JP4273553B2 - Laminate production method - Google Patents
Laminate production method Download PDFInfo
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- JP4273553B2 JP4273553B2 JP01726699A JP1726699A JP4273553B2 JP 4273553 B2 JP4273553 B2 JP 4273553B2 JP 01726699 A JP01726699 A JP 01726699A JP 1726699 A JP1726699 A JP 1726699A JP 4273553 B2 JP4273553 B2 JP 4273553B2
- Authority
- JP
- Japan
- Prior art keywords
- glass cloth
- epoxy resin
- resin
- intermediate layer
- impregnated
- 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.)
- Expired - Fee Related
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Description
【0001】
【発明の属する技術分野】
本発明は、ガラスクロスの上に中間層樹脂を塗布し、さらに、その上にガラスクロスを載置し、得られた積層体を加熱加圧するコンポジット積層板の製造方法に関するものである。
【0002】
【従来の技術】
ガラスクロスの上に中間層樹脂を塗布し、さらに、その上にガラスクロスを載置し、得られた積層体を加熱加圧するコンポジット積層板の製造方法では、プリプレグ製造時(中間層樹脂塗布後)に中間層樹脂がガラスクロス反対面からしみ出すことがあり、プリプレグ製造設備に樹脂が固着し、これがガラスクロスを破り、安定してプリプレグを製造することができず、生産性が低下するという問題がある。この中間層樹脂のしみ出しを防止するための方法として、ガラスクロスにエポキシ樹脂を含浸乾燥させることが知られている。ガラスクロスにエポキシ樹脂のみを含浸させた場合は、ガラスクロス反対面から中間層樹脂がしみ出さないようにするためには含浸後十分に乾燥させなければならない。このため、得られたコンポジット積層板は、銅箔とプリプレグの密着性が低下する傾向があった。一方、無機充填材等を添加したエポキシ樹脂をガラスクロスに含浸させた場合では、無機充填材等の添加量や粒径が適切でないと中間層樹脂のしみ出しを十分に防止できなかったり、逆にしみ出しを防止できても、積層板の打抜き性が低下するなどの問題があった。
【0003】
【発明が解決しようとする課題】
本発明は、ガラスクロスの上に中間層樹脂を塗布し、さらに、その上にガラスクロスを載置し、得られた積層体を加熱加圧するコンポジット積層板の製造方法において、打抜き性等を低下させることなく中間層樹脂がガラスクロス反対面からしみ出さないようにすることを目的とする。
【0004】
【課題を解決するための手段】
本発明は、ガラスクロスの上に中間層樹脂を塗布し、さらに、その上にガラスクロスを載置し、得られた積層体を加熱加圧するコンポジット積層板の製造方法において、前記ガラスクロスとして、微粒子状無機充填材を全樹脂量に対し1〜5重量%添加したエポキシ樹脂を予め含浸させたガラスクロスを使用することを特徴とする積層板の製造方法に関するものである。
【0005】
【発明の実施の形態】
本発明では、微粒子状無機充填材を1〜5重量%添加したエポキシ樹脂をガラスクロスに含浸することにより、積層板の打抜き性を低下させることなく、プリプレグ製造時中間層樹脂がガラスクロス反対面からしみ出さないようにするものである。
従来からガラスクロスの上に中間層樹脂を塗布し、さらに、その上からガラスクロスを載置する方法によりコンポジット積層板を製造する場合、中間層樹脂がガラスクロスからしみ出さないようにする方法として、ガラスクロスに、エポキシ樹脂を含浸させる方法では、ガラスクロスの織り目空隙に対しエポキシ樹脂の引掛かりが弱く、中間層樹脂が、予めガラスクロスに含浸させたエポキシ樹脂と共に、ガラスクロスの織り目の空隙から抜け落ちる。本発明では、ガラスクロスに含浸させるエポキシ樹脂に微粒子状無機充填材を1〜5重量%添加しておくことにより、ガラスクロスの織り目空隙に微粒子シリカが引掛かり、この空隙を埋め、中間層樹脂が抜け落ちることを防止する。
【0006】
ガラスクロスに含浸させるエポキシ樹脂に微粒子状無機充填材を5重量%を越えて添加すると、微粒子状無機充填材が中間層樹脂とガラスクロスに含浸されたエポキシ樹脂との界面での架橋構造の妨げとなり、中間層樹脂とエポキシ樹脂含浸ガラスクロスとの密着性が弱まり打抜き性が低下する。また、1重量%未満では、中間層樹脂がガラスクロス反対面からしみ出さないためには十分な効果が得られない。
本発明の目的を達成するために、微粒子状無機充填材の粒径は、平均粒径で100nm〜100μmのものが好ましい。100nmより小さいと含浸するワニス粘度が高くなり取扱いが難しくガラスクロスへの含浸性も低下する。100μmより大きいとガラスクロスからしみ出し防止効果が小さくなる。特に好ましい範囲は200〜700nmである。
【0007】
本発明において、ガラスクロスに含浸させるエポキシ樹脂に添加する微粒子状無機充填材は、微粒子シリカ、微粒子アルミニウム化合物、微粒子マグネシウム化合物、微粒子カルシウム化合物等があり、特に限定されないが、粒径が上記200〜700nmの範囲に入る微粒子微粒子シリカが好ましい。
【0008】
本発明において、中間層樹脂としてエポキシ樹脂が使用されるが、ノボラック型エポキシ樹脂、とビスフェノ−ルA型エポキシ樹脂及び又はハロゲン化ビスフェノールA型エポキシ樹脂を主成分とするエポキシ樹脂が耐燃性、耐熱性を向上させるために好ましく使用される。
中間層樹脂には、通常無機充填材を樹脂分100重量部に対して50〜150重量部配合する。無機充填材は特に限定されるものではなく、コンポジット積層板に使用されるものであればいかなるものでも使用可能である。
【0009】
本発明において、ガラスクロスに微粒子シリカ及び又は他の微粒子状無機充填材を添加したエポキシ樹脂を含浸し乾燥後、中間層樹脂を塗布し乾燥する。さらに、その上にガラスクロスを載置して、積層体(プリプレグ)を得る。この積層体を加熱加圧して目的とするコンポジット積層板を得ることができる。
【0010】
【実施例】
実施例1〜2及び比較例1〜2
ガラスクロスに含浸させるエポキシ樹脂ワニスとして、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、臭素化ビスフェノールA型エポキシ樹脂、テトラブロムビスフェノ−ルA、ノボラック樹脂、及び硬化促進剤として2−エチル−4−メチルイミダゾ−ルを使用した。実施例1と比較例2においては、微粒子シリカを添加し、実施例2においては水酸化アルミニウムを添加した。各成分は表1に示す割合にて配合した。
【0011】
【表1】
【0012】
また、中間層樹脂として、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、臭素化ビスフェノールA型エポキシ樹脂、ノボラック樹脂、及び硬化促進剤として2−エチル−4−メチルイミダゾ−ルを用い、無機充填材として水酸化アルミニウムを用いた。各成分は表2に示した割合にて配合した。
【0013】
【表2】
【0014】
(注1)ビスA型エポキシ樹脂:エピクロン850(エポキシ当量190、大日本インキ化学(株)製)
(注2)臭素化ビスA型エポキシ樹脂:GX153(エポキシ当量400、大日本インキ化学(株)製)
(注3)クレゾ−ルノボラック型エポキシ樹脂:エピコ−ト180S75(エポキシ当量210、油化シェルエポキシ(株)製)
(注4)ノボラック型フェノール樹脂:PR−51470(住友デュレズ(株)製)
(注5)微粒子シリカ:カ−プレックス#67(シオノギ製薬(株)製)
(注6)水酸化アルミニウム:CL−310(住友化学(株)製)
【0015】
前記エポキシ樹脂ワニスをガラスクロスに含浸し、次いで、中間層樹脂を塗布し、その上にガラスクロスを載置した。さらに、この両表面に銅箔を重ね、加熱加圧してコンポジット積層板を得た。中間層樹脂塗布後、中間層樹脂のガラスクロス反対面からのしみ出しを観察した。そして、得られたコンポジット積層板の打抜き性を測定した。結果を表3に示す。
【0016】
【表3】
【0017】
(評価方法)
1. 中間層樹脂のしみ出し(プリプレグ製造時)
○:中間層樹脂がガラスクロスの反対面側にしみ出ない。
×:中間層樹脂がガラスクロスの反対面側にしみ出る。
2.打抜き性:エッチングにより銅箔を除去した140×140mmの積層板を、0.7mmφ、2.0mmピッチの連続穴、及び1.0mmφ、2.5mmピッチの連続穴の開けられる金型を用いて100トン打抜きプレス(遠藤プレス(株)製)で打ち抜いた。
○:クラックなし、穴周りに剥離が生じない。
△:クラックなし、穴間を直結しない剥離が生じる。
×:クラック、または、穴間を直結する剥離が生じる。
【0018】
【発明の効果】
本発明は、ガラスクロスの上に中間層樹脂を塗布し、さらに、その上にガラスクロスを載置し、得られた積層体を加熱加圧するコンポジット積層板の製造方法において、ガラスクロスに微粒子シリカを添加したエポキシ樹脂をガラスクロスに含浸させることにより、打抜き性等の特性を低下させること無く、プリプレグ製造時に中間層樹脂がガラスクロス反対面からしみ出さないようにすることができる。従って、本発明の方法は、コンポジット積層板の特性を低下させることなく、生産効率を向上させることが出来るのでその工業的価値は極めて大なるものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a composite laminate, in which an intermediate layer resin is applied on a glass cloth, a glass cloth is further placed thereon, and the obtained laminate is heated and pressed.
[0002]
[Prior art]
In the method for producing a composite laminate in which an intermediate layer resin is coated on a glass cloth, and further the glass cloth is placed on the glass cloth, and the resulting laminate is heated and pressed, the prepreg is manufactured (after the intermediate layer resin is applied). ) The intermediate layer resin may ooze out from the opposite surface of the glass cloth, and the resin adheres to the prepreg manufacturing equipment, which breaks the glass cloth and cannot stably manufacture the prepreg, reducing productivity. There's a problem. As a method for preventing the intermediate layer resin from exuding, it is known that glass cloth is impregnated and dried with an epoxy resin. When the glass cloth is impregnated only with the epoxy resin, it must be sufficiently dried after impregnation in order to prevent the intermediate layer resin from exuding from the opposite surface of the glass cloth. For this reason, the obtained composite laminated board had the tendency for the adhesiveness of copper foil and a prepreg to fall. On the other hand, when glass cloth is impregnated with an epoxy resin to which an inorganic filler or the like is added, the exudation of the intermediate layer resin cannot be sufficiently prevented unless the addition amount or particle size of the inorganic filler or the like is appropriate. Even if the bleeding could be prevented, there was a problem that the punchability of the laminate was lowered.
[0003]
[Problems to be solved by the invention]
The present invention is a method for producing a composite laminate in which an intermediate layer resin is applied onto a glass cloth, and further, the glass cloth is placed thereon, and the resulting laminate is heated and pressed. The purpose is to prevent the intermediate layer resin from oozing out from the opposite surface of the glass cloth.
[0004]
[Means for Solving the Problems]
In the method for producing a composite laminate in which the present invention is applied to an intermediate layer resin on a glass cloth, and further, the glass cloth is placed thereon, and the resulting laminate is heated and pressurized, as the glass cloth, The present invention relates to a method for producing a laminated board characterized by using a glass cloth impregnated with an epoxy resin in which 1 to 5% by weight of a fine inorganic filler is added to the total resin amount.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, by impregnating a glass cloth with an epoxy resin to which 1 to 5% by weight of a fine inorganic filler is added, the intermediate layer resin is opposite to the glass cloth during prepreg production without reducing the punchability of the laminate. It will prevent it from oozing out.
As a method to prevent the intermediate layer resin from exuding from the glass cloth, when a composite laminate is manufactured by applying the intermediate layer resin on the glass cloth and then placing the glass cloth on the glass cloth. In the method of impregnating the glass cloth with the epoxy resin, the epoxy resin is weakly caught with respect to the textured gap of the glass cloth. Fall out of it. In the present invention, by adding 1 to 5% by weight of a fine inorganic filler to the epoxy resin impregnated in the glass cloth, the fine particle silica is caught in the textured void of the glass cloth, and the intermediate layer resin is filled. Prevents falling off.
[0006]
Addition of more than 5% by weight of fine inorganic filler to the epoxy resin impregnated into the glass cloth prevents the fine inorganic filler from cross-linking at the interface between the interlayer resin and the epoxy resin impregnated into the glass cloth. Thus, the adhesiveness between the intermediate layer resin and the epoxy resin-impregnated glass cloth is weakened, and the punchability is lowered. Moreover, if it is less than 1% by weight, a sufficient effect cannot be obtained because the intermediate layer resin does not ooze out from the opposite surface of the glass cloth.
In order to achieve the object of the present invention, the fine particle inorganic filler preferably has an average particle diameter of 100 nm to 100 μm. If it is smaller than 100 nm, the viscosity of the varnish to be impregnated becomes high and handling is difficult, and the impregnation property to the glass cloth is also lowered. If it is larger than 100 μm, the effect of preventing seepage from the glass cloth is reduced. A particularly preferable range is 200 to 700 nm.
[0007]
In the present invention, the fine inorganic filler added to the epoxy resin impregnated into the glass cloth includes fine particle silica, fine particle aluminum compound, fine particle magnesium compound, fine particle calcium compound and the like, although not particularly limited, the particle size is 200 to 200 above. Fine particulate silica falling in the range of 700 nm is preferred.
[0008]
In the present invention, an epoxy resin is used as the intermediate layer resin. A novolac type epoxy resin and an epoxy resin mainly composed of a bisphenol A type epoxy resin and / or a halogenated bisphenol A type epoxy resin are flame resistant and heat resistant. It is preferably used for improving the property.
The intermediate layer resin is usually blended with 50 to 150 parts by weight of an inorganic filler with respect to 100 parts by weight of the resin. The inorganic filler is not particularly limited, and any inorganic filler can be used as long as it is used for the composite laminate.
[0009]
In the present invention, glass cloth is impregnated with an epoxy resin to which fine particle silica and / or other fine inorganic fillers are added and dried, and then an intermediate layer resin is applied and dried. Furthermore, a glass cloth is placed thereon to obtain a laminate (prepreg). The laminate can be heated and pressed to obtain a desired composite laminate.
[0010]
【Example】
Examples 1-2 and Comparative Examples 1-2
As epoxy resin varnish to be impregnated into glass cloth, novolak type epoxy resin, bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, tetrabromobisphenol A, novolac resin, and 2-ethyl as curing accelerator -4-Methylimidazole was used. In Example 1 and Comparative Example 2, fine particle silica was added, and in Example 2, aluminum hydroxide was added. Each component was blended in the proportions shown in Table 1.
[0011]
[Table 1]
[0012]
Further, novolac type epoxy resin, bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolac resin, and 2-ethyl-4-methylimidazole as the curing accelerator are used as the intermediate layer resin, and inorganic. Aluminum hydroxide was used as the filler. Each component was blended in the proportions shown in Table 2.
[0013]
[Table 2]
[0014]
(Note 1) Bis A type epoxy resin: Epicron 850 (epoxy equivalent 190, manufactured by Dainippon Ink & Chemicals, Inc.)
(Note 2) Brominated bis A type epoxy resin: GX153 (epoxy equivalent 400, manufactured by Dainippon Ink & Chemicals, Inc.)
(Note 3) Cresol novolak type epoxy resin: Epicoat 180S75 (epoxy equivalent 210, manufactured by Yuka Shell Epoxy Co., Ltd.)
(Note 4) Novolac type phenolic resin: PR-51470 (manufactured by Sumitomo Durez Co., Ltd.)
(Note 5) Fine particle silica: Carplex # 67 (manufactured by Shionogi Pharmaceutical Co., Ltd.)
(Note 6) Aluminum hydroxide: CL-310 (manufactured by Sumitomo Chemical Co., Ltd.)
[0015]
A glass cloth was impregnated with the epoxy resin varnish, then an intermediate layer resin was applied, and the glass cloth was placed thereon. Further, a copper foil was laminated on both surfaces and heated and pressed to obtain a composite laminate. After application of the intermediate layer resin, the seepage of the intermediate layer resin from the opposite surface of the glass cloth was observed. Then, the punchability of the obtained composite laminate was measured. The results are shown in Table 3.
[0016]
[Table 3]
[0017]
(Evaluation methods)
1. Exudation of intermediate layer resin (during prepreg production)
○: The intermediate layer resin does not ooze out on the opposite side of the glass cloth.
X: The intermediate layer resin oozes out on the opposite side of the glass cloth.
2. Punchability: A 140 × 140 mm laminated plate from which copper foil has been removed by etching is used with a mold that can be drilled with 0.7 mmφ, 2.0 mm pitch continuous holes, and 1.0 mmφ, 2.5 mm pitch continuous holes. Punched with a 100-ton punch press (manufactured by Endo Press).
○: No crack and no peeling around the hole.
(Triangle | delta): There is no crack and peeling which does not directly connect between holes arises.
X: Cracks or peeling that directly connects between holes occurs.
[0018]
【The invention's effect】
The present invention relates to a method for producing a composite laminate in which an intermediate layer resin is coated on a glass cloth, and further, the glass cloth is placed thereon, and the resulting laminate is heated and pressed. By impregnating the glass cloth with the epoxy resin added with the intermediate layer resin, it is possible to prevent the intermediate layer resin from oozing out from the opposite surface of the glass cloth without deteriorating the properties such as punchability. Therefore, since the method of the present invention can improve the production efficiency without deteriorating the properties of the composite laminate, its industrial value is extremely high.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP01726699A JP4273553B2 (en) | 1999-01-26 | 1999-01-26 | Laminate production method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP01726699A JP4273553B2 (en) | 1999-01-26 | 1999-01-26 | Laminate production method |
Publications (2)
Publication Number | Publication Date |
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JP2000211059A JP2000211059A (en) | 2000-08-02 |
JP4273553B2 true JP4273553B2 (en) | 2009-06-03 |
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JP01726699A Expired - Fee Related JP4273553B2 (en) | 1999-01-26 | 1999-01-26 | Laminate production method |
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JP (1) | JP4273553B2 (en) |
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1999
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