JPS6336934B2 - - Google Patents
Info
- Publication number
- JPS6336934B2 JPS6336934B2 JP58234746A JP23474683A JPS6336934B2 JP S6336934 B2 JPS6336934 B2 JP S6336934B2 JP 58234746 A JP58234746 A JP 58234746A JP 23474683 A JP23474683 A JP 23474683A JP S6336934 B2 JPS6336934 B2 JP S6336934B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- weight
- parts
- metal foil
- resin composition
- 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
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、電気用積層板の製造方法に関する。
さらに詳しくは、高度の耐熱性と優れた接着性を
有する電気用積層板の製造方法に関する。ここで
いう電気用積層板とは、例えば各種電子部品の基
板として用いられる金属箔張り積層板を意味し、
その形状は厚みが0.5ないし５mmであるような板
状物をいう。
電気用積層板に用いられるエポキシ樹脂組成物
は、昨今ますます高度の耐熱性と優れた接着性を
要求されてきている。しかしながら、従来のエポ
キシ樹脂組成物では、この高度の耐熱性と優れた
接着性をともに満足するまでには至つていない。
本発明者らは、かかる現状に鑑みて鋭意研究し
た結果、金属箔との接着性を低下させることな
く、耐熱性を向上させたエポキシ樹脂組成物を見
出し、本発明に至つた。
即ち、本発明は、(a)ビスフエノール型固形エポ
キシ樹脂10〜80重量部、(b)Ｏ−クレゾールノボラ
ツクエポキシ樹脂および／またはフエノールノボ
ラツクエポキシ樹脂10〜60重量部、(c)エポキシ基
と反応可能な官能基を有するニトリルブタジエン
ゴム10〜60重量部を必須成分とするエポキシ樹脂
組成物およひ該樹脂組成物を接着性として使用す
る電気用金属箔張り積層板の製造方法である。
本発明においていうビスフエノール型固形エポ
キシ樹脂としては、エポキシ当量300〜6000（ｇ／
eq）のビスフエノールＡ型エポキシ樹脂が使わ
れるが、これに限定されるわけではなく、その配
合量は10〜80重量部、好ましくは30〜60重量部で
ある。
また、Ｏ−クレソールノボラツクエポキシ樹脂
あるいはフエノールノボラツクエポキシ樹脂は、
通常エポキシ当量150〜250（ｇ／eq）のものが使
われ、単独でも併用使用でもよく、その配合量は
10〜60重量部、好ましくは20〜40重量部である。
Ｏ−クレゾールノボラツク樹脂が耐熱性の面で特
に好適である。
さらに、本発明においていうエポキシ基と反応
可能な官能基を有するニトリルブタジエンゴムと
は、末端官能基としてカルボキシル基あるいはア
ミノ基等をもつアクリロニトリル・ブタジエン共
重合ゴムであり、その配合量は10〜60重量部、好
ましくは20〜40重量部である。
本発明のエポキシ樹脂組成物は適当な溶剤、例
えばアセトン、メチルエチルケトン、メチルセロ
ソルブ、エチルセロソルブ、ジメチルホルムアミ
ド等に溶解させて使用することができる。また、
液状エポキシ樹脂、例えばビスフエノールＡ型液
状エポキシ樹脂、エポキシ系希釈剤等に溶解させ
て使用することも可能である。溶剤または液状エ
ポキシの使用量には特に制限はないが、エポキシ
樹脂組成物100重量部に対して30〜300重量部が好
ましい。
本発明のエポキシ樹脂組成物はそのままでも用
いることができるが、エポキシ樹脂の一般的な硬
化剤（アミン類、酸無水物、ジシアンアミド等）
およびイミダゾール誘導体等の硬化促進剤を併用
することが好適でる。また、無機充填剤、例えば
金属酸化物、金属水酸化物、ケイ酸塩鉱物等を配
合してもよい。
本発明のエポキシ樹脂組成物の接着性と耐熱性
をさらに向上させるために、シランカツプリング
剤、例えばエポキシシラン系、アミノシラン系、
メルカプトシラン系、ビニルシラン系シランカツ
プリング剤を添加することができる。シランカツ
プリング剤の添加量は、エポキシ樹脂組成物100
重量部に対して0.1〜10重量部が好ましい。
本発明のエポキシ樹脂組成物は、注型含浸用の
樹脂として有用であり、特に、高い耐熱性と優れ
た接着性を有することから電気用積層板用樹脂お
よび接着剤として好適である。
とりわけ、本発明のエポキシ樹脂組成物は、高
い耐熱性、優れた接着強度、タツクフリーである
こと、シエルフライフの長いこと等から片面また
は両面金属箔張り不飽和ポリエステル積層板の接
着剤として好適に使用できる。すなわち、本発明
のエポキシ樹脂組成物を塗布、プリキユアした金
属箔を、不飽和ポリエステル樹脂を含浸せしめた
基材複数枚と積層硬化して金属箔張り不飽和ポリ
エステル積層板を得ることができる。基材はガラ
スクロス、ガラスマツト等のガラス系基材や、好
ましくはセルロース系基材またはこれらの混抄基
材等が使用できるが、特に好ましくは例えばクラ
フト紙やリンター紙を用いることができ、その場
合例えば、特開昭56−98136号に記載した如く不
飽和ポリエステル樹脂組成物を基材に含浸する前
に処理薬剤により予備含浸することが好ましい。
また、上述の樹脂含浸基材を積層硬化する場合に
は、特開昭56−98136号に開示したように、硬化
の際の成形圧が実質的に無圧の条件で連続的に硬
化させるのが最も良好な方法である。接着剤の塗
布、キユア条件には特に限定はないが、プリキユ
ア100〜150℃で１分〜10分、アフターキユア140
〜170℃で0.1〜１時間が好ましい。
以下実施例により本発明を詳細に説明する。実
施例中「部」とあるのは重量部を意味する。
実施例１、２；比較例１、２
メラミン樹脂（ニカレジンＳ−305、日本カー
バイド製）で予備処理した紙基材を、市販の不飽
和ポリエステル樹脂（ポリマール6304、武田薬品
製）100重量部へベンゾイルパーオキサイド１重
量部を添加した樹脂液で含浸し、これを５層積層
し、表１に示したエポキシ樹脂組成物をそれぞれ
硬化後の厚みが30ミクロンになるように塗布した
後120℃で２分プレキユアした厚さ35ミクロンの
電解銅箔を上側に、同時に厚さ100ミクロンのポ
リエステルフイルムを下側にラミネートし、その
後100℃で20分間無圧の条件下加熱硬化した。一
定長さに切断後、160℃で20分間後硬化を行い、
片面銅箔張り積層板を得た。表２にその特性を示
す。
The present invention relates to a method of manufacturing an electrical laminate.
More specifically, the present invention relates to a method for producing an electrical laminate having high heat resistance and excellent adhesiveness. The electrical laminate herein refers to a metal foil-clad laminate used as a substrate for various electronic components, for example.
Its shape is a plate with a thickness of 0.5 to 5 mm. Epoxy resin compositions used in electrical laminates are now required to have increasingly high heat resistance and excellent adhesive properties. However, conventional epoxy resin compositions have not yet been able to satisfy both this high degree of heat resistance and excellent adhesiveness. As a result of intensive research in view of the current situation, the present inventors have discovered an epoxy resin composition that has improved heat resistance without reducing adhesion to metal foil, leading to the present invention. That is, the present invention provides (a) 10 to 80 parts by weight of a bisphenol type solid epoxy resin, (b) 10 to 60 parts by weight of an O-cresol novolac epoxy resin and/or a phenol novolac epoxy resin, and (c) an epoxy group An epoxy resin composition containing 10 to 60 parts by weight of nitrile butadiene rubber having a functional group capable of reacting with the nitrile butadiene rubber as an essential component, and a method for producing an electrical metal foil-clad laminate using the resin composition as an adhesive. . The bisphenol type solid epoxy resin referred to in the present invention has an epoxy equivalent of 300 to 6000 (g/
eq) bisphenol A type epoxy resin is used, but is not limited thereto, and the blending amount is 10 to 80 parts by weight, preferably 30 to 60 parts by weight. In addition, O-cresol novolac epoxy resin or phenol novolac epoxy resin is
Epoxy equivalents of 150 to 250 (g/eq) are usually used, and they can be used alone or in combination, and the amount of
The amount is 10 to 60 parts by weight, preferably 20 to 40 parts by weight.
O-cresol novolak resin is particularly suitable in terms of heat resistance. Furthermore, the nitrile-butadiene rubber having a functional group capable of reacting with an epoxy group in the present invention is an acrylonitrile-butadiene copolymer rubber having a carboxyl group or an amino group as a terminal functional group, and the blending amount thereof is 10 to 60%. parts by weight, preferably 20 to 40 parts by weight. The epoxy resin composition of the present invention can be used by dissolving it in a suitable solvent such as acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, dimethyl formamide and the like. Also,
It is also possible to use it by dissolving it in a liquid epoxy resin, such as a bisphenol A type liquid epoxy resin, or an epoxy diluent. The amount of the solvent or liquid epoxy used is not particularly limited, but is preferably 30 to 300 parts by weight per 100 parts by weight of the epoxy resin composition. The epoxy resin composition of the present invention can be used as it is, but common curing agents for epoxy resins (amines, acid anhydrides, dicyanamide, etc.)
It is also suitable to use a curing accelerator such as an imidazole derivative. Inorganic fillers such as metal oxides, metal hydroxides, silicate minerals, etc. may also be added. In order to further improve the adhesion and heat resistance of the epoxy resin composition of the present invention, silane coupling agents such as epoxy silane type, amino silane type,
A mercaptosilane type or vinyl silane type silane coupling agent can be added. The amount of silane coupling agent added is 100% of the epoxy resin composition.
It is preferably 0.1 to 10 parts by weight. The epoxy resin composition of the present invention is useful as a resin for casting impregnation, and is particularly suitable as a resin and adhesive for electrical laminates because it has high heat resistance and excellent adhesiveness. In particular, the epoxy resin composition of the present invention is suitable as an adhesive for unsaturated polyester laminates covered with metal foil on one or both sides because of its high heat resistance, excellent adhesive strength, tack-free property, and long shelf life. Can be used. That is, a metal foil coated with the epoxy resin composition of the present invention and pre-cured is laminated and cured with a plurality of base materials impregnated with an unsaturated polyester resin to obtain a metal foil-covered unsaturated polyester laminate. The base material can be a glass base material such as glass cloth or glass matte, preferably a cellulose base material or a mixed base material thereof, and particularly preferably, for example, kraft paper or linter paper can be used. For example, as described in JP-A-56-98136, it is preferable to pre-impregnate the substrate with a treatment agent before impregnating the substrate with the unsaturated polyester resin composition.
In addition, when the above-mentioned resin-impregnated base material is laminated and cured, as disclosed in JP-A No. 56-98136, continuous curing is performed under conditions where the molding pressure during curing is substantially no pressure. is the best method. There are no particular limitations on adhesive application and curing conditions, but pre-curing at 100 to 150°C for 1 to 10 minutes, and after-curing at 140°C.
0.1 to 1 hour at ~170°C is preferred. The present invention will be explained in detail below with reference to Examples. In the examples, "parts" means parts by weight. Examples 1 and 2; Comparative Examples 1 and 2 A paper base material pretreated with melamine resin (Nica Resin S-305, manufactured by Nippon Carbide) was added to 100 parts by weight of a commercially available unsaturated polyester resin (Polymer 6304, manufactured by Takeda Pharmaceutical). Impregnated with a resin solution containing 1 part by weight of benzoyl peroxide, laminated in 5 layers, coated with the epoxy resin composition shown in Table 1 so that the thickness after curing was 30 microns, and heated at 120°C. A 35 micron thick electrolytic copper foil pre-cured for 2 minutes was laminated on the upper side, and at the same time a 100 micron thick polyester film was laminated on the lower side, followed by heat curing at 100° C. for 20 minutes without pressure. After cutting to a certain length, post-cure at 160℃ for 20 minutes.
A single-sided copper foil-clad laminate was obtained. Table 2 shows its characteristics.
【表】【table】
Claims (1)
80重量部 (b) ｏ−クレゾールノボラツクエポキシ樹脂およ
び／またはフエノールノボラツクエポキシ樹脂
10〜60重量部 (c) エポキシ基と反応可能な官能基を有するニト
リルブタジエンゴム10〜60重量部 とからなるエポキシ樹脂組成物の溶液を金属箔に
塗布し、プレキユアした後不飽和ポリエステル樹
脂を含浸した基材複数枚と積層硬化することを特
徴とする電気用金属箔張り積層板の製造方法。 ２ シランカツプリング剤0.1〜10重量部を前記
エポキシ樹脂組成物に配合する第１項記載の電気
用金属箔張り積層板の製造方法。[Claims] 1 (a) Bisphenol type solid epoxy resin 10~
80 parts by weight (b) o-cresol novolac epoxy resin and/or phenol novolac epoxy resin
10 to 60 parts by weight (c) A solution of an epoxy resin composition consisting of 10 to 60 parts by weight of nitrile butadiene rubber having a functional group capable of reacting with an epoxy group is applied to metal foil, and after precuring, an unsaturated polyester resin is applied. A method for manufacturing an electrical metal foil-clad laminate, characterized by laminating and curing a plurality of impregnated base materials. 2. The method for producing an electrical metal foil laminate according to item 1, wherein 0.1 to 10 parts by weight of a silane coupling agent is blended into the epoxy resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58234746A JPS60127348A (en) | 1983-12-12 | 1983-12-12 | Epoxy resin composition and electrical laminated board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58234746A JPS60127348A (en) | 1983-12-12 | 1983-12-12 | Epoxy resin composition and electrical laminated board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60127348A JPS60127348A (en) | 1985-07-08 |
| JPS6336934B2 true JPS6336934B2 (en) | 1988-07-22 |
Family
ID=16975704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58234746A Granted JPS60127348A (en) | 1983-12-12 | 1983-12-12 | Epoxy resin composition and electrical laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60127348A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62171185A (en) * | 1986-01-23 | 1987-07-28 | 日立化成工業株式会社 | Manufacture of flexible printed circuit |
| JP6934312B2 (en) * | 2017-04-04 | 2021-09-15 | Nok株式会社 | Rubber metal laminates and gaskets |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51133383A (en) * | 1975-05-16 | 1976-11-19 | Nippon Shokubai Kagaku Kogyo Co Ltd | A process for manufacturing copper-clad laminate |
| JPS57162764A (en) * | 1981-03-31 | 1982-10-06 | Hitachi Chem Co Ltd | Preparation of chemically platable powder coating |
| JPS5849719A (en) * | 1981-09-18 | 1983-03-24 | Nitto Electric Ind Co Ltd | Rubber-modified epoxy resin and its composition |
-
1983
- 1983-12-12 JP JP58234746A patent/JPS60127348A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60127348A (en) | 1985-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1174856C (en) | Multi-layer structure including prepreg layers and adhesion-promoting layers | |
| US5160783A (en) | Epoxy resin-impregnated glass cloth sheet having adhesive layer | |
| CN105733485B (en) | A kind of resin combination and its application | |
| JPS6336934B2 (en) | ||
| JP3125582B2 (en) | Manufacturing method of metal foil-clad laminate | |
| JPH047115B2 (en) | ||
| JP3539447B2 (en) | Manufacturing method of laminated board | |
| JPH0429393A (en) | coverlay film | |
| JPH04136083A (en) | cover lay film | |
| JPS62115038A (en) | Production of reinforced epoxy resin | |
| JPH06322324A (en) | Bonding sheet | |
| JP4245197B2 (en) | Manufacturing method of prepreg for printed wiring board and metal-clad laminate using the same | |
| JPH07112506A (en) | Manufacturing method of metal foil clad laminate | |
| JPH07214725A (en) | Method for producing metal foil-clad laminate and metal foil used therefor | |
| JPH05315742A (en) | Heat resistant adhesive | |
| JPH0435512B2 (en) | ||
| JP3823649B2 (en) | Prepreg, laminated board and printed wiring board using amide group-containing organic fiber substrate | |
| JPH03112644A (en) | Manufacture of printed-wiring board | |
| JPS6079080A (en) | Adhesive composition | |
| JP2734912B2 (en) | Copper-clad laminate for surface mount printed wiring boards | |
| JPS62116682A (en) | Metal foil adhesive for laminate | |
| JPH06270337A (en) | High heat resistant prepreg | |
| JPH02308595A (en) | Epoxy resin multilayer copper coated laminated board | |
| GB2240546A (en) | Epoxy resin adhesive composition | |
| JPH05286074A (en) | Copper-clad laminate |