JPH0361588B2 - - Google Patents
Info
- Publication number
- JPH0361588B2 JPH0361588B2 JP59066676A JP6667684A JPH0361588B2 JP H0361588 B2 JPH0361588 B2 JP H0361588B2 JP 59066676 A JP59066676 A JP 59066676A JP 6667684 A JP6667684 A JP 6667684A JP H0361588 B2 JPH0361588 B2 JP H0361588B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- sheet
- plating
- laminate
- additive
- 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 - Lifetime
Links
- 238000007747 plating Methods 0.000 claims description 42
- 239000000853 adhesive Substances 0.000 claims description 32
- 230000001070 adhesive effect Effects 0.000 claims description 32
- 239000000654 additive Substances 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 23
- 229920000459 Nitrile rubber Polymers 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 11
- 150000002484 inorganic compounds Chemical class 0.000 claims description 9
- 229910010272 inorganic material Inorganic materials 0.000 claims description 9
- 239000002313 adhesive film Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 150000003904 phospholipids Chemical class 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- 239000012790 adhesive layer Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000005011 phenolic resin Substances 0.000 description 11
- 239000011888 foil Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 229920001568 phenolic resin Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940067606 lecithin Drugs 0.000 description 4
- 235000010445 lecithin Nutrition 0.000 description 4
- 239000000787 lecithin Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 alkyl phenols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
Description
〔産業上の利用分野〕
本発明は、化学銅めつきによる銅の密着性の良
好なアデイテイブめつき用積層板に関するもので
ある。
〔従来技術〕
一般的にアデイテイブめつき用積層板は、いわ
ゆるアデイテイブプロセスにより、印刷回路板を
製造するための基板素材である。
この場合、基板表面の絶縁接着剤としては、ア
クリロニトリル・ブタジエンゴム（以下、NBR
という）とフエノール樹脂とからなる組成のもの
が主として使用されているが、アデイテイブプロ
セス中の各種の溶剤処理によつて、膨潤又はフク
レが発生する等の欠点がある。さらに、銅めつき
皮膜と接着剤層との密着性も弱く、特に印刷回路
板として半田付時に必要な半田耐熱性も不充分で
ある。
このような欠点を改良するために、NBR、フ
エノール樹脂、エポキシ樹脂を含む接着剤もある
が、耐溶剤性は改良されているものの銅めつき皮
膜と接着剤層との密着性が不充分である。
また、NBR、フエノール樹脂及び無機化合物
を含む接着剤もあるが、アデイテイブめつき用積
層板の製造工程において、剥離性シートに該接着
剤を塗布・乾燥して得られたシートを、接着剤面
を内側にして所定枚数の熱硬化性樹脂含浸紙布を
重ね合せ加熱加圧して一体化して両面に接着剤付
基板をつくるに際し、剥離性シートを除去するこ
とが極めて困難である。特に剥離性シートとして
金属箔を用いる場合には、前記接着剤と金属箔と
が密着してしまうため剥離、除去することが極め
て困難である。
また、NBR、フエノール樹脂、無機化合物の
材料選定に当つて、NBR中のアクリロニトリル
の含有量、フエノール樹脂の種類、無機化合物の
種類及び接着剤層の膜厚が不適当であるため、銅
めつき皮膜と接着剤層の優れた密着力を得ること
ができず、また、電気特性上も良好なものが得ら
れなかつた。
〔発明の目的〕
本発明は、従来技術の接着剤層の耐溶剤性不良
及び銅めつき皮膜と接着剤層との密着性不良を改
良すること、及びアデイテイブめつき用積層板製
造に際し剥離シートの簡便な剥離を可能にするこ
とを目的として検討し完成されたものであり、接
着剤層の耐溶剤性及び銅めつき皮膜と接着剤層と
の密着性が良好で、且つ剥離シートを簡単に剥離
できるアデイテイブめつき用積層板を提供するも
のである。
〔発明の構成〕
本発明は、NBR、レゾール型フエーノル樹脂、
水に不溶性で分解温度300℃以上の電気絶縁性の
無機化合物及びリン脂質体とからなる接着剤を剥
離性のシートに塗布し、このシートと任意の枚数
の熱硬化性樹脂含浸紙布とを前記シートの接着剤
塗布面を内側にして重ね合わせ、加熱加圧一体化
することを特徴とするアデイテイブめつき用積層
板の製造方法である。
NBRとしては、ニトリル含有率35％以上の高
アクリルニトリル−ブタジエンゴムを使用する。
その理由はアデイテイブめつきプロセスにおける
各種の有機溶剤及び強酸、強アルカリに耐えるた
めには、耐薬品性に優れている高アクリルニトリ
ル−ブタジエンゴムがよい。特にニトリル含有率
35〜50％のものが好ましい。
レゾール型フエノール樹脂としてはストレート
系のものでもよいが油変性フエノール樹脂、アル
キル変性フエノール樹脂が好ましい。この理由は
NBRとの相溶性及び反応性が良く、いわゆる樹
脂加硫ができるからである。従つて、アデイテイ
ブめつきプロセスにおける耐薬品性を付与するこ
とができる。従つて、このようなフエノール樹脂
としては、分子量94〜500で、変性率については、
油変性フエノールの場合は10〜50％、アルキルフ
エノールの場合５〜30％のものが好ましい。
水に不溶性で分解温度300℃以上の電気絶縁性
の無機化合物としては、例えばSiO2、TiO2、
Al2O3等がある。特に酸やアルカリ水溶液に対す
る不溶性のものが好ましく、この点及び微粉末の
入手しやすさ等よりSiO2が好ましい。
該無機化合物の粒径は平均粒径1mμｍ〜20μｍ
のものがよい。アデイテイブめつきプロセス後の
銅めつき皮膜と接着剤層との密着力を強くするた
めには、一次粒子として5mμｍ〜5μｍのものが好
ましい。
リン脂質体は、加熱加圧によりアデイテイブめ
つき用積層板を製造した後、剥離シートを接着剤
表面より剥離除去しやすくするためのものであ
り、レシチンが好ましい。添加量としては、接着
剤固形分に対し0.1〜５％の範囲内で剥離性の程
度に応じて選定することができる。
各成分の配合割合は、NBR40〜60％、レゾー
ル型フエノール樹脂60〜40％、無機化合物0.5〜
5.0％、リン脂質体0.1〜5.0％がよい。
このような配合物は必要により、あらかじめ適
切な溶剤で溶解しておくことができる。このよう
な接着剤溶液を剥離シートに塗布する。
剥離シートは、金属箔、プラスチツクフイル
ム、紙等が使用可能であるが、接着剤塗布後の乾
燥工程における耐熱性の点から金属箔がよい。特
に、コストの点からアルミ箔が好ましい。
乾燥工程は、熱風により接着剤中の溶剤を乾燥
除去すると共に、接着剤成分のNBRとフエノー
ル樹脂の熱反応をある一定程度まで進めるための
ものである。
接着剤の塗布は、ロールコーター、バーコータ
ー、カーテンフローコート、スワイズロールによ
る転写等により実施でき、これに続いて熱風式乾
燥胴により連続的に乾燥することができる。接着
剤膜厚は、乾燥後20〜200μｍがよい。特に、30
〜120μｍがめつき密着性及び塗布作業上好まし
い。
このようにして得られた接着剤塗布剥離性シー
トを、接着剤面を内側にして所定枚数の熱硬化性
樹脂含浸紙布と重ね合わせ、加熱加圧により一体
化し、接着剤付アデイテイブめつき用積層板をつ
くることができる。
以下、アデイテイブプロセスについて簡単に説
明する。
上記アデイテイブめつき用積層板より剥離性シ
ートを剥離除去する。必要に応じて穴をあけ及び
乾燥処理をした後に、クロム酸／硫酸により接着
剤層を酸化・粗面化し、パラジユウム等による銅
めつきのための活性化処理をし、必要に応じてめ
つきレジストを施し、化学的銅めつきにより導体
回路を形成することができる。更に、必要に応じ
て電気銅めつきを使うこともできる。その後、め
つきレジストは必要に応じて除去してもよい。
〔発明の効果〕
本発明で得られたアデイテイブめつき用積層板
は次のような特長を有している。
１ 接着剤中に、無機化合物の微細な粒子を含有
しているため、クロム酸／硫酸による酸化・粗
面化の際に微細な粗面を形成できる。
２ 従つて、化学的銅めつきにより密着性及び析
出スピードが極めて良好であり、回路形成後の
半田付時に回路のハガレ、フクレ等が皆無であ
る。
３ 適度の割合のNBRとレゾール型フエノール
樹脂により、三次元網目構造が形成されてお
り、さらに無機化合物の補強効果により、めつ
きレジスト形成工程における各種の有機溶剤処
理に対して接着剤層が膨潤、溶解、剥離、変質
等を起こさない。
４ 前記のような特長を損うことなく、剥離性シ
ートの除去が容易である。
〔実施例〕
本発明によるアデイテイブめつき用積層板の製
造法を以下に実施例により説明する。
実施例 １
NBR（アクリロニトリル37％含有） 1000ｇ
レゾール型アルキル変性フエノール樹脂（変性率
20％） 1000
SiO2（平均粒径15mμｍ） 20
レシチン ２
メチルエチルケトン 5000
上記の樹脂混合物を、80℃で３時間撹拌混合し
て接着剤溶液を得た。
この接着剤溶液を50μｍ厚のアルミ箔にロール
コート方式で塗布し、50〜160℃の連続乾燥胴を
通して乾燥した。接着剤膜厚は100μｍであつた。
この接着剤塗布アルミ箔を接着剤面を内側にして
８枚のエポキシ樹脂含浸ガラスクロスの内面に１
枚ずつ重ね合わせ、160℃、100Kg／cm2で120分間
加熱加圧して一体化し、両面に接着剤付の厚み
1.6mmのアデイテイブめつき用積層板を得た。
実施例 ２
NBR（アクリロニトリル含有率35％） 1000ｇ
レゾール型フエノール樹脂 1200
TiO2（平均粒径0.3μｍ） 15
レシチン ３
トルエン 2000
メチルエチルケトン 3000
上記の樹脂混合物を80℃で３時間撹拌混合して
接着剤溶液を得た。
この接着剤溶液を100μｍ厚のポリプロピレン
シートにスクイズロール方式で転写塗布し、50〜
130℃の連続乾燥胴を通して乾燥した。接着剤膜
厚は50μｍであつた。
以下、実施例１と同様にして加熱加圧し、アデ
イテイブめつき用積層板を得た。
比較例 １
NBR（アクリロニトリル含有率35％） 1000ｇ
ノボラツク型アルキル変性フエーノール樹脂
1000ｇ
レシチン ２
メチルエチルケトン 5000
上記の樹脂混合物を80℃で３時間撹拌混合し、
接着剤溶液を得た。この接着剤溶液を厚さ50μｍ
のアルミ箔に塗布し乾燥した。接着剤膜厚は50μ
ｍであつた。
以下、実施例１と同様にしてアデイテイブめつ
き用積層板を得た。
比較例 ２
NBR（アクリロニトリル含有率20％） 1000ｇ
ノボラツク型カシユー変性フエノール樹脂1000
SiO2（平均粒径40mμｍ） ５
メチルエチルケトン 5000
上記樹脂混合物を80℃で３時間撹拌混合して接
着剤溶液を得た。該接着剤溶液を厚さ50μｍのア
ルミ箔に塗布し乾燥した。接着剤膜厚は100μｍ
であつた。
以下、実施例１と同様にしてアデイテイブめつ
き用積層板を得た。
実施例１、実施例２、比較例１、比較例２で得
られたアデイテイブめつき用積層板を次の(a)〜(g)
の工程で、処理し、化学的銅めつきを施した。
特性を評価した結果は第１表の通りであつた。
＜化学銅めつき工程＞
(a) 剥離性シートの除去
(b) クロム酸／硫酸混液処理
(c) 活性化処理
(d) めつきレジスト形成
(e) 化学的銅めつき（めつき厚30μｍ）
(f) めつきレジストの除去
(g) 乾燥
[Industrial Field of Application] The present invention relates to a laminate for additive plating that has good copper adhesion by chemical copper plating. [Prior Art] In general, additive plating laminates are substrate materials for manufacturing printed circuit boards by a so-called additive process. In this case, the insulating adhesive on the substrate surface is acrylonitrile-butadiene rubber (hereinafter referred to as NBR).
Although compositions consisting of a phenolic resin and a phenol resin are mainly used, they have drawbacks such as swelling or blistering caused by various solvent treatments during the additive process. Furthermore, the adhesion between the copper plating film and the adhesive layer is weak, and the soldering heat resistance necessary for soldering, especially for printed circuit boards, is also insufficient. In order to improve these defects, there are adhesives containing NBR, phenolic resin, and epoxy resin, but although the solvent resistance is improved, the adhesion between the copper plating film and the adhesive layer is insufficient. be. There are also adhesives containing NBR, phenolic resins, and inorganic compounds, but in the process of manufacturing laminates for additive plating, the sheet obtained by coating and drying the adhesive on a releasable sheet is coated with the adhesive side. It is extremely difficult to remove the removable sheet when a predetermined number of paper cloths impregnated with a thermosetting resin are stacked on top of each other and heated and pressurized to form a substrate with adhesive on both sides. In particular, when a metal foil is used as the releasable sheet, the adhesive and the metal foil are in close contact with each other, making it extremely difficult to peel and remove the sheet. In addition, when selecting materials for NBR, phenolic resin, and inorganic compounds, copper plating was It was not possible to obtain excellent adhesion between the film and the adhesive layer, and also it was not possible to obtain good electrical properties. [Object of the Invention] The present invention aims to improve the poor solvent resistance of the adhesive layer and the poor adhesion between the copper plating film and the adhesive layer in the prior art, and to improve the poor solvent resistance of the adhesive layer and the poor adhesion between the copper plating film and the adhesive layer, and to provide a release sheet for producing a laminate for additive plating. This product was developed with the aim of enabling easy removal of the adhesive layer, and the adhesive layer has good solvent resistance and adhesion between the copper plating film and the adhesive layer, and the release sheet can be easily removed. To provide a laminate for additive plating that can be peeled off. [Structure of the invention] The present invention provides NBR, resol type phenol resin,
An adhesive consisting of an electrically insulating inorganic compound and a phospholipid substance that is insoluble in water and has a decomposition temperature of 300°C or higher is applied to a removable sheet, and this sheet and an arbitrary number of thermosetting resin-impregnated paper cloth are bonded together. This is a method for producing a laminate for additive plating, which comprises stacking the sheets with the adhesive-coated surfaces facing inside and integrating them under heat and pressure. As NBR, a high acrylonitrile-butadiene rubber with a nitrile content of 35% or more is used.
The reason for this is that high acrylonitrile-butadiene rubber, which has excellent chemical resistance, is preferred in order to withstand various organic solvents, strong acids, and strong alkalis in the additive plating process. Especially the nitrile content
35-50% is preferred. The resol type phenolic resin may be a straight type, but oil-modified phenolic resins and alkyl-modified phenolic resins are preferred. The reason for this is
This is because it has good compatibility and reactivity with NBR and can be used for so-called resin vulcanization. Therefore, chemical resistance in the additive plating process can be imparted. Therefore, such a phenolic resin has a molecular weight of 94 to 500 and a modification rate of
In the case of oil-modified phenols, it is preferably 10 to 50%, and in the case of alkyl phenols, it is preferably 5 to 30%. Examples of electrically insulating inorganic compounds that are insoluble in water and have a decomposition temperature of 300°C or higher include SiO 2 , TiO 2 ,
There are Al 2 O 3 etc. Particularly preferred is one that is insoluble in acid or alkaline aqueous solutions, and SiO 2 is preferred from this point of view and the ease of obtaining fine powder. The particle size of the inorganic compound is an average particle size of 1 mμm to 20 μm.
The one is good. In order to strengthen the adhesion between the copper plating film and the adhesive layer after the additive plating process, it is preferable that the primary particles have a diameter of 5 mm to 5 μm. The phospholipid substance is used to make it easier to peel off and remove the release sheet from the adhesive surface after producing a laminate for additive plating by heating and pressing, and lecithin is preferable. The amount added can be selected within the range of 0.1 to 5% based on the solid content of the adhesive, depending on the degree of releasability. The blending ratio of each component is NBR 40-60%, resol type phenolic resin 60-40%, and inorganic compound 0.5-60%.
5.0%, phospholipid body 0.1-5.0% is good. Such a compound can be dissolved in advance in a suitable solvent, if necessary. Such an adhesive solution is applied to a release sheet. Metal foil, plastic film, paper, etc. can be used as the release sheet, but metal foil is preferable from the viewpoint of heat resistance in the drying process after applying the adhesive. In particular, aluminum foil is preferred from the viewpoint of cost. The drying step is to dry and remove the solvent in the adhesive using hot air, and to advance the thermal reaction between the adhesive components NBR and phenol resin to a certain degree. The adhesive can be applied by a roll coater, a bar coater, curtain flow coating, transfer using a swivel roll, etc., followed by continuous drying using a hot air drying cylinder. The adhesive film thickness is preferably 20 to 200 μm after drying. In particular, 30
~120 μm is preferable in terms of plating adhesion and coating work. The thus obtained adhesive-coated removable sheet is overlaid with a predetermined number of thermosetting resin-impregnated paper cloth with the adhesive side facing inside, and is integrated by heating and pressing. You can make laminates. The additive process will be briefly explained below. The releasable sheet is removed from the additive plating laminate. After drilling holes and drying as necessary, the adhesive layer is oxidized and roughened with chromic acid/sulfuric acid, activated with palladium etc. for copper plating, and as required, a plating resist is applied. A conductor circuit can be formed by chemical copper plating. Furthermore, electrolytic copper plating can be used if necessary. Thereafter, the plating resist may be removed if necessary. [Effects of the Invention] The laminate for additive plating obtained by the present invention has the following features. 1. Because the adhesive contains fine particles of inorganic compounds, a fine roughened surface can be formed during oxidation and roughening with chromic acid/sulfuric acid. 2. Therefore, chemical copper plating provides extremely good adhesion and deposition speed, and there is no peeling or blistering of the circuit during soldering after circuit formation. 3 A three-dimensional network structure is formed by a moderate proportion of NBR and resol type phenolic resin, and the reinforcing effect of the inorganic compound allows the adhesive layer to swell when treated with various organic solvents in the plating resist forming process. , will not cause dissolution, peeling, deterioration, etc. 4. The removable sheet can be easily removed without sacrificing the above-mentioned features. [Example] The method for producing a laminate for additive plating according to the present invention will be explained below using Examples. Example 1 NBR (containing 37% acrylonitrile) 1000g resol type alkyl-modified phenol resin (modification rate
20%) 1000 SiO 2 (average particle size 15 mμm) 20 Lecithin 2 Methyl ethyl ketone 5000 The above resin mixture was stirred and mixed at 80° C. for 3 hours to obtain an adhesive solution. This adhesive solution was applied to a 50 μm thick aluminum foil using a roll coating method and dried through a continuous drying cylinder at 50 to 160°C. The adhesive film thickness was 100 μm.
Place this adhesive coated aluminum foil on the inner surface of 8 pieces of epoxy resin impregnated glass cloth with the adhesive side inside.
Layer each sheet one by one, heat and press at 160℃ and 100Kg/cm 2 for 120 minutes to integrate, with adhesive on both sides.
A 1.6 mm additive plating laminate was obtained. Example 2 NBR (acrylonitrile content 35%) 1000g Resol type phenolic resin 1200 TiO 2 (average particle size 0.3μm) 15 Lecithin 3 Toluene 2000 Methyl ethyl ketone 3000 The above resin mixture was stirred and mixed at 80°C for 3 hours to prepare an adhesive solution. I got it. This adhesive solution was transfer-coated onto a 100 μm thick polypropylene sheet using a squeeze roll method.
It was dried through a continuous drying cylinder at 130°C. The adhesive film thickness was 50 μm. Thereafter, heat and pressure were applied in the same manner as in Example 1 to obtain a laminate for additive plating. Comparative example 1 NBR (acrylonitrile content 35%) 1000g Novolac type alkyl-modified phenolic resin
1000g lecithin 2 methyl ethyl ketone 5000 Stir and mix the above resin mixture at 80℃ for 3 hours,
An adhesive solution was obtained. Apply this adhesive solution to a thickness of 50 μm.
It was applied to aluminum foil and dried. Adhesive film thickness is 50μ
It was m. Thereafter, a laminate for additive plating was obtained in the same manner as in Example 1. Comparative Example 2 NBR (acrylonitrile content 20%) 1000g Novolac type cashew modified phenolic resin 1000 SiO 2 (average particle size 40mμm) 5 Methyl ethyl ketone 5000 The above resin mixture was stirred and mixed at 80°C for 3 hours to obtain an adhesive solution. The adhesive solution was applied to a 50 μm thick aluminum foil and dried. Adhesive film thickness is 100μm
It was hot. Thereafter, a laminate for additive plating was obtained in the same manner as in Example 1. The additive plating laminates obtained in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were subjected to the following procedures (a) to (g).
In the process, it was treated and chemically copper plated. The results of evaluating the properties are shown in Table 1. <Chemical copper plating process> (a) Removal of release sheet (b) Chromic acid/sulfuric acid mixture treatment (c) Activation treatment (d) Plating resist formation (e) Chemical copper plating (plating thickness 30μm) ) (f) Removal of plating resist (g) Drying
【表】
銅めつき皮膜引きはがし強さ及び半田耐熱性の
テスト方法は、JIS C6481による。[Table] Test methods for copper plating peel strength and soldering heat resistance are based on JIS C6481.
Claims (1)
ニトリル・ブタジエンゴム、レゾール型フエノー
ル樹脂、水に不溶性で分解温度300℃以上の電気
絶縁性の無機化合物及びリン脂質体からなる接着
剤を剥離性のシート上に塗布・乾燥し、このシー
トと任意の枚数の熱硬化性樹脂含浸紙布とを、前
記シートの接着剤塗布面を内側にして、重ね合
せ、加熱加圧一体化することを特徴とするアデイ
テイブめつき用積層板の製造方法。 ２ 乾燥後の接着剤膜厚が20μｍ〜200μｍである
ことを特徴とする特許請求の範囲第１項記載のア
デイテイブめつき用積層板の製造方法。[Scope of Claims] 1. An adhesive consisting of acrylonitrile-butadiene rubber with an acrylonitrile content of 35% or more, a resol type phenolic resin, an electrically insulating inorganic compound that is insoluble in water and has a decomposition temperature of 300°C or more, and a phospholipid. Coating and drying on a removable sheet, overlapping this sheet and an arbitrary number of thermosetting resin-impregnated paper cloth with the adhesive coated side of the sheet facing inside, and integrating the sheet with heat and pressure. A method for producing a laminate for additive plating, characterized by: 2. The method for producing a laminate for additive plating according to claim 1, wherein the adhesive film thickness after drying is 20 μm to 200 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59066676A JPS60210449A (en) | 1984-04-05 | 1984-04-05 | Manufacture of laminated board for plating additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59066676A JPS60210449A (en) | 1984-04-05 | 1984-04-05 | Manufacture of laminated board for plating additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60210449A JPS60210449A (en) | 1985-10-22 |
| JPH0361588B2 true JPH0361588B2 (en) | 1991-09-20 |
Family
ID=13322759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59066676A Granted JPS60210449A (en) | 1984-04-05 | 1984-04-05 | Manufacture of laminated board for plating additive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60210449A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6151990A (en) * | 1984-08-22 | 1986-03-14 | 株式会社日立製作所 | Method for manufacturing an insulating substrate with a metalized surface |
| JPH01154590A (en) * | 1987-12-11 | 1989-06-16 | Sumitomo Bakelite Co Ltd | Forming method for circuit |
-
1984
- 1984-04-05 JP JP59066676A patent/JPS60210449A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60210449A (en) | 1985-10-22 |
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