JP2002047395A - Epoxy resin composition, prepreg and copper-clad laminate using it - Google Patents
Epoxy resin composition, prepreg and copper-clad laminate using itInfo
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- JP2002047395A JP2002047395A JP2000235301A JP2000235301A JP2002047395A JP 2002047395 A JP2002047395 A JP 2002047395A JP 2000235301 A JP2000235301 A JP 2000235301A JP 2000235301 A JP2000235301 A JP 2000235301A JP 2002047395 A JP2002047395 A JP 2002047395A
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- epoxy resin
- resin composition
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- molecule
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- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ハロゲン系難燃剤
を使用せずとも優れた難燃性を有し、かつ優れた耐熱
性、寸法安定性を発現するエポキシ樹脂組成物、プリプ
レグ及びそれを用いた銅張積層板に関するものである。TECHNICAL FIELD The present invention relates to an epoxy resin composition, prepreg, which has excellent flame retardancy without using a halogen-based flame retardant, and exhibits excellent heat resistance and dimensional stability. It relates to the used copper-clad laminate.
【０００２】[0002]
【従来の技術】半導体の分野では高密度実装技術の進歩
から従来の面実装からエリア実装に移行していくトレン
ドが進行し、ＢＧＡやＣＳＰなど新しいパッケージが登
場、増加しつつある。そのため以前にもましてインター
ポーザ用リジッド基板が注目されるようになり、高耐
熱、低熱膨張基板の要求が高まってきた。一方、これら
半導体に用いられる樹脂部材は難燃性が求められること
が多い。従来この難燃性を付与するため、エポキシ樹脂
においては臭素化エポキシなどのハロゲン系難燃剤を用
いることが一般的であった。しかし、ハロゲン含有化合
物からダイオキシンが発生するおそれがあることから、
昨今の環境問題の深刻化とともに、ハロゲン系難燃剤を
使用することが回避されるようになり、広く産業界にハ
ロゲンフリーの難燃化システムが求められるようになっ
た。このような時代の要求によってリン系難燃剤が脚光
を浴び、リン酸エステルや赤リンが検討されたが、これ
ら従来のリン系難燃剤は加水分解しやすく樹脂との反応
に乏しいため、耐半田性が低下したり、ガラス転移温度
が低下するという問題があった。2. Description of the Related Art In the field of semiconductors, the trend of shifting from conventional surface mounting to area mounting has progressed due to the progress of high-density mounting technology, and new packages such as BGA and CSP have appeared and are increasing. For this reason, rigid substrates for interposers have attracted more attention than ever before, and demands for substrates having high heat resistance and low thermal expansion have increased. On the other hand, resin members used for these semiconductors are often required to have flame retardancy. Conventionally, in order to impart this flame retardancy, it has been common to use a halogen-based flame retardant such as a brominated epoxy in an epoxy resin. However, since dioxin may be generated from the halogen-containing compound,
With the recent increase in environmental problems, the use of halogen-based flame retardants has been avoided, and a wide range of industries has been demanded for halogen-free flame retardant systems. Phosphorus-based flame retardants have come into the limelight in response to the demands of such times, and phosphate esters and red phosphorus have been studied.However, these conventional phosphorus-based flame retardants are easily hydrolyzed and have a poor reaction with the resin, so that solder resistant There is a problem that the properties are lowered and the glass transition temperature is lowered.
【０００３】[0003]
【発明が解決しようとする課題】本発明はこのような問
題を解決するべくなされたもので、ハロゲンフリーで優
れた難燃性を有し、かつ高耐熱、低熱膨張の特性を発現
しうるエポキシ樹脂組成物、プリプレグ、及び銅張積層
板を提供するものである。DISCLOSURE OF THE INVENTION The present invention has been made to solve such a problem, and is an epoxy which is halogen-free, has excellent flame retardancy, and can exhibit high heat resistance and low thermal expansion characteristics. A resin composition, a prepreg, and a copper-clad laminate are provided.
【０００４】[0004]
【課題を解決するための手段】本発明は、耐熱性に寄与
する多官能エポキシ樹脂、フェノール樹脂系硬化剤、難
燃性や優れた耐加水分解性を有する特定構造のリン化合
物、及び低熱膨張性や低吸水性を発現する特定の球状シ
リカを必須成分として含有する銅張積層板用として好適
なエポキシ樹脂組成物を技術骨子とするものであり、か
かる組成により上記目的を達成するに至った。SUMMARY OF THE INVENTION The present invention provides a polyfunctional epoxy resin which contributes to heat resistance, a phenolic resin-based curing agent, a phosphorus compound having a specific structure having flame retardancy and excellent hydrolysis resistance, and low thermal expansion. The technical gist is an epoxy resin composition suitable for a copper-clad laminate containing a specific spherical silica exhibiting water resistance and low water absorption as an essential component, and the above-described object has been achieved by such a composition. .
【０００５】具体的には、１分子中に３個以上のエポキ
シ基を有するエポキシ樹脂、１分子中に３個以上のフェ
ノール性水酸基を有するフェノール樹脂系硬化剤、９，
１０−ジヒドロ−９−オキサ−１０−ホスファフェナン
トレン−１０−オキシド、及び最大粒径２４μｍ以下
で、平均粒径２μｍ以上５μｍ以下、かつ比表面積が５
ｍ2／ｇ以下の球状溶融シリカを必須成分とすることを
特徴とするエポキシ樹脂組成物、さらにはこれらの成分
に加え、カップリング剤を必須成分として含有すること
を特徴とするエポキシ樹脂組成物、およびこれらのエポ
キシ樹脂組成物を基材に含浸、乾燥して得られるプリプ
レグ、それを用いて加熱成形してなる銅張積層板であ
る。Specifically, an epoxy resin having three or more epoxy groups in one molecule, a phenol resin-based curing agent having three or more phenolic hydroxyl groups in one molecule,
10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a maximum particle size of 24 μm or less, an average particle size of 2 μm to 5 μm, and a specific surface area of 5 μm or less.
An epoxy resin composition comprising spherical fused silica of m 2 / g or less as an essential component, and an epoxy resin composition further comprising a coupling agent as an essential component in addition to these components And a prepreg obtained by impregnating a substrate with these epoxy resin compositions and drying, and a copper-clad laminate formed by heat molding using the prepreg.
【０００６】[0006]
【発明の実施の形態】本発明に用いる、（Ａ）１分子中
に３個以上のエポキシ基を有するエポキシ樹脂として
は、オルソクレゾールノボラックエポキシ樹脂、フェノ
ールノボラックエポキシ樹脂、ビスフェノールＡノボラ
ックエポキシ樹脂などのノボラック型エポキシ樹脂、ト
リスヒドロキシフェニルメタン型エポキシ樹脂および対
応する芳香族環がアルキル化されたエポキシ樹脂などの
誘導体、１，１，２，２−テトラキスヒドロキシフェニ
ルエタンのグリシジルエーテル化物、およびその２量
体、３量体などのテトラキスヒドロキシフェニルエタン
型エポキシ樹脂、などが例示される。エポキシ樹脂は、
後述する反応性リン化合物である、９，１０−ジヒドロ
−９−オキサ−１０−ホスファフェナントレン−１０−
オキシドがエポキシ基と反応して樹脂中のエポキシ基が
減少することから、ガラス転移温度を高い状態に保つた
めには、３官能以上のエポキシ樹脂であることが必須で
ある。特に３官能以上のエポキシ樹脂の中でも、ノボラ
ック型エポキシ樹脂（Ａ１）及び、トリスヒドロキシフ
ェニルメタン型エポキシ樹脂とテトラキスヒドロキシフ
ェニルエタン型エポキシ樹脂から選ばれる少なくとも１
種のエポキシ樹脂（Ａ２）を組み合わせた場合、トリス
ヒドロキシフェニルメタン型エポキシ樹脂又はテトラキ
スヒドロキシフェニルエタン型エポキシ樹脂（Ａ２）で
架橋密度を高くしてガラス転移温度を高くでき、一方ノ
ボラック型エポキシ樹脂（Ａ１）によって、前記（Ａ
２）のエポキシ樹脂の欠点である吸水性の大きさや架橋
密度が過度に高くなることによる脆さ、密着性の低下な
どを防ぐことができる。特にノボラック型エポキシ樹脂
（Ａ１）の中でもオルソクレゾールノボラックエポキシ
樹脂が吸水性を低減できるので好ましい。本発明におい
て、エポキシ樹脂組成物中に占める（Ａ）成分の割合は
１０〜５０重量％が好ましい。１０重量％未満では、結
合剤成分が少なくなり、耐熱性が低下するようになる。
５０重量％を越えると、充填材の割合が低下し、熱膨
張、吸水率が増加するので好ましくない。なお、エポキ
シ樹脂として、（Ａ）成分以外のエポキシ樹脂、例えば
ビスフェノールＡ型のエポキシ樹脂をエポキシ樹脂全体
の３０重量％以下配合してもよい。BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin (A) having three or more epoxy groups in one molecule used in the present invention includes orthocresol novolak epoxy resin, phenol novolak epoxy resin, bisphenol A novolak epoxy resin and the like. Derivatives such as novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin and corresponding epoxy resin in which aromatic ring is alkylated, glycidyl etherified product of 1,1,2,2-tetrakishydroxyphenylethane, and dimer thereof Tetrakishydroxyphenylethane-type epoxy resin such as dimer, trimer and the like. Epoxy resin is
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-, a reactive phosphorus compound described below.
Since the oxide reacts with the epoxy group to decrease the epoxy group in the resin, it is essential that the epoxy resin is a trifunctional or higher functional epoxy resin in order to keep the glass transition temperature high. In particular, among trifunctional or higher epoxy resins, at least one selected from a novolak type epoxy resin (A1) and a trishydroxyphenylmethane type epoxy resin and a tetrakishydroxyphenylethane type epoxy resin.
When the epoxy resins (A2) are combined, the glass transition temperature can be increased by increasing the crosslink density with the trishydroxyphenylmethane type epoxy resin or the tetrakishydroxyphenylethane type epoxy resin (A2), while the novolak type epoxy resin ( A1), the (A)
It is possible to prevent the disadvantages of the epoxy resin of 2) such as brittleness due to excessively high water absorption and excessively high crosslinking density, and a decrease in adhesion. In particular, among the novolak-type epoxy resins (A1), ortho-cresol novolak epoxy resin is preferable because the water absorption can be reduced. In the present invention, the proportion of the component (A) in the epoxy resin composition is preferably from 10 to 50% by weight. If it is less than 10% by weight, the amount of the binder component is reduced, and the heat resistance is reduced.
If it exceeds 50% by weight, the proportion of the filler is decreased, and the thermal expansion and the water absorption are undesirably increased. In addition, as the epoxy resin, an epoxy resin other than the component (A), for example, a bisphenol A type epoxy resin may be blended in an amount of 30% by weight or less of the entire epoxy resin.
【０００７】次に成分（Ｂ）１分子中に３個以上のフェ
ノール性水酸基を有するフェノール樹脂系硬化剤として
は、フェノールノボラック、ビスフェノールＡノボラッ
ク、フェノールアラルキル樹脂等が例示されるが、フェ
ノール性水酸基当量が比較的小さく、低官能のモノマー
を容易に除去できるフェノールノボラックが好ましい。
本発明では（Ｂ）成分は、エポキシ樹脂のエポキシ基
と、（Ｂ）成分のフェノール性水酸基およびその他の活
性水素の合計との当量比が０．８以上１．２以下となる
よう添加することが好ましい。この範囲外ではガラス転
移温度の低下や電気特性の低下が生じることがある。The phenolic resin-based curing agent having three or more phenolic hydroxyl groups in one molecule of component (B) is exemplified by phenol novolak, bisphenol A novolak, phenol aralkyl resin and the like. Phenol novolak having a relatively small equivalent weight and capable of easily removing low-functional monomers is preferable.
In the present invention, the component (B) is added so that the equivalent ratio of the epoxy group of the epoxy resin to the total of the phenolic hydroxyl group and other active hydrogen of the component (B) is 0.8 or more and 1.2 or less. Is preferred. Outside this range, the glass transition temperature and the electrical properties may be reduced.
【０００８】本発明の難燃成分である、成分（Ｃ）９，
１０−ジヒドロ−９−オキサ−１０−ホスファフェナン
トレン−１０−オキシドは、リンに結合している水素が
エポキシ基と反応する反応性リン化合物であり、従来の
リン酸エステルや赤リンのように加水分解して吸水性を
高めたり、密着性を低下させたりすることがなく、極め
て優れたリン系難燃剤である。本発明の（Ｃ）成分添加
量は、エポキシ樹脂組成物全体に対して、０．５〜１０
重量％が好ましい。０．５重量％未満では難燃効果が低
下するおそれがあり、１０重量％を越えるとガラス転移
温度が低下する場合がある。[0008] Component (C) 9, which is the flame retardant component of the present invention,
10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is a reactive phosphorus compound in which hydrogen bonded to phosphorus reacts with an epoxy group, such as a conventional phosphoric acid ester or red phosphorus. It is an extremely excellent phosphorus-based flame retardant without hydrolyzing to increase water absorption or reducing adhesion. Component (C) of the present invention is added in an amount of 0.5 to 10 based on the entire epoxy resin composition.
% By weight is preferred. If it is less than 0.5% by weight, the flame-retardant effect may be reduced. If it exceeds 10% by weight, the glass transition temperature may be lowered.
【０００９】本発明の成分（Ｄ）は、最大粒径２４μｍ
以下で、平均粒径２μｍ以上５μｍ以下、かつ比表面積
が５ｍ2／ｇ以下の球状溶融シリカである。多量に充填
材を添加し低熱膨張性と樹脂の流動性を両立させるには
球状溶融シリカが他の充填材に勝っており最適である。
球状溶融シリカの中でも最大粒径２４μｍ以下で、平均
粒径２μｍ以上５μｍ以下、かつＢＥＴ法による比表面
積が５ｍ2／ｇ以下の球状溶融シリカが好ましい。最大
粒径が２４μｍを超える粗粒が含まれると銅箔と基材の
間で粗粒に起因する空間ができ、吸湿した場合に水が滞
留して半田耐熱が悪化したり、銅張積層板板の外観が悪
化したりする。また平均粒径が２μｍより小さい場合や
比表面積が５ｍ2／ｇを超える場合、粒子の２次凝集に
より前述粗粒が含まれる場合と同様の問題が生じる場合
がある。この球状溶融シリカはエポキシ樹脂組成物中５
０重量％以上を占めると熱膨張、吸水率が小さくなるの
で好ましい。ただし、９０重量％を越えるとエポキシ樹
脂組成物中の無機充填材の割合が大きすぎて含浸等の操
作が困難となる。また必要に応じて特性を妨げない範囲
で他の充填材を使用してもよい。この場合、最大粒径２
４μｍ以下で、平均粒径２μｍ以上５μｍ以下、かつ比
表面積が５ｍ2／ｇ以下の球状溶融シリカ以外の球状シ
リカをはじめとして従来公知の充填材を、半田耐熱性等
の特性を悪化させない程度において、任意に使用可能で
ある。The component (D) of the present invention has a maximum particle size of 24 μm.
Spherical fused silica having an average particle size of 2 μm or more and 5 μm or less and a specific surface area of 5 m 2 / g or less. In order to achieve both low thermal expansion and resin fluidity by adding a large amount of filler, spherical fused silica is optimal because it is superior to other fillers.
Among spherical fused silica, spherical fused silica having a maximum particle size of 24 μm or less, an average particle size of 2 μm or more and 5 μm or less, and a specific surface area by a BET method of 5 m 2 / g or less is preferable. When coarse particles having a maximum particle size of more than 24 μm are contained, a space caused by the coarse particles is formed between the copper foil and the base material, and when moisture is absorbed, water stays and the solder heat resistance deteriorates. The appearance of the board may deteriorate. When the average particle size is smaller than 2 μm or when the specific surface area exceeds 5 m 2 / g, the same problem as the case where the coarse particles are contained may occur due to secondary aggregation of the particles. This spherical fused silica is 5% in the epoxy resin composition.
When the content is 0% by weight or more, thermal expansion and water absorption are reduced, which is preferable. However, when the content exceeds 90% by weight, the proportion of the inorganic filler in the epoxy resin composition is too large, and operations such as impregnation become difficult. If necessary, other fillers may be used as long as the properties are not hindered. In this case, the maximum particle size 2
Conventionally known fillers including spherical silica other than spherical fused silica having an average particle diameter of 4 μm or less, an average particle diameter of 2 μm or more and 5 μm or less, and a specific surface area of 5 m 2 / g or less are used so far as the properties such as solder heat resistance are not deteriorated. , Can be used arbitrarily.
【００１０】本発明の樹脂組成物にさらにカップリング
剤を用いると、樹脂と充填材の界面のぬれ性が向上し好
ましい。特にシロキサン結合の繰り返し単位を２個以上
有し、かつアルコキシ基を有するシリコーンオイル型カ
ップリング剤（Ｅ）はプリプレグ製造時の高温にさらさ
れても揮発することなく、充填材表面にコーティングさ
れるので好ましく用いられる。この場合、汎用シランカ
ップリング剤との併用が充填材とのぬれ性と充填材表面
へのカップリング剤の定着性のバランスがとれ効果的で
ある。本発明では（Ｅ）成分は、エポキシ樹脂組成物全
体に対して、０．１〜５重量％が好ましい。０．１重量
％未満では充填材の表面全体にカップリング剤を分散さ
せることができない可能性がある。また５重量％を越え
るとガラス転移温度が低下する場合がある。It is preferable to further use a coupling agent in the resin composition of the present invention since the wettability at the interface between the resin and the filler is improved. In particular, the silicone oil type coupling agent (E) having two or more repeating units of siloxane bonds and having an alkoxy group is coated on the surface of the filler without volatilization even when exposed to a high temperature during prepreg production. It is preferably used. In this case, the combined use with the general-purpose silane coupling agent is effective in balancing the wettability with the filler and the fixability of the coupling agent on the surface of the filler. In the present invention, the content of the component (E) is preferably 0.1 to 5% by weight based on the entire epoxy resin composition. If the amount is less than 0.1% by weight, the coupling agent may not be dispersed on the entire surface of the filler. If it exceeds 5% by weight, the glass transition temperature may decrease.
【００１１】本発明のエポキシ樹脂組成物は必要に応じ
て、上記成分以外の添加剤を特性を損なわない範囲で添
加することができる。本発明のエポキシ樹脂組成物は溶
剤を用いてワニスとして、または無溶剤にて基材に塗布
しプリプレグを得ることができる。基材としてはガラス
織布、ガラス不織布、その他有機基材などを用いること
ができる。本発明のエポキシ樹脂組成物は繊維基材に含
浸、乾燥することによりプリプレグが得られ、このプリ
プレグの１枚又は複数枚を銅箔とともに加熱成形して銅
張積層板が得られる。これらのプリプレグ及び銅張積層
板も本発明に含まれるものである。The epoxy resin composition of the present invention may optionally contain additives other than the above components as long as the properties are not impaired. The epoxy resin composition of the present invention can be applied to a substrate as a varnish using a solvent or without a solvent to obtain a prepreg. As the substrate, a glass woven fabric, a glass nonwoven fabric, or another organic substrate can be used. The epoxy resin composition of the present invention is impregnated into a fiber base material and dried to obtain a prepreg, and one or more of the prepregs is heat-formed together with a copper foil to obtain a copper-clad laminate. These prepregs and copper-clad laminates are also included in the present invention.
【００１２】[0012]
【実施例】実施例１ オルソクレゾールノボラックエポキシ樹脂（大日本イン
キ化学製エピクロンＮ−６６５）２５重量部（以下、部
と略す）、フェノールノボラック（軟化点１０５℃）
９．５部、９，１０−ジヒドロ−９−オキサ−１０−ホ
スファフェナントレン−１０−オキシド（三光化学製Ｈ
ＣＡ）５部、およびエポキシ樹脂と硬化剤量の合計１０
０部に対し２−フェニル−４−メチルイミダゾールを
０．０３部をメチルエチルケトンとメチルセロソルブの
混合溶剤に溶解した後、この溶液にエポキシシランカッ
プリング剤（日本ユニカー製Ａ−１８７）０．４部、シ
リコーンオイル型カップリング剤Ａ（日本ユニカー製Ｍ
ＡＣ２１０１）０．１部を加え撹拌し、続いて球状溶融
シリカＡ（２４μｍ以上をカットした平均粒径４μｍの
球状溶融シリカ、比表面積２ｍ2／ｇ ）６０部をいかり
型撹拌羽根で撹拌しながら少しずつ添加した。全成分を
混合したところで高速攪拌機を用いて１０分撹拌した。
作製したワニスを用いてガラスクロス（厚さ１８０μ
ｍ、日東紡績製）に含浸し、１５０℃の加熱炉で６分乾
燥してワニス固形分（プリプレグ中、ガラスクロスを除
く成分）が約５０重量％のプリプレグを得た。このプリ
プレグを所定枚数重ね、両面に厚み１２μｍの銅箔を重
ねて、圧力４０ｋｇｆ／ｃｍ2 、温度１９０℃で１２０
分加熱加圧成形を行い両面銅張積層板を得た。EXAMPLES Example 1 Orthocresol novolak epoxy resin (Epiclon N-665 manufactured by Dainippon Ink and Chemicals, Inc.) 25 parts by weight (hereinafter abbreviated as "part"), phenol novolak (softening point 105 ° C)
9.5 parts, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (H manufactured by Sanko Chemical Co., Ltd.)
CA) 5 parts, and the total amount of epoxy resin and curing agent is 10
After dissolving 0.03 part of 2-phenyl-4-methylimidazole in a mixed solvent of methyl ethyl ketone and methyl cellosolve with respect to 0 part, 0.4 part of an epoxysilane coupling agent (A-187 manufactured by Nippon Unicar) is added to this solution. , Silicone oil type coupling agent A (M made by Nippon Unicar)
0.1 parts of AC2101) and stirred, and subsequently, 60 parts of spherical fused silica A (spherical fused silica having an average particle diameter of 4 μm obtained by cutting 24 μm or more, specific surface area 2 m 2 / g) was stirred with an irrigating stirring blade. It was added in small portions. When all the components were mixed, the mixture was stirred for 10 minutes using a high-speed stirrer.
A glass cloth (thickness: 180 μ
m, manufactured by Nitto Boseki Co., Ltd.) and dried in a heating furnace at 150 ° C. for 6 minutes to obtain a prepreg having a varnish solid content (components other than glass cloth in the prepreg) of about 50% by weight. The prepregs piled predetermined number, superimposed copper foil with a thickness of 12μm on both sides, pressure 40 kgf / cm 2, at a temperature 190 ° C. 120
A two-sided copper-clad laminate was obtained by heat and pressure molding.
【００１３】得られた両面銅張積層板の評価方法を〜
に、ＢＧＡの評価方法を、に示す。 ガラス転移温度 厚さ０．６ｍｍの両面銅張積層板を全面エッチングし、
得られた積層板から１０ｍｍ×６０ｍｍのテストピース
を切り出し、動的粘弾性測定装置を用いて３℃／分で昇
温し、ｔａｎδのピーク位置をガラス転移温度とした。 線膨張係数 厚さ１．２ｍｍの両面銅張積層板を全面エッチングし、
得られた積層板から２ｍｍ×２ｍｍのテストピースを切
り出し、ＴＭＡを用いてZ方向の線膨張係数を５℃／分
で測定した。 難燃性 厚さ０．６ｍｍの両面銅張積層板を全面エッチングし、
得られた積層板からＵＬ−９４規格、垂直法により測定
した。 半田耐熱性 厚さ０．４ｍｍの両面銅張積層板を作製し、ＪＩＳＣ６
４８１に準じた方法でテストピースを４枚作製し、プレ
ッシャークッカー１２５℃４時間吸湿処理を行った後、
２６０℃の半田槽に１２０秒浸漬して外観異常が現れた
数を調べた。The evaluation method of the obtained double-sided copper-clad laminate is as follows.
The BGA evaluation method is shown in FIG. Glass transition temperature Double-sided copper-clad laminate with a thickness of 0.6 mm is entirely etched,
A test piece of 10 mm × 60 mm was cut out from the obtained laminate, and the temperature was raised at 3 ° C./min using a dynamic viscoelasticity measuring apparatus, and the peak position of tan δ was taken as the glass transition temperature. Coefficient of linear expansion The whole surface of the double-sided copper-clad laminate with a thickness of 1.2 mm is etched,
A test piece of 2 mm × 2 mm was cut out from the obtained laminate, and the linear expansion coefficient in the Z direction was measured at 5 ° C./min using TMA. Flame retardant Double-sided copper-clad laminate with a thickness of 0.6mm is etched over the entire surface,
It measured from the obtained laminated board by UL-94 standard and a vertical method. Solder heat resistance A double-sided copper-clad laminate with a thickness of 0.4 mm was manufactured and JISC6
After preparing four test pieces by a method according to 481 and performing a moisture absorption treatment at 125 ° C. for 4 hours with a pressure cooker,
It was immersed in a solder bath at 260 ° C. for 120 seconds and the number of appearance abnormalities was examined.
【００１４】パッケージ反り量 実施例で作製した厚さ０．４ｍｍの両面銅張積層板をＢ
ＧＡ用に回路加工した。この回路基板（リジッドインタ
ーポーザ）と封止材料に住友ベークライト製ＥＭＥ−７
７２０を用いて、金型温度１８０℃、注入圧力７５ｋｇ
／ｃｍ2 、硬化時間２分で２２５ｐＢＧＡ（パッケージ
サイズは２４×２４ｍｍ、厚さ１．１７ｍｍ、シリコン
チップはサイズ９×９ｍｍ、厚さ０．３５ｍｍ、チップ
と回路基板のボンディングパッドとを２５μｍ径の金線
でボンディングしている。）を成形し、１７５℃、８時
間で後硬化した。室温に冷却後、パッケージのゲート部
から対角線方向に、パッケージ上面の高さの変位を表面
粗さ計により測定し、ゲート部を基準とした最大の変位
値を反り量とした。単位はμｍ。 ＢＧＡ耐半田クラック性 と同様の方法で得たパッケージ８個を、８５℃、相対
湿度６０％の環境下で２４０時間放置した後、ＪＥＤＥ
Ｃの方法に準じてＩＲリフロー処理を行った。処理後の
内部の剥離、及びクラックの有無を超音波探傷機で観察
し、不良パッケージの個数を数えた。不良パッケージの
個数がｎ個であるとき、ｎ／８と表示する。Package warpage A double-sided copper-clad laminate having a thickness of 0.4 mm produced in the embodiment
Circuit processed for GA. This circuit board (rigid interposer) and the sealing material are EME-7 manufactured by Sumitomo Bakelite.
Using 720, mold temperature 180 ° C, injection pressure 75kg
/ Cm 2 , 225 pBGA with a curing time of 2 minutes (package size: 24 × 24 mm, thickness: 1.17 mm, silicon chip size: 9 × 9 mm, thickness: 0.35 mm, chip and bonding pad of circuit board having diameter of 25 μm) (Bonded with a gold wire.) And post-cured at 175 ° C. for 8 hours. After cooling to room temperature, the displacement of the height of the package upper surface was measured diagonally from the gate portion of the package by a surface roughness meter, and the maximum displacement value based on the gate portion was defined as the amount of warpage. The unit is μm. Eight packages obtained by the same method as in the BGA solder crack resistance were left in an environment of 85 ° C. and a relative humidity of 60% for 240 hours.
IR reflow treatment was performed according to the method of C. After the treatment, the presence of peeling and cracks in the inside was observed with an ultrasonic flaw detector, and the number of defective packages was counted. When the number of defective packages is n, it is displayed as n / 8.
【００１５】実施例２〜１４及び比較例１〜６ 表１及び表２に示す配合にて、実施例１と同様の方法で
両面銅張積層板を得た。評価方法も前述の通りである。
評価結果を表１及び表２の下欄に示す。本発明のエポキ
シ樹脂組成物を用いて得られた銅張積層板は、ハロゲン
化合物を使用していないにもかかわらず優れた難燃性を
有し、積層板単体及びＩＣパッケージでの評価において
優れた半田耐熱性を示し、加えて成形後の反りも極めて
小さい。Examples 2 to 14 and Comparative Examples 1 to 6 Double-sided copper-clad laminates were obtained in the same manner as in Example 1 with the formulations shown in Tables 1 and 2. The evaluation method is also as described above.
The evaluation results are shown in the lower columns of Tables 1 and 2. The copper-clad laminate obtained using the epoxy resin composition of the present invention has excellent flame retardancy despite not using a halogen compound, and is excellent in evaluation of a laminate alone and an IC package. In addition, it shows excellent soldering heat resistance and, in addition, the warpage after molding is extremely small.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】表の注 １）球状溶融シリカＡ：２４μｍ以上をカットした平均
粒径４μｍの球状溶融シリカ、比表面積２ｍ2／ｇ ２）球状溶融シリカＢ：２４μｍ以上をカットした平均
粒径３μｍの球状溶融シリカ、比表面積４ｍ2／ｇ ３）球状溶融シリカＣ：２４μｍ以上をカットした平均
粒径２．５μｍの球状溶融シリカ、比表面積４．５ｍ2
／ｇ ４）球状溶融シリカＤ：２４μｍ以上の粗粒がカットさ
れていない平均粒径２２μｍの球状溶融シリカ、比表面
積２．７ｍ2／ｇ ５）球状溶融シリカＥ：平均粒径０．６μｍの球状溶融
シリカ、比表面積６ｍ2／ｇ ６）破砕状溶融シリカＦ：平均粒径１８μｍの破砕状溶
融シリカ、比表面積２．２ｍ2／ｇ ７）平均粒径５μｍのタルク ８）平均粒径１２μｍの水酸化アルミニウム ９）エポキシシランカップリング剤：日本ユニカー製Ａ
１８７ １０）シリコーンオイル型カップリング剤Ａ：日本ユニ
カー製ＭＡＣ２１０１ １１）シリコーンオイル型カップリング剤Ｂ：日本ユニ
カー製ＭＡＣ２３０１ １２）オルソクレゾールノボラックエポキシ樹脂：大日
本インキ化学製エピクロＮ−６６５ １３）フェノールノボラックエポキシ樹脂：大日本イン
キ化学製エピクロンＮ−７７５ １４）テトラキスヒドロキシフェニルエタン型エポキシ
樹脂：油化シェルエポキシ製エピコートＥ１０３１Ｓ １５）トリスヒドロキシフェニルメタン型エポキシ樹
脂：油化シェルエポキシ製エピコートＥ１０３２ １６）ビスフェノールＡノボラックエポキシ樹脂：軟化
点７０℃、エポキシ当量２０１ １７）ビスフェノールＡ型エポキシ樹脂：エポキシ当量
２５０ １８）フェノールノボラック：軟化点１０５℃、水酸基
当量１０４ １９）ビスフェノールＡノボラック：軟化点１１５℃、
水酸基当量１２９ ２０）フェノールアラルキル樹脂：三井化学製ＸＬ−２
２５ ２１）９，１０−ジヒドロ−９−オキサ−１０−ホスフ
ァフェナントレン−１０−オキシド（三光化学製ＨＣ
Ａ） ２２）２−フェニル−４−メチルイミダゾール：配合量
はエポキシ樹脂と硬化剤の合計量１００部に対する量 ２３）平均粒径３μｍの破砕状溶融シリカＧ、比表面積
１５ｍ2／ｇNotes to Table 1) Spherical fused silica A: Spherical fused silica having an average particle diameter of 4 μm cut from 24 μm or more, specific surface area 2 m 2 / g 2) Spherical fused silica B: Spherical fused silica having an average particle diameter cut from 24 μm or more 3 μm Spherical fused silica, specific surface area 4 m 2 / g 3) Spherical fused silica C: spherical fused silica having an average particle size of 2.5 μm obtained by cutting 24 μm or more, specific surface area 4.5 m 2
/ G 4) Spherical fused silica D: Spherical fused silica having an average particle size of 22 μm in which coarse particles of 24 μm or more are not cut, specific surface area 2.7 m 2 / g 5) Spherical fused silica E: Average particle size of 0.6 μm Spherical fused silica, specific surface area 6 m 2 / g 6) crushed fused silica F: crushed fused silica having an average particle size of 18 μm, specific surface area 2.2 m 2 / g 7) talc having an average particle size of 5 μm 8) average particle size 12 μm 9) Epoxysilane coupling agent: A manufactured by Nippon Unicar
187 10) Silicone oil type coupling agent A: MAC2101 manufactured by Nippon Unicar 11) Silicone oil type coupling agent B: MAC2301 manufactured by Nippon Unicar 12) Orthocresol novolak Epoxy resin: Epichrom N-665 manufactured by Dainippon Ink and Chemicals 13) Phenol novolak Epoxy resin: Epicron N-775 manufactured by Dainippon Ink and Chemicals, Inc. 14) Tetrakishydroxyphenylethane type epoxy resin: Epicoat E1031S manufactured by Yuka Shell Epoxy 15) Trishydroxyphenylmethane type epoxy resin: Epicoat E1032 manufactured by Yuka Shell Epoxy 16) Bisphenol A Novolak epoxy resin: softening point 70 ° C, epoxy equivalent 201 17) bisphenol A type epoxy resin: epoxy equivalent 250 18) phenol novolak: soft Point 105 ° C., a hydroxyl equivalent of 104 19) bisphenol A novolac: softening point 115 ° C.,
Hydroxyl equivalent 129 20) Phenol aralkyl resin: XL-2 manufactured by Mitsui Chemicals
25 21) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HC manufactured by Sanko Chemical Co., Ltd.)
A) 22) 2-Phenyl-4-methylimidazole: The amount is based on 100 parts of the total amount of the epoxy resin and the curing agent. 23) Crushed fused silica G having an average particle size of 3 μm, specific surface area of 15 m 2 / g.
【００１９】[0019]
【発明の効果】本発明のエポキシ樹脂組成物は、ハロゲ
ン系難燃剤を使用せずとも優れた難燃性を有し、高耐
熱、低熱膨張の特性を有している。従って、本発明のエ
ポキシ樹脂組成物から得られた銅張積層板は半田耐熱性
に優れ、反りの小さいＩＣパッケージ用基板を提供で
き、関連産業に大きく寄与することができる。The epoxy resin composition of the present invention has excellent flame retardancy without using a halogen-based flame retardant, and has high heat resistance and low thermal expansion characteristics. Therefore, the copper-clad laminate obtained from the epoxy resin composition of the present invention has excellent solder heat resistance and can provide a substrate for an IC package with a small warpage, which can greatly contribute to related industries.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０５Ｋ 1/03 ６１０ Ｈ０５Ｋ 1/03 ６１０Ｌ ６１０Ｒ Ｆターム(参考） 4F072 AA04 AA07 AB09 AB30 AD27 AF06 AF21 AG03 AH02 AH22 AJ04 AK05 AK14 AL13 4J002 CC042 CC062 CD061 CD071 CE002 DJ017 EW136 EX068 FD017 FD136 FD142 GF00 GQ00 4J036 AC02 AC03 AF08 DA05 DC40 FA05 FA13 FB06 FB08 JA08──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) H05K 1/03 610 H05K 1/03 610L 610R F term (Reference) 4F072 AA04 AA07 AB09 AB30 AD27 AF06 AF21 AG03 AH02 AH22 AJ04 AK05 AK14 AL13 4J002 CC042 CC062 CD061 CD071 CE002 DJ017 EW136 EX068 FD017 FD136 FD142 GF00 GQ00 4J036 AC02 AC03 AF08 DA05 DC40 FA05 FA13 FB06 FB08 JA08
Claims (8)
を有するエポキシ樹脂、（Ｂ）１分子中に３個以上のフ
ェノール性水酸基を有するフェノール樹脂系硬化剤、
（Ｃ）９，１０−ジヒドロ−９−オキサ−１０−ホスフ
ァフェナントレン−１０−オキシド、及び（Ｄ）最大粒
径２４μｍ以下で、平均粒径２μｍ以上５μｍ以下、か
つ比表面積が５ｍ2／ｇ以下の球状溶融シリカを必須成
分とすることを特徴とするエポキシ樹脂組成物。(A) an epoxy resin having three or more epoxy groups in one molecule; (B) a phenolic resin-based curing agent having three or more phenolic hydroxyl groups in one molecule;
(C) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and (D) a maximum particle diameter of 24 μm or less, an average particle diameter of 2 μm or more and 5 μm or less, and a specific surface area of 5 m 2 / g. An epoxy resin composition comprising the following spherical fused silica as an essential component.
ルメタン型エポキシ樹脂、テトラキスヒドロキシフェニ
ルエタン型エポキシ樹脂及びノボラック型エポキシ樹脂
から選ばれる少なくとも１種のエポキシ樹脂である請求
項１記載のエポキシ樹脂組成物。2. The epoxy resin composition according to claim 1, wherein the component (A) is at least one epoxy resin selected from a trishydroxyphenylmethane type epoxy resin, a tetrakishydroxyphenylethane type epoxy resin and a novolak type epoxy resin. object.
脂（Ａ１）及び、トリスヒドロキシフェニルメタン型エ
ポキシ樹脂とテトラキスヒドロキシフェニルエタン型エ
ポキシ樹脂から選ばれる少なくとも１種のエポキシ樹脂
（Ａ２）である請求項１記載のエポキシ樹脂組成物。3. The component (A) is a novolak epoxy resin (A1) and at least one epoxy resin (A2) selected from a trishydroxyphenylmethane epoxy resin and a tetrakishydroxyphenylethane epoxy resin. Item 7. The epoxy resin composition according to Item 1.
る請求項１，２又は３記載のエポキシ樹脂組成物。4. The epoxy resin composition according to claim 1, wherein component (B) is phenol novolak.
を有するエポキシ樹脂、（Ｂ）１分子中に３個以上のフ
ェノール性水酸基を有するフェノール樹脂系硬化剤、
（Ｃ）９，１０−ジヒドロ−９−オキサ−１０−ホスフ
ァフェナントレン−１０−オキシド、（Ｄ）最大粒径２
４μｍ以下で、平均粒径２μｍ以上５μｍ以下、かつ比
表面積が５ｍ2／ｇ以下の球状溶融シリカ、及び（Ｅ）
カップリング剤を必須成分とすることを特徴とするエポ
キシ樹脂組成物。(A) an epoxy resin having three or more epoxy groups in one molecule, (B) a phenolic resin-based curing agent having three or more phenolic hydroxyl groups in one molecule,
(C) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (D) maximum particle size 2
(E) spherical fused silica having a particle size of 4 μm or less, an average particle size of 2 μm or more and 5 μm or less, and a specific surface area of 5 m 2 / g or less;
An epoxy resin composition comprising a coupling agent as an essential component.
し単位を２個以上有し、かつアルコキシ基を有するシリ
コーンオイル型カップリング剤である請求項５記載のエ
ポキシ樹脂組成物。6. The epoxy resin composition according to claim 5, wherein the component (E) is a silicone oil type coupling agent having at least two siloxane bond repeating units and having an alkoxy group.
キシ樹脂組成物を繊維基材に含浸、乾燥してなることを
特徴とするプリプレグ。7. A prepreg obtained by impregnating a fiber base material with the epoxy resin composition according to claim 1 and drying it.
てなることを特徴とする銅張積層板。8. A copper-clad laminate obtained by heating and molding the prepreg according to claim 7.
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|---|---|---|---|
| JP2000235301A JP4714970B2 (en) | 2000-08-03 | 2000-08-03 | Epoxy resin composition, prepreg, and copper-clad laminate using the same |
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|---|---|
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ID=18727535
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053645A (en) * | 2000-08-04 | 2002-02-19 | Sumitomo Bakelite Co Ltd | Epoxy resin composition, prepreg and copper clad laminated board produced by using the same |
| JP2002060468A (en) * | 2000-08-16 | 2002-02-26 | Sumitomo Bakelite Co Ltd | Epoxy resin composition, prepreg, and copper-clad laminate using the prepreg |
| JP2002088141A (en) * | 2000-09-13 | 2002-03-27 | Sumitomo Bakelite Co Ltd | Epoxy resin composition, prepreg and copper-clad laminate using the same |
| JP2006222409A (en) * | 2005-01-17 | 2006-08-24 | Hitachi Chem Co Ltd | Printed wiring board resin composition, prepreg, metal-clad laminated board, and printed wiring board |
| JP2007231246A (en) * | 2006-01-31 | 2007-09-13 | Hitachi Chem Co Ltd | Resin composition, prepreg, and metal-clad laminate board |
| US20200172724A1 (en) * | 2017-06-09 | 2020-06-04 | Nagase Chemtex Corporation | Epoxy resin composition, electronic component mounting structure, and method for producing the same |
| CN113637289A (en) * | 2021-06-17 | 2021-11-12 | 上海道宜半导体材料有限公司 | Epoxy resin composition and preparation method and application thereof |
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| JP2002038022A (en) * | 2000-07-21 | 2002-02-06 | Toppan Printing Co Ltd | Insulating resin composition for multilayer printed wiring board, multilayer printed wiring board using the same, and production method using the same |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053645A (en) * | 2000-08-04 | 2002-02-19 | Sumitomo Bakelite Co Ltd | Epoxy resin composition, prepreg and copper clad laminated board produced by using the same |
| JP4639439B2 (en) * | 2000-08-04 | 2011-02-23 | 住友ベークライト株式会社 | Epoxy resin composition, prepreg, and copper-clad laminate using the same |
| JP2002060468A (en) * | 2000-08-16 | 2002-02-26 | Sumitomo Bakelite Co Ltd | Epoxy resin composition, prepreg, and copper-clad laminate using the prepreg |
| JP2002088141A (en) * | 2000-09-13 | 2002-03-27 | Sumitomo Bakelite Co Ltd | Epoxy resin composition, prepreg and copper-clad laminate using the same |
| JP4729778B2 (en) * | 2000-09-13 | 2011-07-20 | 住友ベークライト株式会社 | Epoxy resin composition, prepreg, and copper-clad laminate using the same |
| JP2006222409A (en) * | 2005-01-17 | 2006-08-24 | Hitachi Chem Co Ltd | Printed wiring board resin composition, prepreg, metal-clad laminated board, and printed wiring board |
| JP2007231246A (en) * | 2006-01-31 | 2007-09-13 | Hitachi Chem Co Ltd | Resin composition, prepreg, and metal-clad laminate board |
| US20200172724A1 (en) * | 2017-06-09 | 2020-06-04 | Nagase Chemtex Corporation | Epoxy resin composition, electronic component mounting structure, and method for producing the same |
| US11608435B2 (en) * | 2017-06-09 | 2023-03-21 | Nagase Chemtex Corporation | Epoxy resin composition, electronic component mounting structure, and method for producing the same |
| CN113637289A (en) * | 2021-06-17 | 2021-11-12 | 上海道宜半导体材料有限公司 | Epoxy resin composition and preparation method and application thereof |
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