JP2004074799A - Insulating substrate to which copper is bonded - Google Patents
Insulating substrate to which copper is bonded Download PDFInfo
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- JP2004074799A JP2004074799A JP2003291585A JP2003291585A JP2004074799A JP 2004074799 A JP2004074799 A JP 2004074799A JP 2003291585 A JP2003291585 A JP 2003291585A JP 2003291585 A JP2003291585 A JP 2003291585A JP 2004074799 A JP2004074799 A JP 2004074799A
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- JP
- Japan
- Prior art keywords
- adhesive
- weight
- trade name
- manufactured
- butadiene rubber
- 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.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 17
- 239000010949 copper Substances 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 title claims abstract description 9
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 30
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims description 39
- 230000001070 adhesive effect Effects 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 13
- 238000007747 plating Methods 0.000 description 11
- 238000007788 roughening Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000007772 electroless plating Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CFRNDJFRRKMHTL-UHFFFAOYSA-N [3-octanoyloxy-2,2-bis(octanoyloxymethyl)propyl] octanoate Chemical compound CCCCCCCC(=O)OCC(COC(=O)CCCCCCC)(COC(=O)CCCCCCC)COC(=O)CCCCCCC CFRNDJFRRKMHTL-UHFFFAOYSA-N 0.000 description 2
- KLMREMBURZNLTP-UHFFFAOYSA-J [F-].[Na+].S(O)(O)(=O)=O.[Cr+3].[F-].[F-].[F-] Chemical compound [F-].[Na+].S(O)(O)(=O)=O.[Cr+3].[F-].[F-].[F-] KLMREMBURZNLTP-UHFFFAOYSA-J 0.000 description 2
- JZULKTSSLJNBQJ-UHFFFAOYSA-N chromium;sulfuric acid Chemical compound [Cr].OS(O)(=O)=O JZULKTSSLJNBQJ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 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 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、絶縁基材に関し、さらに詳細には、エポキシ樹脂と架橋したアクリロニトリルブタジエンゴム粒子とを含有する接着剤によって、銅と接着状態にある絶縁基材に関する。 The present invention relates to an insulating substrate, and more particularly, to an insulating substrate bonded to copper by an adhesive containing epoxy resin and crosslinked acrylonitrile butadiene rubber particles.
周知のように、アディティブ法プリント配線板は、接着剤付き絶縁基材に無電解めっきで必要な配線パターンを形成するものである。 As is well known, an additive printed wiring board forms a necessary wiring pattern on an insulating base material with an adhesive by electroless plating.
例えば、めっき触媒等を含有する絶縁基材上にめっき触媒を含有する接着剤層を形成し、１４０〜１９０℃の温度で２０〜９０分加熱して硬化させる。次いで、回路形成部以外をめっきレジストでマスクし、無電解めっき銅との接着力を向上するための前処理として、クロム−硫酸等の酸化性エッチング液で回路形成部の接着剤表面を選択的に化学粗化する。その後、中和及び水洗工程を経て無電解めっき液に浸漬し、回路部に銅を析出させて配線パターンを形成する。 (4) For example, an adhesive layer containing a plating catalyst is formed on an insulating substrate containing a plating catalyst and the like, and cured by heating at a temperature of 140 to 190 ° C. for 20 to 90 minutes. Next, the portions other than the circuit forming portion are masked with a plating resist, and as a pretreatment for improving the adhesive force with electroless plated copper, the adhesive surface of the circuit forming portion is selectively treated with an oxidizing etching solution such as chromium-sulfuric acid. To be chemically roughened. Then, after a neutralization and water washing process, it is immersed in an electroless plating solution, and copper is deposited on a circuit portion to form a wiring pattern.
このようなアディティブ法プリント配線板用接着剤としては、一般にめっき銅との接着性が良いアクリロニトリルブタジエンゴムを主成分とし、かつ耐熱性を確保するためにアルキルフェノール樹脂でアクリロニトリルブタジエンゴムを架橋し、また電気特性を確保するためにエポキシ樹脂を配合する。さらに、接着剤塗膜の補強や化学粗化時の接着剤凹凸増加のために、無機充填剤等を配合した接着剤が提案されてきた。このような接着剤に関する技術を開示するものとしては、特許文献１〜４等がある。
ところで、近年、電子機器の小型化、多機能化に伴い、プリント配線板はより配線密度
を増す必要が生じており、配線幅の細線化が急激に進行している。このような背景から、回路導体を支える接着剤塗膜は、絶縁性が重要な特性となりつつある。
In recent years, as electronic devices have become smaller and more multifunctional, it has become necessary to increase the wiring density of printed wiring boards, and wiring widths have been rapidly reduced. Against this background, the adhesive coating supporting the circuit conductor is becoming an important property in terms of insulation.
このため、一般的には、絶縁性がエポキシ樹脂等より劣るアクリロニトリルブタジエンゴムの配合量を減らし、エポキシ樹脂の配合量を増すことが行われる。しかしながら、この場合、粗化液溶解性がアクリロニトリルブタジエンゴムより著しく低いエポキシ樹脂を増加するために、粗化の凹凸が小さくなり、このため、めっき銅との接着力は実用上使用できないレベルまで低下してしまう。また、細線化になるほど、めっき銅との接着力が高いことが有利になることは言うまでもない。 Therefore, in general, the amount of acrylonitrile-butadiene rubber, whose insulation is inferior to that of epoxy resin, is reduced, and the amount of epoxy resin is increased. However, in this case, in order to increase the epoxy resin whose solubility of the roughening solution is significantly lower than that of the acrylonitrile-butadiene rubber, the roughness of the roughening is reduced, and therefore, the adhesive strength with the plated copper is reduced to a level that cannot be used practically. Resulting in. It goes without saying that the thinner the wire, the more advantageous it is that the adhesive strength to the plated copper becomes higher.
本発明は、絶縁性を損なうことなく、めっき銅との接着力に優れた接着剤によって銅と接着状態にある絶縁基材を提供することを目的とする。 An object of the present invention is to provide an insulating base material that is in an adhesion state with copper by an adhesive having excellent adhesion to plated copper without impairing insulation properties.
本発明の絶縁基材は、絶縁基材表面に塗布する接着剤が、エポキシ樹脂と架橋したアクリロニトリルブタジエンゴム粒子を含有することを特徴とする。 絶 縁 The insulating base material of the present invention is characterized in that the adhesive applied to the surface of the insulating base material contains acrylonitrile-butadiene rubber particles crosslinked with an epoxy resin.
本発明に用いる架橋したアクリロニトリルブタジエンゴム粒子は、乳化重合後のエマルジョン状態でアクリロニトリルブタジエンゴムを架橋した一次平均粒子径約５０〜５００nmの微小高分子粒子架橋ゴム粒子であり、カルボキシル基変成または未変成のアクリロニトリルブタジエンゴムの何れも使用できる。 The crosslinked acrylonitrile-butadiene rubber particles used in the present invention are crosslinked rubber particles of fine polymer particles having a primary average particle diameter of about 50 to 500 nm obtained by cross-linking acrylonitrile-butadiene rubber in an emulsion state after emulsion polymerization. Any of the acrylonitrile butadiene rubbers can be used.
その配合量は、接着剤中に２〜４０重量％であることが好ましい。その理由は、２重量％未満では、めっき銅との接着力向上に効果がなく、４０重量％を超えると、接着剤表面の粘着性が増し、後工程でのごみの付着等の問題が生じてくるためである。 The compounding amount is preferably 2 to 40% by weight in the adhesive. The reason is that if it is less than 2% by weight, there is no effect in improving the adhesive strength with the plated copper, and if it exceeds 40% by weight, the tackiness of the surface of the adhesive increases, and problems such as adhesion of dust in a later step occur. To come.
この架橋ＮＢＲを含有する基本となる樹脂組成は、アディティブ法配線板に用いられる一般的な樹脂組成が適用でき、耐めっき液性、塗膜形成性、粗化性等を考慮して、エポキシ樹脂、及び好ましくはアクリロニトリルブタジエンゴム、レゾール型フェノール樹脂、無機充填剤等を含む混合物である。 As the basic resin composition containing this crosslinked NBR, a general resin composition used for an additive method wiring board can be applied, and in consideration of plating solution resistance, coating film forming property, roughening property, etc., epoxy resin is used. And preferably a mixture containing acrylonitrile butadiene rubber, a resol type phenol resin, an inorganic filler and the like.
エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂が例示される。 ビ ス As the epoxy resin, a bisphenol A type epoxy resin is exemplified.
本発明において、接着剤中に無電解めっきの析出核となるめっき触媒を含有することができる。めっき触媒としては、元素周期率表の８族及び４Ｂ族の金属の塩あるいは酸化物が使用できる。例えば、白金、バラジウム、スズ等の化合物が用いられ、固体粒子あるいは有機溶媒に溶解させるか、又は他の樹脂とともに溶解分散させた溶液状態として、接着剤中に混合することができる。めっき触媒の接着剤中の配合量は、２〜１５重量％の範囲であれば、無電解めっきによって銅が析出する。 に お い て In the present invention, the adhesive may contain a plating catalyst that serves as a deposition nucleus for electroless plating. As the plating catalyst, salts or oxides of metals of Groups 8 and 4B of the periodic table can be used. For example, a compound such as platinum, palladium, tin or the like is used, and can be dissolved in solid particles or an organic solvent, or can be mixed with an adhesive in a solution state of being dissolved and dispersed together with another resin. If the amount of the plating catalyst in the adhesive is in the range of 2 to 15% by weight, copper is deposited by electroless plating.
上記接着剤の各成分は、有機溶媒中で混練り混合された溶液状混合物に調製される。用いる有機溶媒としては、トルエン、メチルエチルケトン、アセトン、メチルイソブチルケトン、キシレン、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、３−エトキシプロピオン酸エチル、プロピレングリコールモノメチルエーテル等の単独又は混合系を用いることができる。 各 Each component of the adhesive is prepared as a solution mixture kneaded and mixed in an organic solvent. As the organic solvent to be used, a single or mixed system of toluene, methyl ethyl ketone, acetone, methyl isobutyl ketone, xylene, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and propylene glycol monomethyl ether can be used.
本発明に係る絶縁基材としては、フェノール樹脂系又はエポキシ樹脂系、あるいは無機系又は有機複合物からなる基材等を用いることができる。 基材 As the insulating base material according to the present invention, a base material made of a phenol resin or epoxy resin, or an inorganic or organic composite can be used.
前記接着剤は、絶縁基材に１０〜５０μm塗布され、１４０〜１９０℃の温度で３０〜９０分加熱硬化が行われる。 接着 The adhesive is applied to the insulating base material in a thickness of 10 to 50 μm, and is heated and cured at a temperature of 140 to 190 ° C. for 30 to 90 minutes.
無電解めっきを析出させるに際しては、接着剤表面を化学的に粗化して接着に適した形状にする。化学的粗化に用いる粗化液は、クロム−硫酸系、クロム−硫酸−フッ化ナトリウム系、アルカリ−過マンガン酸系、ホウフッ化水素酸−重クロム酸系等が使用できる。また、パターン形成は、めっきレジストをスクリーン印刷、あるいはフォトマスクを紫外線硬化し現像して形成する。これらのめっきレジストは、化学的粗化処理工程の前あるいは処理した後で行われる。 析出 When depositing electroless plating, the surface of the adhesive is chemically roughened to a shape suitable for bonding. As a roughening solution used for chemical roughening, a chromium-sulfuric acid system, a chromium-sulfuric acid-sodium fluoride system, an alkali-permanganate system, a borofluoric acid-bichromic system system, and the like can be used. The pattern is formed by screen-printing a plating resist or by curing and developing a photomask with ultraviolet rays. These plating resists are performed before or after the chemical roughening process.
本発明に用いられる架橋ＮＢＲは、微小な粒子状であり、この架橋ＮＢＲが粗化液に溶解することで、接着剤表面に、接着に適した微小凹凸形状を形成することができる。また、架橋したＮＢＲであるため、配合量に比例した絶縁性の低下が全くない。 (4) The crosslinked NBR used in the present invention is in the form of fine particles, and by dissolving the crosslinked NBR in the roughening liquid, it is possible to form, on the surface of the adhesive, fine irregularities suitable for bonding. In addition, since it is a crosslinked NBR, there is no decrease in insulation in proportion to the blending amount.
以下、実施例によって、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
以下に示す接着剤成分を、ガラス布エポキシ積層板であるＬＥ−１６８（日立化成工業株式会社製、商品名）にディップコート法で塗布し、膜厚２５μmの接着剤層を両面に形成した。
（接着剤組成）
・架橋ＮＢＲ、
ＸＥＲ−９１（日本合成ゴム株式会社製、商品名）・・・・・２０重量部
・ビスフェノールＡ型エポキシ樹脂、
エピコート１００１（油化シェル株式会社製、商品名）・・・２０重量部
・アクリロニトリルブタジエンゴム、
ニポール１０３１（日本ゼオン株式会社製、商品名）・・・・５０重量部
・アルキルフェノール樹脂、
ヒタノール２４００（日立化成工業株式会社製、商品名）・・・５重量部
・熱硬化剤、
２Ｅ４ＭＺ（四国化成株式会社製、商品名）・・・・・・・０．１重量部
・充填剤（ケイ酸ジルコニウム）
ミクロパックス（白水化学株式会社製、商品名）・・・・・・１０重量部
・無電解めっき用触媒（塩化パラジウムの樹脂混合物）
ＰＥＣ−８（日立化成工業株式会社製、商品名）・・・・・・・４重量部
The adhesive component shown below was applied to LE-168 (trade name, manufactured by Hitachi Chemical Co., Ltd.), a glass cloth epoxy laminate, by dip coating to form an adhesive layer having a thickness of 25 μm on both surfaces.
(Adhesive composition)
・ Cross-linked NBR,
XER-91 (Nippon Synthetic Rubber Co., Ltd., trade name) 20 parts by weight Bisphenol A type epoxy resin,
Epicoat 1001 (trade name, manufactured by Yuka Shell Co., Ltd.): 20 parts by weight ・ Acrylonitrile butadiene rubber,
Nipol 1031 (trade name, manufactured by Zeon Corporation) ... 50 parts by weight-Alkyl phenol resin,
Hitanol 2400 (trade name, manufactured by Hitachi Chemical Co., Ltd.): 5 parts by weight
2E4MZ (Shikoku Chemicals Co., Ltd., trade name) 0.1 parts by weight Filler (zirconium silicate)
Micropacks (trade name, manufactured by Hakusui Chemical Co., Ltd.) 10 parts by weight ・ Catalyst for electroless plating (resin mixture of palladium chloride)
PEC-8 (trade name, manufactured by Hitachi Chemical Co., Ltd.): 4 parts by weight
次に、この接着剤層を形成させた絶縁基材を、１７０℃で６０分間加熱して硬化させた。さらに、めっき用レジストであるＳＲ−３０００（日立化成工業株式会社製、商品名）をラミネートして、回路形成用フォトマスクを介して紫外線露光し、現像した。次に、クロム−硫酸−フッ化ナトリウム（クロム酸４０ｇ／ｌ、濃硫酸３００ｍｌ／ｌ、フッ化ナトリウム１０ｇ／ｌ）の粗化液に４０℃で５分間浸漬して、接着剤露出部のみ選択的に化学粗化し、その後中和、水洗した。さらに、無電解銅めっき浴であるＣＣ−４１液（日立化成工業株式会社製、商品名）に投入して、３５μmのめっき銅を析出させた後、１６０℃で６０分間アニーリングして、アディティブ法プリント配線板を作製した。 Next, the insulating substrate on which the adhesive layer was formed was cured by heating at 170 ° C. for 60 minutes. Further, a plating resist SR-3000 (trade name, manufactured by Hitachi Chemical Co., Ltd.) was laminated, exposed to ultraviolet light through a circuit-forming photomask, and developed. Next, it is immersed in a roughening solution of chromium-sulfuric acid-sodium fluoride (chromic acid 40 g / l, concentrated sulfuric acid 300 ml / l, sodium fluoride 10 g / l) at 40 ° C. for 5 minutes, and only the exposed portion of the adhesive is selected. Chemically roughened, then neutralized and washed with water. Further, the solution was put into a CC-41 solution (trade name, manufactured by Hitachi Chemical Co., Ltd.) as an electroless copper plating bath to precipitate 35 μm of plated copper, and then annealed at 160 ° C. for 60 minutes to obtain an additive method. A printed wiring board was manufactured.
接着剤組成として、実施例１と比較して絶縁性を向上させた組成、すなわちエポキシ樹脂を増量した配合系として、以下の組成を用いた。その他は、実施例１と同様にして、アディティブ法プリント配線板を作製した。
（接着剤組成）
・架橋ＮＢＲ、
ＸＥＲ−９１（日本合成ゴム株式会社製、商品名）・・・・・２０重量部
・ビスフェノールＡ型エポキシ樹脂、
エピコート１００１（油化シェル株式会社製、商品名）・・・５０重量部
・アクリロニトリルブタジエンゴム、
ニポール１０３１（日本ゼオン株式会社製、商品名）・・・・２０重量部
・アルキルフェノール樹脂、
ヒタノール２４００（日立化成工業株式会社製、商品名）・・・５重量部
・熱硬化剤、
２Ｅ４ＭＺ（四国化成株式会社製、商品名）・・・・・・・０．１重量部
・充填剤（ケイ酸ジルコニウム）
ミクロパックス（白水化学株式会社製、商品名）・・・・・・１０重量部
・無電解めっき用触媒（塩化パラジウムの樹脂混合物）
ＰＥＣ−８（日立化成工業株式会社製、商品名）・・・・・・・４重量部
As the adhesive composition, the following composition was used as a composition in which the insulating property was improved as compared with Example 1, that is, as a compounding system in which an epoxy resin was increased. Except for this, the additive method printed wiring board was manufactured in the same manner as in Example 1.
(Adhesive composition)
・ Cross-linked NBR,
XER-91 (Nippon Synthetic Rubber Co., Ltd., trade name) 20 parts by weight Bisphenol A type epoxy resin,
Epicoat 1001 (trade name, manufactured by Yuka Shell Co., Ltd.): 50 parts by weight ・ Acrylonitrile butadiene rubber,
Nipol 1031 (manufactured by Nippon Zeon Co., Ltd., trade name) 20 parts by weight alkylphenol resin,
Hitanol 2400 (trade name, manufactured by Hitachi Chemical Co., Ltd.): 5 parts by weight
2E4MZ (Shikoku Chemicals Co., Ltd., trade name) 0.1 parts by weight Filler (zirconium silicate)
Micropacks (trade name, manufactured by Hakusui Chemical Co., Ltd.) 10 parts by weight ・ Catalyst for electroless plating (resin mixture of palladium chloride)
PEC-8 (trade name, manufactured by Hitachi Chemical Co., Ltd.): 4 parts by weight
実施例２の接着剤組成において、架橋ＮＢＲの配合量を増加した。その他は、実施例２と同様にして、アディティブ法プリント配線板を作製した。
（接着剤組成）
・架橋ＮＢＲ、
ＸＥＲ−９１（日本合成ゴム株式会社製、商品名）・・・・・３５重量部
・ビスフェノールＡ型エポキシ樹脂、
エピコート１００１（油化シェル株式会社製、商品名）・・・５０重量部
・アクリロニトリルブタジエンゴム、
ニポール１０３１（日本ゼオン株式会社製、商品名）・・・・１５重量部
・アルキルフェノール樹脂、
ヒタノール２４００（日立化成工業株式会社製、商品名）・・・５重量部
・熱硬化剤、
２Ｅ４ＭＺ（四国化成株式会社製、商品名）・・・・・・・０．１重量部
・充填剤（ケイ酸ジルコニウム）
ミクロパックス（白水化学株式会社製、商品名）・・・・・・１０重量部
In the adhesive composition of Example 2, the amount of the crosslinked NBR was increased. Otherwise, in the same manner as in Example 2, an additive method printed wiring board was manufactured.
(Adhesive composition)
・ Cross-linked NBR,
XER-91 (Nippon Synthetic Rubber Co., Ltd., trade name) 35 parts by weight Bisphenol A type epoxy resin,
Epicoat 1001 (trade name, manufactured by Yuka Shell Co., Ltd.): 50 parts by weight ・ Acrylonitrile butadiene rubber,
Nipol 1031 (manufactured by Nippon Zeon Co., Ltd., trade name) 15 parts by weight Alkyl phenol resin,
Hitanol 2400 (trade name, manufactured by Hitachi Chemical Co., Ltd.): 5 parts by weight
2E4MZ (Shikoku Chemicals Co., Ltd., trade name) 0.1 parts by weight Filler (zirconium silicate)
Micropacks (trade name, manufactured by Hakusui Chemical Co., Ltd.): 10 parts by weight
比較例１〜２
実施例１と実施例２において、接着剤中の架橋ＮＢＲを用いない組成とした。その他は、各実施例と同様にして、アディティブ法プリント配線板を作製した。
Comparative Examples 1-2
In Examples 1 and 2, the composition was such that the crosslinked NBR in the adhesive was not used. Otherwise, an additive method printed wiring board was manufactured in the same manner as in each example.
以上のようにして作製したアディティブ法プリント配線板の特性結果を表１に示す。 Table 1 shows the characteristic results of the additive printed wiring board manufactured as described above.
以上に説明したように、接着剤組成中に架橋したアクリロニトリルブタジエンゴム粒子を用いることで、絶縁性、耐熱性を損なうことなくめっき銅との接着力を向上できる接着剤によって、銅と接着状態にある絶縁基材を提供することができる。
As described above, by using acrylonitrile-butadiene rubber particles cross-linked in the adhesive composition, insulation, an adhesive capable of improving the adhesive strength with plated copper without impairing the heat resistance, the adhesive state with copper. A certain insulating substrate can be provided.
Claims (3)
3. The insulating substrate according to claim 1, wherein the crosslinked acrylonitrile butadiene rubber particles have an average particle size of 50 to 100 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003291585A JP3975984B2 (en) | 2003-08-11 | 2003-08-11 | Insulating substrate in adhesive state with copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003291585A JP3975984B2 (en) | 2003-08-11 | 2003-08-11 | Insulating substrate in adhesive state with copper |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27651294A Division JP3517996B2 (en) | 1994-11-10 | 1994-11-10 | Additive adhesive for printed circuit boards |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004074799A true JP2004074799A (en) | 2004-03-11 |
| JP3975984B2 JP3975984B2 (en) | 2007-09-12 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011086729A (en) * | 2009-10-14 | 2011-04-28 | Hitachi Chem Co Ltd | Laminated board for wiring board and method of manufacturing the same, resin film for primer layer, and multilayer wiring board and method of manufacturing the same |
| CN104015456A (en) * | 2014-06-11 | 2014-09-03 | 郭长奇 | Production method of anion insulation composite plate |
| US20140378580A1 (en) * | 2012-05-16 | 2014-12-25 | Hitachi Industrial Equipment Systems Co., Ltd. | Epoxy-Vinyl Copolymerization Type Liquid Resin Composition, Cured Product of the Same, Electronic/Electric Apparatus using the Cured Product, and Method of Producing the Cured Product |
| CN110055006A (en) * | 2019-04-18 | 2019-07-26 | 广东东华光电科技有限公司 | A kind of antiultraviolet thermal isolation film and its manufacturing process |
-
2003
- 2003-08-11 JP JP2003291585A patent/JP3975984B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011086729A (en) * | 2009-10-14 | 2011-04-28 | Hitachi Chem Co Ltd | Laminated board for wiring board and method of manufacturing the same, resin film for primer layer, and multilayer wiring board and method of manufacturing the same |
| US20140378580A1 (en) * | 2012-05-16 | 2014-12-25 | Hitachi Industrial Equipment Systems Co., Ltd. | Epoxy-Vinyl Copolymerization Type Liquid Resin Composition, Cured Product of the Same, Electronic/Electric Apparatus using the Cured Product, and Method of Producing the Cured Product |
| US9493605B2 (en) * | 2012-05-16 | 2016-11-15 | Hitachi Industrial Equipment Systems Co., Ltd. | Epoxy-vinyl copolymerization type liquid resin composition, cured product of the same, electronic/electric apparatus using the cured product, and method of producing the cured product |
| CN104015456A (en) * | 2014-06-11 | 2014-09-03 | 郭长奇 | Production method of anion insulation composite plate |
| CN110055006A (en) * | 2019-04-18 | 2019-07-26 | 广东东华光电科技有限公司 | A kind of antiultraviolet thermal isolation film and its manufacturing process |
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| Publication number | Publication date |
|---|---|
| JP3975984B2 (en) | 2007-09-12 |
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