JPS6012232B2 - Manufacturing method for metal foil laminates - Google Patents
Manufacturing method for metal foil laminatesInfo
- Publication number
- JPS6012232B2 JPS6012232B2 JP55008134A JP813480A JPS6012232B2 JP S6012232 B2 JPS6012232 B2 JP S6012232B2 JP 55008134 A JP55008134 A JP 55008134A JP 813480 A JP813480 A JP 813480A JP S6012232 B2 JPS6012232 B2 JP S6012232B2
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated polyester
- polyester resin
- resin sheet
- metal foil
- crosslinking agent
- 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
- 239000002184 metal Substances 0.000 title claims description 14
- 229910052751 metal Inorganic materials 0.000 title claims description 14
- 239000011888 foil Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 45
- 239000012792 core layer Substances 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 229920006305 unsaturated polyester Polymers 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- -1 pulp Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
Description
【発明の詳細な説明】
この発明は金属箔張り積層板の製法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a metal foil-clad laminate.
一般に、不飽和ポリエステル樹脂銅張積層板は、銅箔と
不飽和ポリエステルコア層との接着状態が悪い。In general, unsaturated polyester resin copper-clad laminates have poor adhesion between the copper foil and the unsaturated polyester core layer.
このような欠点を解消するために、銅箔と不飽和ポリエ
ステルコア層との間に、サプライナー用のェボキシ樹脂
含浸プリプレグを挿入することが考えられた。このよう
にすることにより、銅箔とサプライナー（ェポキシ樹脂
含浸プリプレグの硬化により生成）との接着状態はよく
なるが、サブラィナ−と不飽和ポリエステルコア層との
接着状態はよくならず、ここから剥離しやすかった。こ
のサブライナ−と不飽和ポリエステルコァ層との接着状
態を向上させるために、不飽和ポリエステルコア層に光
を照射することがさらに考えられた。このようにするこ
とにより、サブラィナ−と不飽和ポリエステルコア層と
の接着状態はかなりよくなるが、まだ満足できるほどで
はな０かつた。そこで、この発明者らは、これをさらに
改善するために研究を重ねた結果、不飽和ポリエステル
樹脂シート状体として、１分子中に二重結合とェポキシ
基とをもつ架橋剤を含有する不飽和ポリェタステル樹脂
シート状体を用いると、金属箔のみならず、サプライナ
ーとコア層との接着状態も良好な金属箔張り積層板が得
られるようになることを見いだしこの発明を完成した。In order to eliminate such drawbacks, it has been considered to insert an epoxy resin-impregnated prepreg for the supplier between the copper foil and the unsaturated polyester core layer. By doing this, the adhesion between the copper foil and the supplier (produced by curing the epoxy resin-impregnated prepreg) is improved, but the adhesion between the subliner and the unsaturated polyester core layer is not improved, and peeling occurs from there. It was easy. In order to improve the adhesion between the subliner and the unsaturated polyester core layer, it has been further considered to irradiate the unsaturated polyester core layer with light. By doing this, the adhesion between the subliner and the unsaturated polyester core layer was considerably improved, but it was still not satisfactory. Therefore, as a result of repeated research to further improve this, the inventors of the present invention developed an unsaturated polyester resin sheet containing a crosslinking agent having a double bond and an epoxy group in one molecule. This invention was completed by discovering that by using a polyetastel resin sheet, a metal foil-clad laminate with good adhesion not only between the metal foil but also between the supplier and the core layer can be obtained.
すなわち、この発明は、コア層用の不飽和ポリエステル
樹脂シート状体にェポキシ樹脂含浸プリブレグを重ねる
工程と、このェポキシ樹脂含浸プリプレグを前記の不飽
和ポリエステル樹脂シート状体に重ねる前後の少なくと
も一方の段階で不飽和ポＩＪェステル樹脂シート状体に
光照射をする工程と、前記の光照射ののち前記の不飽和
ポリエステル樹脂シート状体に重ねられた前記のヱポキ
シ樹脂含浸プリプレグの上に金属箔を重ねて全体を加熱
加圧成形する工程を備える金属箔張り積層板の製法であ
って、不飽和ポリエステル樹脂シ−ト状体として、１分
子中に二重結合とェポキシ基とをもつ架橋剤を含有する
不飽和ポリエステル樹脂シート状体を用いることを特徴
とする金属箔張り積層板の製法をその要旨とするもので
ある。That is, the present invention includes a step of stacking an epoxy resin-impregnated prepreg on an unsaturated polyester resin sheet for a core layer, and at least one of the steps before and after stacking the epoxy resin-impregnated prepreg on the unsaturated polyester resin sheet. a step of irradiating the unsaturated polyester resin sheet with light, and after the light irradiation, overlaying the metal foil on the prepreg impregnated with the above unsaturated polyester resin, which has been overlaid on the unsaturated polyester resin sheet. A method for manufacturing a metal foil-clad laminate comprising the step of heating and press-forming the entire sheet, the unsaturated polyester resin sheet containing a crosslinking agent having a double bond and an epoxy group in one molecule. The gist thereof is a method for manufacturing a metal foil-clad laminate, which is characterized by using an unsaturated polyester resin sheet.
つぎに、この発明を詳しく説明する。コァ層用の不飽和
ポリエステル樹脂シート状体は、例えば不飽和ポリエス
テル樹脂、１分子中に二重結合とヱポキシ基とをもつ架
橋剤、光重合開始剤、無機充填剤を所定の割合で配合し
、これに必要なときには補強材等をさらに配合してニー
ダー、ロール等の混練機により混練しプレスしてシート
状にしたり、押出機によりシート状に押し出したりする
ことによりつくられる。Next, this invention will be explained in detail. The unsaturated polyester resin sheet for the core layer is made by blending, for example, an unsaturated polyester resin, a crosslinking agent having a double bond and an epoxy group in one molecule, a photopolymerization initiator, and an inorganic filler in a predetermined ratio. When necessary, reinforcing materials and the like are further added to the mixture, and the mixture is kneaded and pressed using a kneading machine such as a kneader or roll to form a sheet, or it is extruded into a sheet using an extruder.
通常、不飽和ポリエステル樹脂シート状体は、厚みが３
肋以下に設定される。すなわち、このように厚みを設定
すると、後記のような光照射（通常、紫外線照射）の際
にシート状態の全体がＢステージ化するようになるから
である。ここで不飽和ポリエステル樹脂シート状体の製
造原料について説明する。不飽和ポリエステル樹脂とし
ては、グリコール、不飽和二塩基酸、飽和二塩基酸を用
い通常のようにして合成されたものが用いられる。架橋
剤としては、１分子中に二重結合とェポキシ基とをもつ
もの、例えば、グリシジルメタクリレート、グリシジル
アクリレート、グリシジルアリルエーテル等が単独でま
たは併せて用いられる。これらは、通常、不飽和ポリエ
ステル樹脂に対して５重量％（以下「％」と略す）以上
の割合で使用される。光重合開始材としては、ベンゾイ
ン、ベンゾィンメチルエーテル、ベンゾインエチルエー
テル、ベンゾインイソプｏピルエーテル、ベンゾフヱノ
ン、ジアセチル、アントラキノン等が用いられる。これ
らは、通常、不飽和ポリエステル樹脂に対して０．１〜
２％の割合で使用される。無機充填材としては、炭酸カ
ルシウム、シリカ粉末、クレー、マィカ、水和アルミナ
、タルク等が用いられる。これらは、通常、不飽和ポリ
エステル樹脂に対して５０〜５００％の割合で使用され
る。補強材としては、ガラス繊維、パルプ、合成繊維（
ポリエステル繊維、ビニロン繊維、ナイロン繊維、アク
リル繊維）等が用いられる。これらは必要に応じて使用
される。ェポキシ樹脂舎浸プリプレグは、サブラィナ−
用に用いられるもので、ェポキシ樹脂をガラス布、不織
布、マット、紙等に含浸させたものである。Usually, the unsaturated polyester resin sheet has a thickness of 3
It is set below the ribs. That is, if the thickness is set in this manner, the entire sheet state becomes B-staged upon light irradiation (usually ultraviolet ray irradiation) as described below. Here, raw materials for producing the unsaturated polyester resin sheet will be explained. As the unsaturated polyester resin, one synthesized in a conventional manner using glycol, unsaturated dibasic acid, or saturated dibasic acid is used. As the crosslinking agent, those having a double bond and an epoxy group in one molecule, such as glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, etc., are used alone or in combination. These are usually used in a proportion of 5% by weight or more (hereinafter abbreviated as "%") based on the unsaturated polyester resin. As the photopolymerization initiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, diacetyl, anthraquinone, etc. are used. These are usually 0.1 to 0.1 to unsaturated polyester resin.
Used at a rate of 2%. As the inorganic filler, calcium carbonate, silica powder, clay, mica, hydrated alumina, talc, etc. are used. These are usually used in a proportion of 50 to 500% based on the unsaturated polyester resin. As reinforcement materials, glass fiber, pulp, synthetic fiber (
Polyester fibers, vinylon fibers, nylon fibers, acrylic fibers), etc. are used. These are used as needed. Epoxy resin prepreg is a subliner.
It is used for various purposes, and is made by impregnating glass cloth, nonwoven fabric, mat, paper, etc. with epoxy resin.
このものは、加熱により硬化する。金属箔としては、通
常、鋼箔が用いられる。This material is cured by heating. Steel foil is usually used as the metal foil.
この発明は、以上のような原料を用い、例えばつぎのよ
うにして金属箔張り積層板を製造する。すなわち、コア
層用の不飽和ポリエステル樹脂シート状体に水銀灯より
光（紫外線）照射をする。その結果、シート状体中の樹
脂分がＢステージ化する。つぎに、光照射を経た不飽和
ポリエステル樹脂シート状体の両面にェポキシ樹脂舎浸
プリプレグを重ね、表面側のェポキシ樹脂含浸プリプレ
グの上にさらに銅箔を重ねて全体を熱圧成形する。その
結果、図面に示すような不飽和ポリエステル樹脂鋼張積
層板が得られる。図において、１は不飽和ポリエステル
コア層、２はサプライナー、３は銅箔である。このよう
にして得られた不飽和ポリエステル樹脂鋼張積層板は、
銅箔３とサプライナー２との接着状態が良好であり、し
かもサプライナー２と不飽和ポリエステルコア層１との
接着状態も極めて良好であり、層間剥離が全く生じない
のである。In the present invention, a metal foil-clad laminate is manufactured using the above-mentioned raw materials, for example, in the following manner. That is, the unsaturated polyester resin sheet for the core layer is irradiated with light (ultraviolet light) from a mercury lamp. As a result, the resin content in the sheet material becomes B stage. Next, epoxy resin impregnated prepreg is layered on both sides of the unsaturated polyester resin sheet that has undergone light irradiation, copper foil is further layered on top of the epoxy resin impregnated prepreg on the front side, and the whole is hot-press molded. As a result, an unsaturated polyester resin steel clad laminate as shown in the drawings is obtained. In the figure, 1 is an unsaturated polyester core layer, 2 is a supplier, and 3 is a copper foil. The unsaturated polyester resin steel clad laminate thus obtained is
The adhesion state between the copper foil 3 and the supplier 2 is good, and the adhesion state between the supplier 2 and the unsaturated polyester core layer 1 is also extremely good, so that no delamination occurs at all.
このように、サプライナー２と不飽和ポリエステルコア
層１との接着状態が良好になるのはつぎのような理由に
よると考えられる。すなわち、不飽和ポリエステルコア
層１中の架橋剤（１分子中に二重結合とェポキシ基とを
もつ）は、その二重結合部分がコァ層１中の不飽和ポリ
エステル樹脂の架橋剤として働らき、ェポキシ基部分が
コァ層１と接しているサプライナー２中の硬化剤成分と
反応し橋かけ構造をつくる。この橋かけ構造により、コ
ア層１とサプライナー２との接着状態が極めて良好にな
るものと考えられる。なお、以上の説明では、不飽和ポ
リエステル樹脂シート状体に光照射をしたのちェポキシ
樹脂含浸プリプレグを重ねているが、ェポキシ樹脂含浸
プリプレグを重ねたのちに光照射をしてもよいのである
（この場合、光はプリプレグを通して照射されることに
なる。The reason why the adhesive state between the supplier 2 and the unsaturated polyester core layer 1 is improved in this way is considered to be as follows. That is, the crosslinking agent (having a double bond and an epoxy group in one molecule) in the unsaturated polyester core layer 1 has a double bond that acts as a crosslinking agent for the unsaturated polyester resin in the core layer 1. , the epoxy group reacts with the curing agent component in the supplier 2 that is in contact with the core layer 1 to form a crosslinked structure. It is considered that this bridging structure makes the adhesion between the core layer 1 and the supplier 2 extremely good. In the above explanation, the unsaturated polyester resin sheet is irradiated with light and then the epoxy resin-impregnated prepreg is layered, but it is also possible to layer the epoxy resin-impregnated prepreg and then irradiate it with light. In this case, the light will be irradiated through the prepreg.
）つぎに、実施例について比較例と併せて説明する。) Next, Examples will be described together with Comparative Examples.
〔実施例 １〜３〕
ィソフタル酸５モル、エチレングリコール７モル、プロ
ピレングリコール３．５モルフラスコに仕込み、窒素の
存在下において２００ｑｏの酸価が３１になるまで反応
させた。[Examples 1 to 3] 5 moles of isophthalic acid, 7 moles of ethylene glycol, and 3.5 moles of propylene glycol were charged into a flask and reacted in the presence of nitrogen until the acid value of 200 qo reached 31.
つぎに、フマル酸を５モル仕込んで反応を続け、酸化１
＆軟化温度９が０の不飽和ポリエステル樹脂■を得た。
つぎに、不飽和ポリエステル樹脂凶１０の重量部（以下
「部」と称す）、水和アルミナ３０庇郭、ベンゾイソ１
部、ガラス短繊維４碇部および後記の表に示す架橋剤を
同表に示す量だけ配合し、これをニーダ−で混練し「厚
み１．５肋のスベーサーを用いて１００ｑｏ，３０ｋ９
ノ係の条件でプレスし厚み１．５肌の不飽和ポリエステ
ル樹脂シート状体をつくった。つぎに、この不飽和ポリ
エステル樹脂シート状体に、８０Ｗ／伽の高圧水銀等に
より紫外線を３０００ｍｉ／地の割合で照射しＢステー
ジ化した。つぎに、この不飽和ポリエステル樹脂シート
状体の上に、ュポキシ樹脂ワニス（シェル社製ェピコー
ト８２７を１０碇郡とジシアンジアミドを１部とＭＥＫ
を１０礎部混合したもの）をガラス布に含浸してなるェ
ポキシ樹脂含浸プリプレグ（サブラィナ−用）を重ね、
表面側のェポキシ樹脂舎浸プリプレグの上に厚み３５ム
の銅箔をさらに重ねて１７０ｑｏ，３０ｋ９／地の条件
で１時間熱圧成形して不飽和ポリエステル樹脂鋼張積層
板を得た。〔実施例 ４〕
テレフタル酸ジメチル５モル、フマル酸５モル、エチレ
ングリコール１．１モルを用い、通常のようにして軟化
温度９ｇ０の不飽和ポリエステル樹脂を合成した。Next, 5 moles of fumaric acid were charged and the reaction was continued to oxidize 1
& An unsaturated polyester resin (2) with a softening temperature of 9 and a softening temperature of 0 was obtained.
Next, 10 parts by weight (hereinafter referred to as "parts") of unsaturated polyester resin, 30 parts of hydrated alumina, and 1 part of benzoisomer were added.
1 part, 4 parts of short glass fiber, and the crosslinking agent shown in the table below were blended in the amount shown in the same table, and kneaded in a kneader to make 100 qo, 30 k9
An unsaturated polyester resin sheet having a thickness of 1.5 mm was produced by pressing under the following conditions. Next, this unsaturated polyester resin sheet was irradiated with ultraviolet rays at a rate of 3000 mi/ground using high-pressure mercury of 80 W/g to give it a B stage. Next, on this unsaturated polyester resin sheet, a supoxy resin varnish (10 coats of Epicoat 827 manufactured by Shell Co., Ltd., 1 part of dicyandiamide, and MEK) was applied.
Layer epoxy resin-impregnated prepreg (for subliner) made by impregnating glass cloth with
A copper foil with a thickness of 35 mm was further layered on the epoxy resin soaked prepreg on the front side, and hot-press molded for 1 hour under conditions of 170 qo, 30 k9/ground to obtain an unsaturated polyester resin steel-clad laminate. [Example 4] An unsaturated polyester resin having a softening temperature of 9 g0 was synthesized in a conventional manner using 5 moles of dimethyl terephthalate, 5 moles of fumaric acid, and 1.1 moles of ethylene glycol.
つぎに、不飽和ポリエステル樹脂１０礎都、クレー２５
碇都、ベンゾインメチルエーテル１．２部、ビニロン繊
維５部、ジアリルフタレート１の部、グリシジルメタク
リレート１碇都の割合で配合し、これを２鞠押出機で押
し出し、厚み１．２側の不飽和ポリエステル樹脂シート
状体をつくった。つぎに、この不飽和ポリエステル樹脂
シート状体に、８０Ｗ／伽の高圧水銀灯により紫外線を
２０００肌ｉ／流の割合で照射してＢステージ化した。
これ以降は実施例１〜３と同機にして不飽和ポリエステ
ル樹脂鋼張積層板を得た。〔比較例 １，２〕
不飽和ポリエステル樹脂シート状体に含有させる架橋剤
として、後記の表に示す架橋剤を用いた。Next, unsaturated polyester resin 10 foundations, clay 25
A mixture of Ikarito, 1.2 parts of benzoin methyl ether, 5 parts of vinylon fiber, 1 part of diallyl phthalate, and 1 part of glycidyl methacrylate was extruded using a 2-mari extruder to form an unsaturated layer with a thickness of 1.2. A polyester resin sheet was made. Next, this unsaturated polyester resin sheet was irradiated with ultraviolet rays at a rate of 2,000 skin i/flow using a high-pressure mercury lamp of 80 W/g to give it a B stage.
From this point on, unsaturated polyester resin steel-clad laminates were obtained using the same machine as in Examples 1 to 3. [Comparative Examples 1 and 2] As the crosslinking agent contained in the unsaturated polyester resin sheet, the crosslinking agents shown in the table below were used.
それ以外は実施例１〜３と同様にして不飽和ポリエステ
ル樹脂鋼張積層板を得た。以上の実施例および比較例で
得られた不飽和ポリエステル樹脂鋼張積層板の鋼箔の引
剥し強度と、サプライナーとコア層との間の引剥し強度
（層間引剥し強度）を調べた。Other than that, unsaturated polyester resin steel-clad laminates were obtained in the same manner as in Examples 1 to 3. The peel strength of the steel foil of the unsaturated polyester resin steel-clad laminates obtained in the above Examples and Comparative Examples and the peel strength between the supplier and the core layer (interlaminar peel strength) were investigated.
その結果を後記の表に示した。実施例の銅張積層板は、
鋼箔の引剥し強度およびサプライナーとコア層との間の
引剥し強度が共に大である。これに対し、比較例の銅張
積層板は、銅箔の引剥し強度は大であるがサブラィナ−
とコア層との間の引剥し強度が小さいことがわかる。The results are shown in the table below. The copper clad laminate of the example is
Both the peel strength of the steel foil and the peel strength between the supplier and the core layer are high. On the other hand, the copper-clad laminate of the comparative example has high peel strength of the copper foil, but the subliner
It can be seen that the peel strength between the material and the core layer is small.
図面はこの発明にかかる不飽和ポリエステル樹脂銅張積
層板の断面図である。
１…・・・不飽和ポリエステルコア層、２・・・・・・
サプライナー、３・・・・・・鋼箔。The drawing is a sectional view of an unsaturated polyester resin copper-clad laminate according to the present invention. 1... Unsaturated polyester core layer, 2...
Supplier, 3... Steel foil.
Claims (1)
ポキシ樹脂含浸プリプレグを重ねる工程と、このエポキ
シ樹脂含浸プリプレグを前記の不飽和ポリエステル樹脂
シート状体に重ねる前後の少なくとも一方の段階で不飽
和ポリエステル樹脂シート状体に光照射をする工程と、
前記の光照射ののち前記の不飽和ポリエステル樹脂シー
ト状体に重ねられた前記のエポキシ樹脂含浸プリプレグ
の上に金属箔を重ねて全体を加熱加圧成形する工程を備
える金属箔張り積層板の製法であって、不飽和ポリエス
テル樹脂シート状体として、１分子中に二重結合とエポ
キシ基とをもつ架橋剤を含有する不飽和ポリエステル樹
脂シート状体を用いることを特徴とする金属箔張り積層
板の製法。 ２ １分子中に二重結合とエポキシ基とをもつ架橋剤が
、グリシジルメタクリレート、グリシジルアクリレート
およびグリシジルアリルエーテルからなる群から選ばれ
た少なくとも一つの架橋剤である特許請求の範囲第１項
記載の金属箔張り積層板の製法。 ３ １分子中に二重結合とエポキシ基とをもつ架橋剤の
含有量が、不飽和ポリエステル樹脂シート状体中の不飽
和ポリエステル樹脂に対して５重量％以上になるように
選ばれている特許請求の範囲第１項または第２項記載の
金属箔張り積層板の製法。[Scope of Claims] 1. A step of stacking an epoxy resin-impregnated prepreg on an unsaturated polyester resin sheet for a core layer, and at least one of the steps before and after stacking the epoxy resin-impregnated prepreg on the unsaturated polyester resin sheet. A step of irradiating the unsaturated polyester resin sheet with light,
A method for producing a metal foil-clad laminate comprising the step of overlaying a metal foil on the epoxy resin-impregnated prepreg layered on the unsaturated polyester resin sheet after the light irradiation, and heating and press-molding the whole. A metal foil-clad laminate, characterized in that an unsaturated polyester resin sheet containing a crosslinking agent having a double bond and an epoxy group in one molecule is used as the unsaturated polyester resin sheet. manufacturing method. 2. The crosslinking agent having a double bond and an epoxy group in one molecule is at least one crosslinking agent selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, and glycidyl allyl ether. Manufacturing method for metal foil laminates. 3. A patent in which the content of a crosslinking agent having a double bond and an epoxy group in one molecule is selected to be 5% by weight or more based on the unsaturated polyester resin in the unsaturated polyester resin sheet. A method for manufacturing a metal foil-clad laminate according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55008134A JPS6012232B2 (en) | 1980-01-26 | 1980-01-26 | Manufacturing method for metal foil laminates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55008134A JPS6012232B2 (en) | 1980-01-26 | 1980-01-26 | Manufacturing method for metal foil laminates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56105923A JPS56105923A (en) | 1981-08-22 |
| JPS6012232B2 true JPS6012232B2 (en) | 1985-03-30 |
Family
ID=11684810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55008134A Expired JPS6012232B2 (en) | 1980-01-26 | 1980-01-26 | Manufacturing method for metal foil laminates |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6012232B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9480148B2 (en) | 2011-02-21 | 2016-10-25 | Panasonic Intellectual Property Management Co., Ltd. | Metal-clad laminate and printed wiring board |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61213115A (en) * | 1985-03-18 | 1986-09-22 | Shin Kobe Electric Mach Co Ltd | Manufacture of insulation board for printinted circuit |
-
1980
- 1980-01-26 JP JP55008134A patent/JPS6012232B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9480148B2 (en) | 2011-02-21 | 2016-10-25 | Panasonic Intellectual Property Management Co., Ltd. | Metal-clad laminate and printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56105923A (en) | 1981-08-22 |
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