JP2002264158A - Method for producing laminated plate - Google Patents
Method for producing laminated plateInfo
- Publication number
- JP2002264158A JP2002264158A JP2001071980A JP2001071980A JP2002264158A JP 2002264158 A JP2002264158 A JP 2002264158A JP 2001071980 A JP2001071980 A JP 2001071980A JP 2001071980 A JP2001071980 A JP 2001071980A JP 2002264158 A JP2002264158 A JP 2002264158A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin
- weight
- glass
- parts
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐トラッキング性
に優れたコンポジット積層板の製造方法に関するもので
あり、更にはガラス織布とガラス不織布との複合プリプ
レグを連続的に製造することができ、従って製造工程を
短縮することができ、効率のよいコンポジット積層板の
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite laminate having excellent tracking resistance, and more particularly, to a method for continuously producing a composite prepreg of a glass woven fabric and a glass nonwoven fabric, Therefore, the present invention relates to a method for efficiently producing a composite laminate in which the production steps can be shortened.
【０００２】[0002]
【従来の技術】印刷回路基板として、ガラス不織布を中
間層基材としガラス織布を表面層基材とし、エポキシ樹
脂を含浸させ加熱加圧成形したコンポジット積層板は、
従来、ガラス不織布に中間層樹脂を含浸させ乾燥したプ
リプレグとガラス織布に脂環式エポキシ樹脂や、不飽和
ポリエステル樹脂系等の芳香族環の少ないタイプのエポ
キシ樹脂を含浸させ乾燥したプリプレグをそれぞれ別個
に製造し、加熱加圧成形時に重ね合わせて製造されてい
る。耐トラッキング性向上のため表面層に脂環式エポキ
シ樹脂や、不飽和ポリエステル樹脂系等の芳香族環の少
ないタイプの樹脂が用いられるが、耐熱性不足、金属箔
との引き剥がし強さが弱い等の問題があった。また、コ
ンポジット積層板の製造において、環境への負荷を小さ
くする目的から、溶剤使用量の削減、熱エネルギーの低
減のために、ガラス織布に溶剤量の少ない樹脂ワニスを
塗布し、次いで、溶剤量の少ないペースト状の中間層樹
脂を塗布し、ガラス不織布を重ね合わせ、加熱乾燥して
プリプレグを作製し、このプリプレグ２枚をガラス不織
布を内側にして重ね合わせ加熱加圧成形してコンポジッ
ト積層板を製造することが検討されている。しかし、こ
のような製造方法においては、プリプレグ作製時、加熱
乾燥後に中間層樹脂の気泡が残る傾向にあり、この気泡
の除去が困難であるという問題があった。プリプレグ中
に気泡が残存すると、積層板は耐熱性が低下することと
なる。2. Description of the Related Art As a printed circuit board, a composite laminate made of glass non-woven fabric as an intermediate layer base material, glass woven fabric as a surface layer base material, impregnated with epoxy resin, and heated and pressed,
Conventionally, a prepreg dried by impregnating an interlayer resin into a glass non-woven fabric and a prepreg dried by impregnating an alicyclic epoxy resin or an epoxy resin with a small number of aromatic rings such as an unsaturated polyester resin into a glass woven fabric, respectively. It is manufactured separately and is superimposed upon heating and press forming. Alicyclic epoxy resin or resin with less aromatic ring such as unsaturated polyester resin is used for the surface layer to improve tracking resistance, but insufficient heat resistance, weak peeling strength with metal foil And so on. Also, in the production of composite laminates, in order to reduce the load on the environment, to reduce the amount of solvent used, to reduce thermal energy, apply a resin varnish with a small amount of solvent to the glass woven fabric, A small amount of paste-like intermediate layer resin is applied, a glass nonwoven fabric is laminated, and dried by heating to prepare a prepreg. Two prepregs are laminated with the glass nonwoven fabric inside, and heated and pressed to form a composite laminate. The manufacture of However, such a production method has a problem in that bubbles of the intermediate layer resin tend to remain after heating and drying during prepreg production, and it is difficult to remove these bubbles. If air bubbles remain in the prepreg, the laminate will have reduced heat resistance.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記従来技
術の問題点に鑑み、耐熱性、耐トラッキング特性及び銅
箔とプリプレグの密着性をより向上させたコンポジット
積層板を得ることを課題とする。SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a composite laminate having improved heat resistance, tracking resistance and adhesion between a copper foil and a prepreg. I do.
【０００４】[0004]
【課題を解決するための手段】本発明は、（１）（ａ）
ガラス織布の上に非臭素化エポキシ樹脂及び前記樹脂１
００重量部に対し無機充填剤１０〜２００重量部を含む
エポキシ樹脂ワニス（Ａ）を塗布し、（ｂ）その上から
ガラス不織布を重ね合わせ乾燥した後、（ｃ）ノボラッ
ク型エポキシ樹脂、ビスフェノ−ルＡ型エポキシ樹脂及
びノボラック樹脂硬化剤を含む中間層エポキシ樹脂組成
物に無機充填材を前記樹脂組成物に対し８０〜１５０％
添加した中間層樹脂ワニス（Ｂ）を塗布し、乾燥してプ
リプレグとし、（ｄ）このプリプレグ２枚をガラス不織
布を内側にして重ね合わせ加熱加圧することを特徴とす
るコンポジット積層板の製造方法、（２）中間層樹脂ワ
ニス（Ｂ）の固形分が重量比でガラス不織布の５〜１５
倍である第（１）項記載のコンポジット積層板の製造方
法、（３）中間層樹脂ワニス（Ｂ）を塗布し乾燥後に、
ガラス織布側に非臭素化エポキシ樹脂及び前記樹脂１０
０重量部に対し無機充填剤１０〜２００重量部を含むエ
ポキシ樹脂ワニス（Ｃ）を塗布する第（１）項記載のコ
ンポジット積層板の製造方法、である。The present invention provides (1) (a)
Non-brominated epoxy resin and said resin 1 on woven glass cloth
An epoxy resin varnish (A) containing 10 to 200 parts by weight of an inorganic filler with respect to 00 parts by weight is applied, (b) a glass nonwoven fabric is overlaid and dried thereon, and then (c) a novolak-type epoxy resin, An inorganic filler is added to the intermediate layer epoxy resin composition containing the A-type epoxy resin and the novolak resin curing agent in an amount of 80 to 150% based on the resin composition.
A method for producing a composite laminate, comprising applying the added interlayer resin varnish (B), drying to form a prepreg, and (d) laminating and heating and pressing the two prepregs with the glass nonwoven fabric inside. (2) The solid content of the intermediate layer resin varnish (B) is 5 to 15% by weight of the glass nonwoven fabric.
(1) The method for producing a composite laminate according to item (1), (3) applying an intermediate layer resin varnish (B) and drying the same,
Non-brominated epoxy resin and said resin 10 on the glass woven fabric side
The method for producing a composite laminate according to (1), wherein an epoxy resin varnish (C) containing 10 to 200 parts by weight of an inorganic filler is applied to 0 parts by weight.
【０００５】[0005]
【発明の実施の形態】本発明で用いるガラス織布は、と
くに限定されるものではなく、通常のエポキシ樹脂ガラ
ス積層板用のものが使用される。例えば、７６２８スタ
イルが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The glass woven fabric used in the present invention is not particularly limited, and an ordinary epoxy resin glass laminate is used. For example, 7628 style is given.
【０００６】本発明でエポキシ樹脂ワニス（Ａ）に用い
る非臭素化エポキシ樹脂には、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、ノボラッ
ク型エポキシ樹脂等が挙げられる。これらの中でもビス
フェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹
脂が低コストの点で好ましく用いられる。また、本発明
でエポキシ樹脂ワニス（Ａ）に用いる無機充填材は、水
酸化アルミニウム、炭酸カルシウム、クレー、タルク、
シリカ等であり、特に限定されないが、水酸化アルミニ
ウムを主成分とするものが、耐トラッキング特性のため
に好ましい。本発明のエポキシ樹脂ワニスでは非臭素化
エポキシ樹脂１００重量部に対して無機充填材１０〜２
００重量部、好ましくは４０〜１００重量部配合する。
かかる組成で、耐トラッキング性、耐熱性が良好であ
り、銅箔や中間層の樹脂との密着性も優れているからで
ある。１０重量部未満では耐トラッキング特性が低下
し、２００重量部を超えると耐熱性が低下する。ここで
塗布するエポキシ樹脂ワニスは、溶媒に硬化剤を溶解し
非臭素化エポキシ樹脂を混合したもので、溶媒、硬化剤
は、特に限定されるものではない。エポキシ樹脂ワニス
の量は、固形分でガラス織布１００重量部に対して５０
〜１５０重量部が好ましい。５０重量部より少ないと中
間層樹脂あるいはガラス不織布との密着性が低下し、種
々の特性が低下する。１５０重量部より多いと樹脂分が
過剰となり、積層板の熱時特性が低下するようになる。The non-brominated epoxy resin used for the epoxy resin varnish (A) in the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin and the like. Among these, bisphenol A type epoxy resin and novolak type epoxy resin are preferably used in terms of low cost. The inorganic filler used for the epoxy resin varnish (A) in the present invention includes aluminum hydroxide, calcium carbonate, clay, talc,
Silica and the like are not particularly limited, but those containing aluminum hydroxide as a main component are preferable for their tracking resistance. In the epoxy resin varnish of the present invention, the inorganic filler 10 to 2 is used with respect to 100 parts by weight of the non-brominated epoxy resin.
00 parts by weight, preferably 40 to 100 parts by weight.
This is because such a composition has good tracking resistance and heat resistance, and also has excellent adhesion to the copper foil and the resin of the intermediate layer. If the amount is less than 10 parts by weight, the tracking resistance decreases, and if it exceeds 200 parts by weight, the heat resistance decreases. The epoxy resin varnish applied here is obtained by dissolving a curing agent in a solvent and mixing a non-brominated epoxy resin, and the solvent and the curing agent are not particularly limited. The amount of the epoxy resin varnish was 50 parts by weight based on 100 parts by weight of
~ 150 parts by weight are preferred. If the amount is less than 50 parts by weight, the adhesion to the interlayer resin or the glass non-woven fabric is reduced, and various characteristics are reduced. If the amount is more than 150 parts by weight, the resin content will be excessive, and the thermal properties of the laminate will deteriorate.
【０００７】ガラス不織布は、通常単位面積当たりの重
量２５〜１５０ｇ／ｍ2 のものが使用される。加熱乾燥
条件は、１２０〜１８０℃、１〜５分間程度が好まし
い。As the glass nonwoven fabric, one having a weight per unit area of 25 to 150 g / m 2 is usually used. The heating and drying conditions are preferably from 120 to 180 ° C. for about 1 to 5 minutes.
【０００８】本発明の中間層樹脂ワニス（Ｂ）に用いる
ノボラック型エポキシ樹脂、ビスフェノールＡ型エポキ
シ樹脂及びノボラック樹脂硬化剤は特に限定されない。
難燃化のために、エポキシ樹脂はその一部または全部に
ハロゲン化したものを使用することができる。ここで、
ノボラック型エポキシ樹脂は硬化後の樹脂の架橋密度を
大きくし、積層板の耐熱性や機械的強度を高くするため
に配合されるものであり、エポキシ樹脂中４０〜８０重
量％が好ましい。４０重量％より少ないと前記効果が十
分でなく、８０重量％より多いと加工特性の低下とな
る。The novolak type epoxy resin, bisphenol A type epoxy resin and novolak resin curing agent used in the intermediate resin varnish (B) of the present invention are not particularly limited.
Epoxy resins partially or wholly halogenated for flame retardancy can be used. here,
The novolak type epoxy resin is compounded to increase the crosslink density of the cured resin and to increase the heat resistance and mechanical strength of the laminated board, and preferably accounts for 40 to 80% by weight of the epoxy resin. If the amount is less than 40% by weight, the above effect is not sufficient, and if it is more than 80% by weight, the processing characteristics are deteriorated.
【０００９】本発明の中間層樹脂ワニス（Ｂ）に用いる
無機充填材は、熱膨張率の低減、寸法安定性の向上等の
ために配合される。無機充填材は、水酸化アルミニウ
ム、炭酸カルシウム、クレー、タルク、シリカ等であ
り、特に限定されないが、水酸化アルミニウムを主成分
とするものが、難燃性、ドリル加工性のために好まし
い。無機充填材の配合量は、中間層に用いる樹脂組成物
を基準として８０〜１５０重量部である。この配合量が
８０重量部未満では前記特性の改善が不十分であり、１
５０重量部を超えると成形性が低下し、熱時特性も低下
するようになる。無機充填材としは、中間層樹脂ワニス
の固形分は、通常、通常、６５〜９５重量％（無機充填
材も固形分として計算）で使用可能であり、好ましくは
８０〜９５重量％であり、ペースト状である。充填材含
有中間層樹脂の塗布量はガラス不織布１００重量部に対
して５００〜１５００重量部が好ましい。５００重量部
より少ないと熱時特性の低下、プリプレグ間の密着性の
低下が生じるようになり、１５００重量部より多いと成
形性が低下し、熱時特性も低下するようになる。なお、
中間層樹脂ワニス塗布後の加熱乾燥条件は、１２０〜１
８０℃、１〜５分間程度が好ましい。The inorganic filler used in the resin varnish (B) for the intermediate layer of the present invention is blended for the purpose of reducing the coefficient of thermal expansion and improving the dimensional stability. The inorganic filler is aluminum hydroxide, calcium carbonate, clay, talc, silica or the like, and is not particularly limited, but those containing aluminum hydroxide as a main component are preferable for flame retardancy and drill workability. The compounding amount of the inorganic filler is 80 to 150 parts by weight based on the resin composition used for the intermediate layer. If the amount is less than 80 parts by weight, the above-mentioned properties are not sufficiently improved.
If the amount exceeds 50 parts by weight, the moldability decreases, and the properties when heated also deteriorate. As the inorganic filler, the solid content of the interlayer resin varnish can be generally used at 65 to 95% by weight (the inorganic filler is also calculated as a solid content), preferably 80 to 95% by weight, It is a paste. The coating amount of the filler-containing intermediate layer resin is preferably from 500 to 1500 parts by weight based on 100 parts by weight of the glass nonwoven fabric. If the amount is less than 500 parts by weight, the properties at the time of heating and the adhesiveness between the prepregs will decrease. In addition,
The heating and drying conditions after application of the intermediate layer resin varnish are 120 to 1
80 ° C. and about 1 to 5 minutes are preferable.
【００１０】なお、本発明において、中間層樹脂ワニス
を塗布した後加熱乾燥する前に、ガラス織布の側から初
めに塗布するエポキシ樹脂ワニスと同様の組成を有する
エポキシ樹脂ワニス（Ｃ）を塗布するにより、コンポジ
ット積層板の表面層に樹脂を十分に存在させ、銅箔との
密着性や耐熱性を向上させることができる。このエポキ
シ樹脂ワニスの量はガラス織布１００重量部に対して２
０〜１００重量部が好ましい。２０重量部より少ないと
上記効果が小さく、１００重量部より多いと樹脂量が多
すぎて成形性の低下や寸法安定性の低下等を生じるよう
になる。In the present invention, the epoxy resin varnish (C) having the same composition as the epoxy resin varnish applied first from the side of the glass woven fabric is applied before heating and drying after applying the intermediate layer resin varnish. By doing so, the resin can be sufficiently present in the surface layer of the composite laminate, and the adhesion to the copper foil and the heat resistance can be improved. The amount of the epoxy resin varnish was 2 parts per 100 parts by weight of the glass woven fabric.
0-100 parts by weight are preferred. When the amount is less than 20 parts by weight, the above effect is small, and when the amount is more than 100 parts by weight, the amount of the resin is too large, so that the moldability and the dimensional stability are reduced.
【００１１】尚、本発明では得られたプリプレグをガラ
ス不織布側を内側にして２枚重ね合わせ加熱加圧成形す
ることによりコンポジット積層板が得られる。成形条件
は、積層板の厚さにもよるが、通常、温度１５０〜１８
０℃、圧力２０〜５０ｋｇ／ｃｍ2 で、３０〜９０分で
ある。このようにして得られたコンポジット積層板は、
気泡がなく、銅箔とプリプレグ及び表面層と中間層の密
着性が良好であり、耐熱性が優れている。In the present invention, a composite laminate is obtained by laminating two prepregs with the glass non-woven fabric side facing inward and heating and pressing them. The molding conditions depend on the thickness of the laminate, but are usually at a temperature of 150-18.
0 ° C., pressure 20-50 kg / cm 2 , 30-90 minutes. The composite laminate thus obtained is
There are no bubbles, the adhesion between the copper foil and the prepreg and between the surface layer and the intermediate layer is good, and the heat resistance is excellent.
【００１２】次に、本発明において、プリプレグを製造
するまでの工程の一例（概略）を図１に示す。巻き出し
装置から巻き出されたガラス織布１の上面に非臭素化エ
ポキシ樹脂ワニス（Ａ）２をコーター３により所定量塗
布し、その上面よりガラス不織布４を重ね合わせた後、
乾燥装置５を通し溶剤を加熱蒸発させる。その後、中間
層樹脂ワニス（Ｂ）６をコーター７により所定厚み塗布
する。コーター７としては、コンマロールコーター、ナ
イフコーター、ダイスコーター、リバースコーター等が
ある。中間層樹脂（ｂ）は多量の無機充填材を含有して
いる。充填材の分離を防止し、塗布後に樹脂組成物がガ
ラス不織布中に良好に保持されるために、ワニス粘度を
高粘度のペースト状にすることが好ましい。このときの
使用される塗布方式は、高粘度材料を塗布できる方式、
例えばコンマロールコーター、ナイフコーターが好まし
い。従って、中間層樹脂（ｂ）を高粘度のペースト状に
することにより、溶剤使用量は削減され、その後の加熱
乾燥に要するエネルギーも少なくなる。Next, in the present invention, an example (schematic) of a process up to the production of a prepreg is shown in FIG. A non-brominated epoxy resin varnish (A) 2 is applied to the upper surface of the glass woven fabric 1 unwound from the unwinding device by a coater 3 in a predetermined amount, and a glass nonwoven fabric 4 is overlaid from the upper surface thereof.
The solvent is heated and evaporated through the drying device 5. After that, an intermediate layer resin varnish (B) 6 is applied by a coater 7 to a predetermined thickness. Examples of the coater 7 include a comma roll coater, a knife coater, a die coater, and a reverse coater. The intermediate layer resin (b) contains a large amount of an inorganic filler. In order to prevent separation of the filler and to keep the resin composition in the glass nonwoven fabric well after application, it is preferable that the varnish has a high-viscosity paste. The coating method used at this time is a method that can apply a high viscosity material,
For example, a comma roll coater and a knife coater are preferable. Accordingly, by forming the intermediate layer resin (b) into a paste having a high viscosity, the amount of solvent used is reduced, and the energy required for subsequent heating and drying is also reduced.
【００１３】好ましくは、次いで、ガラス織布側に非臭
素化エポキシ樹脂ワニス（Ａ）と同様な組成の非臭素化
エポキシ樹脂ワニス（Ｃ）８を塗布する。この塗布は通
常ロールコーター９により行われるが、これに限定され
るものではない。その後、乾燥装置１０を通して加熱乾
燥することにより、ガラス織布上にガラス不織布が重ね
合わされたエポキシ樹脂含浸複合プリプレグ１２を得
る。加熱乾燥条件は、１２０〜１８０℃、１〜５分間程
度である。その後、このプリプレグをカッター１１によ
り所定長さに切断する。あるいは、切断しないで連続成
形に供することも可能である。Preferably, a non-brominated epoxy resin varnish (C) 8 having the same composition as the non-brominated epoxy resin varnish (A) is applied to the glass woven fabric side. This coating is usually performed by a roll coater 9, but is not limited thereto. Thereafter, by heating and drying through a drying device 10, an epoxy resin impregnated composite prepreg 12 in which a glass nonwoven fabric is superimposed on a glass woven fabric is obtained. The heating and drying conditions are 120 to 180 ° C. for about 1 to 5 minutes. Thereafter, the prepreg is cut into a predetermined length by the cutter 11. Alternatively, it is also possible to perform continuous molding without cutting.
【００１４】続いて、その上からガラス不織布を重ね合
わせ加熱乾燥する。加熱乾燥条件は、通常１２０〜１８
０℃、１〜５分間程度である。さらに、その上から、ノ
ボラック型エポキシ樹脂、ビスフェノ−ルＡ型エポキシ
樹脂及びノボラック樹脂硬化剤を主成分とするエポキシ
樹脂組成物に無機充填材を前記樹脂組成物１００重量部
に対し８０〜１５０重量部添加した中間層樹脂ワニス
（Ｂ）を塗布する。Subsequently, a glass non-woven fabric is overlaid on top of it and heated and dried. The heating and drying conditions are usually 120 to 18
0 ° C., about 1 to 5 minutes. Further, an inorganic filler is added to the epoxy resin composition containing a novolak type epoxy resin, a bisphenol A type epoxy resin and a novolak resin curing agent as a main component at 80 to 150 parts by weight based on 100 parts by weight of the resin composition. The intermediate layer resin varnish (B) added in part is applied.
【００１５】[0015]
【実施例】以下、本発明について、実施例及び比較例に
より、具体的に説明する。始めと終わりにガラス織布
（１８０ｇ／ｍ2 ）に塗布する非臭素化エポキシ樹脂ワ
ニス（Ａ）及び（Ｃ）として、非臭素化ビスフェノ−ル
Ａ型エポキシ樹脂としてエピコート８５０（エポキシ当
量３９０、油化シェル（株）製）、非臭素化ノボラック
樹脂としてエピコート１８０Ｓ（エポキシ当量２１０、
油化シェル（株）製）、硬化促進剤として２−エチル−
４−メチルイミダゾ−ルを使用し、無機フィラーとして
水酸化アルミニウム（住友化学（株）製、ＣＬ−３１
０）を用い、表１に示した割合にて配合した。溶剤とし
てアセトンを使用し、固形分７０重量％とした。また、
ガラス不織布（１００ｇ／ｍ2 ）に含浸する中間層樹脂
ワニス（Ｂ）として、ビスフェノ−ルＡ型エポキシ樹脂
としてエピクロン８５０（エポキシ当量１９０、大日本
インキ（株）製）、臭素化ビスフェノ−ルＡ型エポキシ
樹脂としてＧＸ１５３（エポキシ当量４００、大日本イ
ンキ化学（株）製）、クレゾ−ルノボラック型エポキシ
樹脂として、エピコ−ト１８０Ｓ７５（エポキシ当量２
１０、油化シェルエポキシ（株）製）、ノボラック樹脂
としてＰＲ−５１４７０（住友デュレズ（株）製）、硬
化促進剤として２−エチル−４−メチルイミダゾ−ルを
使用し、無機フィラーとして水酸化アルミニウム（住友
化学（株）製、ＣＬ−３１０）を用い、表１に示した割
合にて配合した。溶剤としてアセトンを使用し、固形分
８０重量％とした。The present invention will be specifically described below with reference to examples and comparative examples. Epicoat 850 (epoxy equivalent 390, oil equivalent) as non-brominated bisphenol A type epoxy resin as non-brominated epoxy resin varnishes (A) and (C) applied to glass woven fabric (180 g / m 2 ) at the beginning and end Shell Co., Ltd.), Epicoat 180S (epoxy equivalent 210, non-brominated novolak resin)
Yuka Shell Co., Ltd.), 2-ethyl- as a curing accelerator
Using 4-methylimidazole, aluminum hydroxide (CL-31 manufactured by Sumitomo Chemical Co., Ltd.) as an inorganic filler
0) and blended at the ratios shown in Table 1. Acetone was used as a solvent to obtain a solid content of 70% by weight. Also,
As an intermediate resin varnish (B) impregnated in a glass nonwoven fabric (100 g / m 2 ), as a bisphenol A type epoxy resin, Epicron 850 (epoxy equivalent 190, manufactured by Dainippon Ink Co., Ltd.), brominated bisphenol A GX153 (epoxy equivalent: 400, manufactured by Dainippon Ink and Chemicals, Inc.) as a type epoxy resin, and Epicoat 180S75 (epoxy equivalent: 2) as a cresol novolac type epoxy resin.
10, Yuka Shell Epoxy Co., Ltd.), PR-51470 (Sumitomo Durez Co., Ltd.) as a novolak resin, 2-ethyl-4-methylimidazole as a curing accelerator, and hydroxylation as an inorganic filler. Aluminum (manufactured by Sumitomo Chemical Co., Ltd., CL-310) was used in the proportions shown in Table 1. Acetone was used as a solvent to obtain a solid content of 80% by weight.
【００１６】実施例では、前記非臭素化エポキシ樹脂ワ
ニス（Ａ）をガラス織布に、ガラス織布１００重量部に
対して１００重量部塗布し、その上からガラス不織布を
重ね合わせ乾燥した。さらに、その上から中間層樹脂ワ
ニス（Ｂ）をガラス不織布１００重量部に対して１００
０重量部塗布した。次いでガラス織布の側から非臭素化
エポキシ樹脂ワニス（Ｃ）をガラス織布１００重量部に
対して５０重量部塗布し、加熱乾燥してプリプレグと得
た。このプリプレグ２枚をガラス不織布側を内側にして
重ね合わせ、さらに、両表面に銅箔を重ね、加熱加圧成
形してコンポジット積層板を得た。In the examples, 100 parts by weight of the non-brominated epoxy resin varnish (A) was applied to 100 parts by weight of the glass woven fabric on a glass woven fabric. Further, the intermediate layer resin varnish (B) was applied from above to 100 parts by weight of the glass nonwoven fabric.
0 parts by weight was applied. Next, 50 parts by weight of a non-brominated epoxy resin varnish (C) was applied to 100 parts by weight of the glass woven fabric from the side of the glass woven fabric, and dried by heating to obtain a prepreg. The two prepregs were laminated with the glass nonwoven fabric side inside, and copper foil was further laminated on both surfaces, and heated and pressed to obtain a composite laminate.
【００１７】比較例では、前記非臭素化エポキシ樹脂ワ
ニス（Ａ）をガラス織布に塗布し、その上から中間層樹
脂ワニス（Ｂ）を塗布し、さらに、その上からガラス不
織布を重ね合わせた。次いでガラス織布の側から非臭素
化エポキシ樹脂ワニス（Ｃ）を塗布し、加熱乾燥してプ
リプレグと得た。このプリプレグ２枚をガラス不織布側
を内側にして重ね合わせ、さらに、両表面に銅箔を重
ね、加熱加圧成形してコンポジット積層板を得た。な
お、樹脂ワニスの塗布量はすべて無機フィラーを含む固
形分換算であり、実施例と比較例とは同じ量である。In the comparative example, the non-brominated epoxy resin varnish (A) was applied to a glass woven fabric, an intermediate resin varnish (B) was applied thereon, and a glass nonwoven fabric was further laminated thereon. . Next, a non-brominated epoxy resin varnish (C) was applied from the glass woven fabric side, and dried by heating to obtain a prepreg. The two prepregs were laminated with the glass nonwoven fabric side inside, and copper foil was further laminated on both surfaces, and heated and pressed to obtain a composite laminate. The application amount of the resin varnish is all in terms of solid content including an inorganic filler, and is the same as that of the examples and the comparative examples.
【００１８】[0018]
【表１】 [Table 1]
【００１９】プリプレグ及び成形されたコンポジット積
層板について、特性を評価し、表２に示す特性を得た。
実施例で得られたコンポジット積層板は、耐トラッキン
グ性が優れているとともに、プリプレグでの気泡が少な
く、従って半田耐熱性に優れている。The properties of the prepreg and the formed composite laminate were evaluated, and the properties shown in Table 2 were obtained.
The composite laminate obtained in the examples has excellent tracking resistance, has few bubbles in the prepreg, and therefore has excellent solder heat resistance.
【００２０】[0020]
【表２】 [Table 2]
【００２１】（評価方法） １．プリプレグの含有気泡量：プリプレグを切断し研磨
した断面２×２ｍｍを電子顕微鏡（ＳＥＭ）写真を撮
る。その断面写真について０．２ｍｍ格子板を用い、気
泡を有する部分の格子面積を測定する。断面における気
泡含有部分の格子面積の占める割合を計算し、プリプレ
グの含有気泡量とする。 ○：プリプレグの含有気泡量が３０％未満(a)、又は５
０％未満(b)である。 ×：プリプレグの含有気泡量が３０％以上(a)、又は５
０％以上(b)である。 ２．ガラス転移温度（ＤＭＡ法）：周波数６０Ｈｚでの
回転振動による粘弾性データを用い測定した。測定は３
℃昇温で行った。 ３．耐トラッキング特性：ＩＥＣ法により測定した。 ４．半田耐熱性：ＪＩＳ Ｃ ６４８１に準じて測定し
た。試験片は、煮沸２時間の吸湿処理を行った後、２６
０℃の半田槽に１２０秒浸漬した後の外観の異常の有無
を観察した。(Evaluation method) Bubble content of prepreg: An electron microscope (SEM) photograph is taken of a 2 × 2 mm section of the prepreg cut and polished. Using a 0.2 mm grid plate for the cross-sectional photograph, the grid area of the portion having bubbles is measured. The percentage of the lattice area of the bubble-containing portion in the cross section is calculated, and is defined as the amount of bubbles contained in the prepreg. ：: the content of air bubbles in the prepreg is less than 30% (a) or 5
It is less than 0% (b). ×: The content of bubbles in the prepreg is 30% or more (a) or 5
0% or more (b). 2. Glass transition temperature (DMA method): Measured using viscoelastic data obtained by rotational vibration at a frequency of 60 Hz. Measurement is 3
This was carried out at an elevated temperature of ° C. 3. Tracking resistance: Measured by the IEC method. 4. Solder heat resistance: Measured according to JIS C6481. The test piece was subjected to a moisture absorption treatment for 2 hours after boiling, and then 26
After immersion in a solder bath at 0 ° C. for 120 seconds, the presence or absence of abnormality in the appearance was observed.
【００２２】[0022]
【発明の効果】本発明の製造方法は、過剰な乾燥を行う
ことなく、プリプレグの中間層樹脂に含まれる気泡を低
減することができるので、銅箔とプリプレグの密着性が
低下することなく、耐熱性を良好に維持しつつコンポジ
ット積層板を効率良く製造することができ、さらに、表
面層樹脂として非臭素化エポキシ樹脂及び無機充填材を
使用しているので、耐トラッキング特性の優れたコンポ
ジット積層板が得られ、その工業的価値は極めて大なる
ものである。The production method of the present invention can reduce bubbles contained in the intermediate layer resin of the prepreg without excessive drying, so that the adhesion between the copper foil and the prepreg does not decrease. Composite laminates can be manufactured efficiently while maintaining good heat resistance. Furthermore, since non-brominated epoxy resin and inorganic filler are used as the surface layer resin, the composite laminate has excellent tracking resistance. A board is obtained, whose industrial value is of great value.
【図１】 本発明において、プリプレグを製造するまで
の工程（一例）の概略図である。FIG. 1 is a schematic view of a process (an example) up to manufacturing a prepreg in the present invention.
１ ガラス織布 ２ エポキシ樹脂 ３ コーター ４ ガラス不織布 ５ 乾燥装置 ６ 中間層エポキシ樹脂 ７ コーター ８ エポキシ樹脂 ９ ロールコーター １０ 乾燥装置 １１ カッター １２ エポキシ樹脂含浸プリプレグ DESCRIPTION OF SYMBOLS 1 Glass woven fabric 2 Epoxy resin 3 Coater 4 Glass nonwoven fabric 5 Drying device 6 Intermediate layer epoxy resin 7 Coater 8 Epoxy resin 9 Roll coater 10 Drying device 11 Cutter 12 Epoxy resin impregnated prepreg
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） Ｃ０８Ｊ 5/24 ＣＦＣ Ｃ０８Ｊ 5/24 ＣＦＣ ４Ｊ０３６ Ｃ０８Ｋ 3/00 Ｃ０８Ｋ 3/00 Ｃ０８Ｌ 63/00 Ｃ０８Ｌ 63/00 Ｃ // Ｂ２９Ｋ 63:00 Ｂ２９Ｋ 63:00 105:08 105:08 Ｂ２９Ｌ 31:34 Ｂ２９Ｌ 31:34 Ｆターム(参考） 4F072 AA04 AA07 AB09 AB28 AD15 AD23 AD28 AE02 AE08 AF03 AF04 AF06 AG03 AH02 AH25 AK14 AL12 4F100 AA00A AA00B AB17C AB33C AG00A AG00B AK53A AK53B BA02 BA03 BA07 BA08 BA10A BA10C CA02B CA23A CA23B CC00A CC00B DG12A DG15B DH02A DH02B EH46A EH46B GB43 JJ03 JL11 4F201 AA39 AB11 AC03 AD16 AG03 AH36 BA03 BC01 BC12 BC21 BC29 BC33 BD02 BM04 BM13 BM14 BM16 4F204 AA39 AB11 AC03 AD16 AG03 AH36 FB01 FB22 FG03 FG09 FJ30 4J002 CD001 CD051 CD061 DE146 DE236 DJ016 DJ036 DJ046 FD016 GF00 GQ00 4J036 AA01 AD08 AF06 FA05 FB08 JA08 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) C08J 5/24 CFC C08J 5/24 CFC 4J036 C08K 3/00 C08K 3/00 C08L 63/00 C08L 63/00 C // B29K 63:00 B29K 63:00 105: 08 105: 08 B29L 31:34 B29L 31:34 F term (reference) 4F072 AA04 AA07 AB09 AB28 AD15 AD23 AD28 AE02 AE08 AF03 AF04 AF06 AG03 AH02 AH25 AK14 AL12 4F100 AA00A AA00B AB17B AG00A AG00B AK53A AK53B BA02 BA03 BA07 BA08 BA10A BA10C CA02B CA23A CA23B CC00A CC00B DG12A DG15B DH02A DH02B EH46A EH46B GB43 JJ03 JL11 4F201 AA39 AB11 AC03 AD16 AG03 AB02 BC12 BC12 BC12 BC12 BC12 BC12 BC12 BC12 BC FB22 FG03 FG09 FJ30 4J002 CD001 CD051 CD061 DE146 DE236 DJ016 DJ036 DJ046 FD016 GF00 GQ00 4J036 AA01 AD08 AF06 FA05 FB08 JA08
Claims (3)
シ樹脂及び前記樹脂１００重量部に対し無機充填剤１０
〜２００重量部を含むエポキシ樹脂ワニス（Ａ）を塗布
し、（ｂ）その上からガラス不織布を重ね合わせ乾燥し
た後、（ｃ）ノボラック型エポキシ樹脂、ビスフェノ−
ルＡ型エポキシ樹脂及びノボラック樹脂硬化剤を含む中
間層エポキシ樹脂組成物に無機充填材を前記樹脂組成物
に対し８０〜１５０％添加した中間層樹脂ワニス（Ｂ）
を塗布し、乾燥してプリプレグとし、（ｄ）このプリプ
レグ２枚をガラス不織布を内側にして重ね合わせ加熱加
圧することを特徴とするコンポジット積層板の製造方
法。1. A non-brominated epoxy resin on a glass woven fabric and an inorganic filler 10 per 100 parts by weight of the resin.
Epoxy resin varnish (A) containing 部 200 parts by weight, and (b) a glass nonwoven fabric overlaid thereon and dried, and then (c) a novolak-type epoxy resin, bisphenol-
Intermediate layer resin varnish (B) in which an inorganic filler is added to an intermediate layer epoxy resin composition containing an A-type epoxy resin and a novolak resin curing agent in an amount of 80 to 150% based on the resin composition.
(D) two prepregs are placed on top of each other with the glass non-woven fabric inside, and heated and pressed to obtain a prepreg.
比でガラス不織布の５〜１５倍である請求項１記載のコ
ンポジット積層板の製造方法。2. The method for producing a composite laminate according to claim 1, wherein the solid content of the intermediate resin varnish (B) is 5 to 15 times the weight of the glass nonwoven fabric by weight.
に、ガラス織布側に非臭素化エポキシ樹脂及び前記樹脂
１００重量部に対し無機充填剤１０〜２００重量部を含
むエポキシ樹脂ワニス（Ｃ）を塗布する請求項１記載の
コンポジット積層板の製造方法。3. An epoxy resin varnish containing a non-brominated epoxy resin on the glass woven fabric side and 10 to 200 parts by weight of an inorganic filler with respect to 100 parts by weight of the resin after coating and drying the resin varnish (B) for the intermediate layer. The method for producing a composite laminate according to claim 1, wherein C) is applied.
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|---|---|---|---|
| JP2001071980A JP3998914B2 (en) | 2001-03-14 | 2001-03-14 | Laminate production method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001071980A JP3998914B2 (en) | 2001-03-14 | 2001-03-14 | Laminate production method |
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| Publication Number | Publication Date |
|---|---|
| JP2002264158A true JP2002264158A (en) | 2002-09-18 |
| JP3998914B2 JP3998914B2 (en) | 2007-10-31 |
Family
ID=18929626
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001071980A Expired - Fee Related JP3998914B2 (en) | 2001-03-14 | 2001-03-14 | Laminate production method |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003236868A (en) * | 2002-02-19 | 2003-08-26 | Sumitomo Bakelite Co Ltd | Method for manufacturing composite laminated sheet |
| JP2015178627A (en) * | 2015-05-22 | 2015-10-08 | ダウ グローバル テクノロジーズ エルエルシー | Metal stabilizers for epoxy resins and dispersion process |
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|---|---|---|---|---|
| JPH05163373A (en) * | 1991-12-13 | 1993-06-29 | Sumitomo Bakelite Co Ltd | Production of laminate board |
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| JPH06100708A (en) * | 1992-09-24 | 1994-04-12 | Shin Kobe Electric Mach Co Ltd | Composite laminated sheet |
| JPH08267664A (en) * | 1995-03-28 | 1996-10-15 | Sumitomo Bakelite Co Ltd | Manufacture of laminate |
| JPH1017684A (en) * | 1996-07-02 | 1998-01-20 | Sumitomo Bakelite Co Ltd | Production of prepreg and laminate |
| JPH11246741A (en) * | 1998-02-27 | 1999-09-14 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for laminate |
| JP2001260157A (en) * | 2000-03-22 | 2001-09-25 | Sumitomo Bakelite Co Ltd | Method for manufacturing laminated sheet |
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2001
- 2001-03-14 JP JP2001071980A patent/JP3998914B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05163373A (en) * | 1991-12-13 | 1993-06-29 | Sumitomo Bakelite Co Ltd | Production of laminate board |
| JPH05309789A (en) * | 1992-05-13 | 1993-11-22 | Toshiba Chem Corp | Production of composite copper clad laminated sheet |
| JPH06100708A (en) * | 1992-09-24 | 1994-04-12 | Shin Kobe Electric Mach Co Ltd | Composite laminated sheet |
| JPH08267664A (en) * | 1995-03-28 | 1996-10-15 | Sumitomo Bakelite Co Ltd | Manufacture of laminate |
| JPH1017684A (en) * | 1996-07-02 | 1998-01-20 | Sumitomo Bakelite Co Ltd | Production of prepreg and laminate |
| JPH11246741A (en) * | 1998-02-27 | 1999-09-14 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for laminate |
| JP2001260157A (en) * | 2000-03-22 | 2001-09-25 | Sumitomo Bakelite Co Ltd | Method for manufacturing laminated sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003236868A (en) * | 2002-02-19 | 2003-08-26 | Sumitomo Bakelite Co Ltd | Method for manufacturing composite laminated sheet |
| JP2015178627A (en) * | 2015-05-22 | 2015-10-08 | ダウ グローバル テクノロジーズ エルエルシー | Metal stabilizers for epoxy resins and dispersion process |
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| Publication number | Publication date |
|---|---|
| JP3998914B2 (en) | 2007-10-31 |
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