrarily selected are captured by an image analyzer and displayed values are 0.9 or more. As the image analysis apparatus, for example, “SPICCA-II” manufactured by Nippon Avionics Co., Ltd. is used.
[0010]
In TEM (transmission electron microscope) observation, ultrafine silica is dispersed and photographed at a predetermined magnification (100,000 to 1,000,000 times depending on the size of the particles), through structure formation observation and image analysis. Done. As a method for dispersing the ultrafine silica, for example, a very small amount of sample is ultrasonically dispersed in an acetone solvent, and the diluted solution is suction filtered through a membrane filter to dry the powder in a dispersed state. Thereafter, the powder remaining on the filter is observed with a TEM.
[0011]
The particle diameter is measured by a laser scattered light method. An example of the apparatus is a particle size measuring instrument (model LS-230 type) manufactured by Coulter. When measuring the average particle diameter D50 or 100% equivalent diameter D100, pure water or ethanol is used as the dispersion medium, and ultrasonic waves are applied to disperse the sample.
[0012]
Silica ultrafine powder is a method of spheroidizing silicon particles by throwing them into a high temperature field formed by a chemical flame or an electric furnace (for example, Japanese Patent No. 1568168), and spraying silicon particle slurry into the flame. It can be manufactured by a method of spheroidizing while oxidizing. The vapor phase high temperature thermal decomposition method of silicon tetrachloride is not suitable for the present invention because the produced silica ultrafine powder has a structure structure.
[0013]
The silane coupling agent used in the present invention does not need to be a special one, and a general product is sufficient. Examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and the like. These compounds may be used as they are or after hydrolysis to form partial condensates, or two or more of them may be used simultaneously. The amount of the silane coupling agent used may be an amount necessary for coating the surface of the silica ultrafine powder, specifically 0.05 to 10 parts by mass with respect to 100 parts by mass of the silica ultrafine powder. .
[0014]
Conventional methods can be employed as a treatment method using a silane coupling agent. For example, there are a spray method in which a silane coupling agent is directly sprayed, and a solution method in which a silane coupling agent is dissolved in water or an organic solvent and impregnated with silica ultrafine powder. Preferably, the former is a method in which a silane coupling agent is sprayed into an air stream at a stage of a temperature of 50 to 350 ° C. from the production of the silica ultrafine powder to the collection, thereby generating secondary aggregation. Can be significantly suppressed.
[0015]
As an epoxy resin used by this invention, it is 1 type, or 2 or more types, such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a cresol novolak type epoxy resin, and an alicyclic epoxy resin. The epoxy equivalent of the epoxy resin is preferably 100 to 5000, particularly 150 to 600.
[0016]
The epoxy resin varnish usually contains an epoxy resin or an epoxy resin and a curing agent thereof as essential components. You may contain the hardening accelerator for accelerating | stimulating reaction etc. of a solvent and an epoxy resin, and a hardening | curing agent as needed.
[0017]
As the curing agent, polyfunctional phenols such as dicyandiamide, diaminodiphenylmethane, phenol novolac and cresol novolac are used. Examples of the solvent include alcohol solvents such as methanol and ethanol, and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Two or more curing agents or solvents can be used in combination.
[0018]
An example of the composition of the epoxy resin varnish of the present invention is 5 to 60 parts by mass of silica ultrafine powder per 100 parts by mass of the epoxy resin.
[0019]
In order to disperse the silica ultrafine powder in the epoxy resin, it is preferable to use an apparatus called a high-pressure homogenizer. The basic configuration of the high-pressure homogenizer includes a high-pressure generating unit that pressurizes the epoxy resin varnish and a throttle mechanism. As the high-pressure generating unit, a high-pressure pump generally called a plunger pump is preferably employed. High-pressure pumps are available in a series, double, triple, etc., and powers include pneumatic, electric, hydraulic, etc., but the epoxy resin varnish can be pressurized to 50-350 MPa. Those are preferred. When such a high-pressure homogenizer is used, the dispersion efficiency is remarkably improved compared to the case where dispersion is performed using a dispersion apparatus such as a conventional media medium type dispersion machine, and the epoxy resin is extremely stable in a short time treatment. A varnish can be obtained.
[0020]
Examples of the high-pressure homogenizer include “Ultimizer” manufactured by Sugino Machine, “Nanomizer” manufactured by Nanomizer, “MicroFluidizer” manufactured by Microfluidics, “Nanomaker” manufactured by Miracle, and the like.
[0021]
In order to manufacture a resin substrate using the epoxy resin varnish of the present invention, for example, a method of manufacturing a resin substrate by impregnating an epoxy resin varnish into a glass cloth substrate and laminating the fiber substrate is generally used. It is done.
[0022]
【Example】
Hereinafter, the present invention will be further described with reference to examples and comparative examples.
[0023]
The silica ultrafine powder production furnace is equipped with a double-pipe LPG-oxygen mixed burner at the top of the furnace so that an internal flame and an external flame can be formed. A two-fluid nozzle is attached. Then, slurry is injected into the flame from the center of the two-fluid nozzle and oxygen is injected from the periphery thereof. The formation of the flame is performed by injecting a mixed gas of LPG-oxygen for forming the outer flame and the inner flame from the pores of the respective injection ports of the double tube structure burner, and the amount of LPG and oxygen gas The flame condition is adjusted by controlling the above. The heat-treated product that has passed through the flame is sent to a collection system by a blower.
[0024]
Mixing 30 parts of metal silicon powder (average particle size 10.5 μm) (mass part, the same shall apply hereinafter) and 70 parts of water to prepare an aqueous slurry (solid content 20%), and in the flame from the center of the two-fluid nozzle (The temperature was about 1900 ° C.) at a speed of 12.0 kg / hour, and the produced silica ultrafine powder was collected by a bag filter.
[0025]
Example 1
85 parts of a liquid epoxy resin (YD-128), 30 parts of a solvent (methyl ethyl ketone) and 15 parts of silica ultrafine powder were mixed and premixed. This was kneaded for 10 minutes at a rotation speed of 600 rpm and a revolution speed of 2000 rpm using a simple kneader (trade name “Awatori Nertaro AR-360M” manufactured by Shinky Corporation), and the viscosity (at 1 rpm) was measured. In addition, the sedimentation stability was measured by measuring the sediment components generated after standing for 1 month and expressed as mass% with respect to the initial silica content. The solvent was removed from the epoxy resin varnish obtained by kneading with a vacuum dryer, and 4.88 g of a curing agent 4,4′-diaminodiphenylmethane (DDM) (Wako Pure Chemicals special grade reagent) was added to 20 g of this. The depressurization method was performed for a minute, and the mixture was poured into a tetrafluoroethylene resin mold (5 mm × 5 mm × 20 mm). Thereafter, curing was performed at 150 ° C. for 1 hour and subsequently at 200 ° C. for 2 hours, and the thermal expansion coefficient of the cured product from room temperature to 250 ° C. was measured.
[0026]
Example 2
Example 1 except that instead of kneading the preliminary mixture with a simple kneader, a high-pressure homogenizer (trade name “Ultimizer” manufactured by Sugino Machine Co., Ltd.) was used and the dispersion treatment (kneading) was performed 5 times at a pressure of 150 MPa. Similarly, a cured product was produced, and the coefficient of thermal expansion was measured.
[0027]
Example 3
A silane coupling agent (γ-glycidoxypropyltrimethoxysilane “manufactured by Shin-Etsu Chemical Co., Ltd.” is used in a piping section at a temperature of about 270 ° C. while the produced silica ultrafine powder is pneumatically transported to a collection system (bag filter) by a blower. KBM-403 ") is sprayed to produce a silica ultrafine powder treated with a silane coupling agent according to Example 1, and a cured product is produced in the same manner as in Example 1 except that this is used. The coefficient of thermal expansion was measured. In addition, the silane coupling agent sprayed what mixed 2.5 parts with 100 parts of water so that it might become a ratio of 0.5 part as a silane coupling agent per 100 parts of silica ultrafine powder.
[0028]
Example 4
A cured product was produced in the same manner as in Example 2 except that the ultrafine silica powder treated with the silane coupling agent produced in Example 3 was used, and the coefficient of thermal expansion was measured.
[0029]
Example 5
A silica ultrafine powder was produced in the same manner as in Example 2 except that the solid content concentration of the aqueous slurry of metal silicon powder was 65%. A cured product was produced in the same manner as in Example 2 except that this silica ultrafine powder was used, and the coefficient of thermal expansion was measured.
[0030]
Example 6
A silica ultrafine powder treated with a silane coupling agent was produced in the same manner as in Example 4 except that the solid content concentration of the aqueous slurry of metal silicon powder was 65%. A cured product was produced in the same manner as in Example 4 except that the ultrafine silica powder treated with this silane coupling agent was used, and the coefficient of thermal expansion was measured.
[0031]
Comparative Example 1
A cured product was produced in the same manner as in Example 1 except that a commercially available silica ultrafine powder (trade name “Aerosil 130” manufactured by Nippon Aerosil Co., Ltd.) was used, and the coefficient of thermal expansion was measured.
[0032]
Comparative Example 2
A cured product was produced in the same manner as in Example 2 except that “Aerosil 130” was used, and the coefficient of thermal expansion was measured.
[0033]
Comparative Example 3
“Aerosil 130” is put into a mixer, stirred at 2000 rpm, and kept in a fluid state, and sprayed with a silane coupling agent (γ-glycidoxypropyltrimethoxysilane “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) Subsequently, it heat-processed at 150 degreeC for 1 hour, and obtained the silica ultrafine powder by which the silane coupling process was carried out. A cured product was produced in the same manner as in Example 1 except that this silica ultrafine powder was used, and the coefficient of thermal expansion was measured.
[0034]
Comparative Example 4
A cured product was produced in the same manner as in Example 2 except that “Aerosil 130” subjected to silane coupling treatment produced in Comparative Example 3 was used, and the coefficient of thermal expansion was measured.
[0035]
The above results are shown in Table 2, and the characteristics of the silica ultrafine powder are shown in Table 1.
[0036]
[Table 1]
[Table 2]
As is clear from the comparison between Examples 1 to 6 and Comparative Examples 1 to 4, the epoxy resin varnish for a resin substrate of the present invention has highly dispersed silica particles, and the silica particles are extremely bonded and aggregated. It is difficult to occur and has excellent sedimentation stability. As a result, a resin substrate such as a printed wiring board manufactured using the same is remarkably improved in various characteristics such as a lower coefficient of thermal expansion than a conventional product.
[0039]
【Effect of the invention】
According to the present invention, the silica particles in the epoxy resin varnish have extremely few bonds / aggregation, and the resin substrate manufactured using the silica particles has a low coefficient of thermal expansion and a high glass transition temperature, and has extremely high thermal characteristics. It will be improved.
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| JP4010420B2 (en) * | 2004-08-16 | 2007-11-21 | 電気化学工業株式会社 | Epoxy resin filler and method for producing the same |
| JP4776398B2 (en) * | 2006-03-03 | 2011-09-21 | 古河マグネットワイヤ株式会社 | Heat-resistant self-bonding wire and heat-resistant voice coil for speakers |
| CN101784614A (en) * | 2008-01-31 | 2010-07-21 | 积水化学工业株式会社 | Resin composition and multilayer resin film employing the same |
| JP5476715B2 (en) * | 2008-12-25 | 2014-04-23 | 味の素株式会社 | Method for producing resin composition varnish |
| CN101704991B (en) * | 2009-11-23 | 2011-08-17 | 南亚塑胶工业股份有限公司 | Thermosetting epoxy resin composition |
| JP2013010899A (en) * | 2011-06-30 | 2013-01-17 | Sekisui Chem Co Ltd | Resin varnish, filtration treatment resin varnish, method of producing the filtration treatment resin varnish, laminated film, and multilayer board |
| JP6546386B2 (en) * | 2014-10-15 | 2019-07-17 | 株式会社アドマテックス | Inorganic filler, method for producing the same, resin composition, and molded article |
| JP6632286B2 (en) * | 2015-09-18 | 2020-01-22 | アシザワ・ファインテック株式会社 | Method for lowering thermal expansion coefficient of resin molding |
| JP7063710B2 (en) * | 2018-04-27 | 2022-05-09 | 株式会社日本触媒 | Method for producing surface-treated silica particles and surface-treated silica particles |
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| JPH05230185A (en) * | 1991-10-29 | 1993-09-07 | Kobe Steel Ltd | Electrically insulating composite sheet material having excellent flexibility |
| JPH08146641A (en) * | 1994-11-24 | 1996-06-07 | Canon Inc | Electrophotographic photoreceptor and electrophotographic device |
| JPH1112267A (en) * | 1997-06-18 | 1999-01-19 | Sumitomo Chem Co Ltd | Production of polyhydric phenol compound, epoxy resin composition and product using the same |
| JPH1160912A (en) * | 1997-08-27 | 1999-03-05 | Toshiba Corp | Resin composition for casting, and insulation spacer comprising the resin composition |
| JP2000239536A (en) * | 1998-12-24 | 2000-09-05 | Tokuyama Corp | Cationic resin-modified silica dispersion and its production |
| JP2000191489A (en) * | 1998-12-28 | 2000-07-11 | Hakusui Tech Co Ltd | Ultrafine, particulate zinc oxide silicone dispersion, its production and ultraviolet screening cosmetic |
| JP3960700B2 (en) * | 1999-02-23 | 2007-08-15 | 電気化学工業株式会社 | Method for producing ultrafine silica |
| JP4112125B2 (en) * | 1999-08-13 | 2008-07-02 | 電気化学工業株式会社 | Method for producing fine spherical silica powder |
| JP4306951B2 (en) * | 2000-11-07 | 2009-08-05 | 電気化学工業株式会社 | Surface-treated fine spherical silica powder and resin composition |
| JP2002275356A (en) * | 2001-03-22 | 2002-09-25 | Denki Kagaku Kogyo Kk | Filler for epoxy resin, and epoxy resin composition |
| JP3886363B2 (en) * | 2001-11-14 | 2007-02-28 | 電気化学工業株式会社 | Method for producing hydrophobic silica fine powder |
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