JP4211070B2 - Method for producing an electroless plating adhesive - Google Patents
Method for producing an electroless plating adhesive Download PDFInfo
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- JP4211070B2 JP4211070B2 JP35026897A JP35026897A JP4211070B2 JP 4211070 B2 JP4211070 B2 JP 4211070B2 JP 35026897 A JP35026897 A JP 35026897A JP 35026897 A JP35026897 A JP 35026897A JP 4211070 B2 JP4211070 B2 JP 4211070B2
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【０００１】
【発明の属する技術分野】
本発明は、有機溶剤中に架橋したアクリロニトリルブタジエンゴム粒子を表面張力低下剤を用いて均一に分散する方法に関する。更に詳しくは、架橋したアクリロニトリルブタジエンゴム粒子を平均１次粒子径０．０１μm〜０．１μmに維持した層間絶縁層をビルドアップ方式で形成する多層配線板の絶縁樹脂に関する。
【０００２】
【従来の技術】
アクリロニトリルブタジエンゴムは、アルキルフェノール樹脂や過酸化物を用いて架橋することにより、耐溶剤性や耐薬品性に優れる性質を有し、また金属やプラスチック等への接着性も高い性質を有する。更に、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どうしを架橋した１次平均粒子径約０．０１〜０．１μmの架橋ゴム粒子は、エポキシ樹脂の耐衝撃性改善やチキソ性向上剤としてその利用分野も広がりつつある。一方、絶縁性材料の分野においてもその利用価値が高まっている。例えば、感光性を付与した絶縁樹脂を回路形成した絶縁基板上に形成し、フォトプロセスにより絶縁樹脂に微少なバイアホールを形成して層間接続する方式である。この場合、層間を電気的に接続する方法は絶縁樹脂表面に無電解銅めっきを施す方法が一般的である。この為、絶縁樹脂には、無電解銅めっきとの高い接着力及び熱的なストレスに耐えうる柔軟性等が要求される。 これらに対して、１次平均粒子径を約０．０１〜０．１μmに維持した架橋アクリロニトリルブタジエンゴム粒子は有効である。しかしながら、１次平均粒子径が約０．０１〜０．１μmの架橋アクリロニトリルブタジエンゴム粒子は、適切な溶剤を用いることで、架橋アクリロニトリルブタジエンゴム粒子単独では１次粒子径状態に維持できても分散する相手樹脂に含まれている溶剤の種類によって膨潤、凝集または溶解するのが一般的である。この為、架橋アクリロニトリルブタジエンゴム粒子を分散する相手樹脂は、溶剤を含まない無溶剤系又は溶剤が限定される樹脂になり、その使用には制限があった。
【０００３】
【発明が解決しようとする課題】
本発明は、前記した１次平均粒子径約０．０１〜０．１μmの架橋アクリロニトリルブタジエンゴム粒子を有機溶剤を使用した場合でも膨潤・溶解させることなく１次粒子径状態で均一に分散させる方法を提案することを課題とした。
【０００４】
【課題を解決するための手段】
本発明は、接着剤組成物として、架橋したアクリロニトリルブタジエンゴム粒子と表面張力低下剤を必須に含む接着剤の製造方法において、架橋したアクリロニトリルブタジエンゴム粒子と表面張力低下剤を最初に混合させることを特徴とする無電解めっき用接着剤の製造方法である。
また本発明は、表面張力低下剤として、アクリル酸エチルとアクリル酸エチルへキシルとの共重合樹脂またはジメチルシリコーン、メチルフェニルシリコーン、メチルハイドロジェンシリコーンの少なくとを１種類以上を用いると好ましい無電解めっき用接着剤の製造方法である。
さらに、本発明は、有機溶剤を除く接着剤組成物１００重量部に対し、表面張力低下剤を０．１〜２０重量部の範囲で配合すると好ましい無電解めっき用接着剤の製造方法である。
【０００５】
【発明の実施の形態】
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１次粒子径約０．０１〜０．１μmの微小高分子量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でも使用できる。また、アクリロニトリルブタジエンゴム粒子を分散するための溶剤としては特に制限するものではないが、低極性溶剤が１次粒子径状態で維持できる点から好ましい。
【０００６】
本発明で使用する接着剤組成物を構成する樹脂成分として用いることが可能な第一の群としてはエポキシ樹脂、ブロム化エポキシ樹脂、ゴム変性エポキシ樹脂、ゴム分散エポキシ樹脂等の脂環式エポキシ樹脂またはビスフェノール−Ａ系エポキシ樹脂及びこれらエポキシ樹脂の酸変性物が挙げられる。特に光照射を行って光硬化を行う場合にはこれらエポキシ樹脂と不飽和酸との変性物が好ましい。不飽和酸としては無水マレイン酸、テトラヒドロフタル酸無水物、イタコン酸無水物、アクリル酸、メタクリル酸等が挙げられる。これらはエポキシ樹脂のエポキシ基に対し当量もしくは当量以下の配合比率で該不飽和カルボン酸を反応させることによって得られる。エポキシ樹脂そのものを用いる場合には光硬化後、未反応部分を例えばシクロヘキサノン、ブチルカルビトールのような溶剤を用いて除去することで像形成が可能である。エポキシ樹脂として適当なカルボン酸変性物を用いることによって現像液としてアルカリ水溶液、水系現像液のような安価で広く普及しているプロセスを適用することが可能である。この時不飽和基を有する酸化合物を用いれば硬化性組成物の光反応性を更に高めることが可能であり、特に有用である。
【０００７】
他の樹脂成分として用いることが可能な第二の群としてはフェノール樹脂、アルキルフェノール樹脂、ノボラックフェノール樹脂、酸変性ノボラックフェノール樹脂、ビスフェノールA、テトラブロモビスフェノールＡのようなフェノール性水酸基を有する樹脂類である。これらは単独で又は混合物としても変性物としても使用が可能である。これらの材料は、溶剤を含有するか否かは制限するものではなく、さらに使用する溶剤も制限するものではない。
【０００８】
本発明で使用する架橋したアクリロニトリルブタジエンゴム粒子を１次平均粒子径状態で均一に分散する為に必要な表面張力低下剤としては、アクリル酸エチルとアクリル酸エチルヘキシルとの共重合樹脂またはジメチルシルコーン、メチルフェニルシリコーン、メチルハイドロジェンシリコーンを用いることができる。アクリル酸エチルとアクリル酸エチルヘキシルとの共重合樹脂として容易に入手可能なものとしては、モダフロー(モンサント社製、商品名)がある。また、ジメチルシリコーンとして容易に入手可能なものとしては、ＳＨ−１９３（東レ・ダウコーニング・シリコーン株式会社製、商品名)やＫＦ９６(信越化学工業株式会社製、商品名)があり、メチルフェニルシリコーンとして容易に入手可能なものとしては、ＳＨ−５１０（東レ・ダウコーニング・シリコーン株式会社製、商品名)やＫＦ５０(信越化学工業株式会社製、商品名)がある。さらに、メチルハイドロジェンシリコーンとして容易に入手可能なものとしては、ＳＨ−１１０７（東レ・ダウコーニング・シリコーン株式会社製、商品名）やＫＦ９９(信越化学工業株式会社製、商品名)がある。これらの表面張力低下剤の配合量は、有機溶剤を除いた接着剤組成物１００重量部に対し、表面張力低下剤を０．１〜２０重量部を配合することが好ましい。表面張力低下剤が０．１重量部未満では、アクリロニトリルブタジエンゴム粒子を平均１次粒子径で分散するのが困難である。また、表面張力低下剤が２０重量部以上になると、主として高温側での分解劣化が生じやすくなる。
【０００９】
また、本発明の接着剤組成物には、微粉末シリカ、水酸化アルミニウム、シリカ、ケイ酸ジルコニウム、炭酸カルシウム、タルク、硫酸バリウム等の無機充填剤を混入すれば、接着剤層の補強並びに化学粗化した際の粗化凹凸を形成しやすいためめっき銅との接着力向上の点から好ましい。本発明の接着剤組成物は通常溶剤で希釈されておりそれを適当な基材の上に塗工し、溶剤を乾燥して塗膜を形成した後に、硬化を行わせる。あるいは前述したように別の基材等に予め塗膜を形成し、それを別の基材に転写積層することでも行える。基材としてはガラス基板、プラスチック基板、金属基板、絶縁性基板、積層板、プリント配線板のようなものが挙げられ、塗膜を保持できるものならば制限されず使用可能である。特に積層基板或いはプリント配線板を用いた場合には既に形成した配線基板上に新たな絶縁層を形成できることからビルドアップ配線板用絶縁材料として用いることが可能である。以下本発明を実施例によって具体的に説明する。
【００１０】
【実施例】
（実施例１）
（１）粒子状の架橋アクリロニトリルブタジエンゴムの固形分１５重量％のメチルエチルケトン溶液（ＸＥＲ−９１ＳＫ１５、日本合成ゴム株式会社製、商品名）を固形分で10重量部を秤量し撹拌した。
（２）アクリル酸エチルとアクリル酸エチルヘキシルとの共重合樹脂のモダフロー（モンサント社製、商品名）を０．４重量部を秤量し、（１）の溶液に徐々に添加した。
（３）接着剤組成物の一つであるエポキシ樹脂（エピコート１００４、油化シェルエポキシ株式会社製、商品名)をシクロヘキサノンに６０重量％溶解した溶液を固形分で８０重量部を更に加えて撹拌した。
（４）エポキシ樹脂の硬化促進剤である２−エチル−４−メチルイミダゾール（四国化成工業株式会社製)を０．８8重量部添加し、３０分間撹拌した。
（５）上記で得られた接着剤組成物のワニスをガラスエポキシ基板（ＬＥ−６７、日立化成工業株式会社製、商品名)に膜厚３０μmになるように塗工、乾燥した後、１６０℃で６０分間加熱硬化した。
（６）上記のガラスエポキシ基板に設けた接着剤層付き基板をエポキシ樹脂で注型し、走査型電子顕微鏡で接着剤層の断面の架橋したアクリロニトリルブタジエンゴムの分散状態を断面観察した。
【００１１】
（実施例２）
実施例１において、表面張力低下剤のモダフローをＳＨ−１９３（ジメチルシリコーン、東レ・ダウコーニング・シリコーン株式会社製、商品名)やＫＦ９６（信越化学工業株式会社製、商品名)に置き換え、その他は同様な方法で行った。
【００１２】
（実施例３）
（１）粒子状架橋アクリロニトリルブタジエンゴムの固形分１５重量％のメチルエチルケトン溶液（ＸＥＲ−９１ＳＫ１５、日本合成ゴム株式会社製、商品名）を固形分で１０重量部を秤量し撹拌した。
（２）アクリル酸エチルとアクリル酸エチルヘキシルとの共重合樹脂のモダフロー（モンサント社製、商品名)を０．４重量部を秤量し、（１）の溶液に徐々に添加した。
（３）酸変成エポキシ樹脂（Ｒ−５２５９、日本化薬株式会社製、商品名)を固形分で８０重量部と水酸化アルミニウム１５重量部を予めビーズミルで混練りして作製したマスターバッチ溶液を上記溶液中に加えた。
（４）光開始剤のイルガキュア６５１（チバガイギー株式会社製、商品名）を５重量部加えて３０分間撹拌した。
（５）１８μｍの両面粗化銅箔を両面に張り付けた銅張りガラス布エポキシ樹脂積層板であるＭＣＬ−Ｅ−６７（日立化成工業株式会社製、商品名）を用い、不要な箇所の銅箔をエッチング除去して、第１の回路を形成した（図１−（ａ）に示す）。基板の片面に、前記の方法で作製したワニスをロールコータを用いて塗布し、８０℃、１０分間乾燥して膜厚５０μｍの絶縁層を形成した（図１−（ｂ）に示す）。
（６）バイアホールとなる部分に遮蔽部を形成したフォトマスクを介して、露光量３００ｍＪ／ｃｍ2の紫外線を照射して（図１−（ｃ）に示す）、さらに未露光部分を、２，２−ブトキシエトキシエタノールを１０体積％、４硼酸ナトリウム８ｇ／ｌを含んだ現像液で３０℃、１分間スプレー処理をしてバイアホールを形成した。
（７）紫外線２Ｊ／ｃｍ2を絶縁層に照射して後露光を行った。
（８）１５０℃、１時間後加熱を行った。
（９）接着剤層を化学粗化するために、粗化液として、ＫＭｎＯ4：６０ｇ／ｌ、ＮａＯＨ：４０ｇ／ｌの水溶液を作製し、５０℃に加温して５分間浸漬処理する。ＫＭｎＯ4浸漬処理後は、ＳｎＣｌ2：３０ｇ／ｌ、ＨＣｌ：３００ｍｌ／ｌの水溶液に室温で５分間浸漬処理して中和し、粗化凹凸形状を形成した。
（１０）第１の絶縁層表面に第２の回路を形成するために、まず、ＰｄＣｌ2を含む無電解めっき用触媒であるＨＳ−２０２Ｂ（日立化成工業株式会社製、商品名）に、室温で１０分間浸漬処理し、水洗し、無電解銅めっきであるＬ−５９めっき液（日立化成工業株式会社製、商品名）に７０℃で３０分間浸漬し、さらに硫酸銅電解めっきを行って、接着剤層表面上に厚さ２０μｍの導体層を形成した（図１−（ｄ））。 次に、めっき導体の不要な箇所をエッチング除去するためにエッチングレジストを形成し、エッチングし、その後エッチングレジストを除去して、第１の回路と接続したバイアホールを含む第２の回路形成を行った（図１−（ｅ）に示す）。
（１１）さらに、多層化するために、第２の回路導体表面を、亜塩素酸ナトリウム：５０ｇ／ｌ，ＮａＯＨ：２０ｇ／ｌ、リン酸三ナトリウム：１０ｇ／ｌの水溶液に８５℃、２０分間浸漬し、水洗して、８０℃、２０分間乾燥して第２の回路導体表面上に酸化銅の凹凸を形成した。
（１２）（２）〜（７）の工程を繰り返して６層の多層配線板を作製した。
【００１３】
（比較例１）
実施例１において、アクリル酸エチルとアクリル酸エチルへキシルとの共重合樹脂のモダフロー(モンサント社製、商品名)を用いずに接着剤組成物のワニスを作製した。その他は、実施例１と同様の方法で行った。
【００１４】
（比較例２）
実施例３において、アクリル酸エチルとアクリル酸エチルへキシルとの共重合樹脂のモダフロー(モンサント社製、商品名)を用いずに接着剤組成物のワニスを作製した。その他は、実施例３と同様の方法で行った。以上の方法で作製した試料や多層配線板の特性を表１に示した。
なお、直径０．１０ｍｍのビア解像性は、０．１０ｍｍのバイアホール直径のフォトマスクを用いて露光、現像した基板のバイアホール形成部を金属顕微鏡及び走査型電子顕微鏡を用いて、バイアホール底部の樹脂残りとビアホール形状を観察し、ビアホール底部に樹脂残りがなく、また、剥がれやへこみのないビアホールが形成できているものを良好とし、それ以外を不良として評価した。ピール強度は、ＪＩＳ Ｃ６４８１に準じ、めっき銅を９０度方向に１０ｍｍ幅で剥離した際の接着力を求めた。
【００１５】
【表１】
架橋したアクリロニトリルブタジエンゴム粒子と表面張力低下剤を最初に混合させるた実施例１、２は、表面張力低下剤を使用しない比較例１に比べ、架橋したアクリロニトリルブタジエンゴム粒子の分散性に遥かに優れている。そしてその方法を用いて作製した実施例３の多層配線板のめっき銅のピール強度は、その方法を用いない比較例２に比べて３倍もの密着性を示す。
【００１７】
【発明の効果】
本発明の無電解めっき用接着剤の製造方法で得られる接着剤は、架橋したアクリロニトリルブタジエンゴム粒子の分散性に優れ凝集物が見られないのでビアの解像性を劣化させることなくピール強度を高めることができる。
【図面の簡単な説明】
【図１】 （ａ）〜（ｅ）は、本発明の多層配線板の製造方法を説明するための各工程の断面図である。
【符号の説明】
１．第１の回路層
２．絶縁基板
３．絶縁層
４．バイアホール
５．第２の回路層
６．銅めっき層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of uniformly dispersing acrylonitrile butadiene rubber particles crosslinked in an organic solvent using a surface tension reducing agent. More specifically, the present invention relates to an insulating resin for a multilayer wiring board in which an interlayer insulating layer in which crosslinked acrylonitrile butadiene rubber particles are maintained at an average primary particle diameter of 0.01 μm to 0.1 μm is formed by a build-up method.
[0002]
[Prior art]
Acrylonitrile butadiene rubber has properties that are excellent in solvent resistance and chemical resistance by cross-linking with an alkylphenol resin or a peroxide, and also has high adhesion to metals, plastics, and the like. Furthermore, crosslinked rubber particles having a primary average particle diameter of about 0.01 to 0.1 μm obtained by crosslinking acrylonitrile butadiene rubbers in an emulsion state after emulsion polymerization are used as an impact resistance improver and a thixotropy improver for epoxy resins. The field is also expanding. On the other hand, its utility value is also increasing in the field of insulating materials. For example, an insulating resin imparted with photosensitivity is formed on an insulating substrate on which a circuit is formed, and a minute via hole is formed in the insulating resin by a photo process to perform interlayer connection. In this case, the method of electrically connecting the layers is generally a method of performing electroless copper plating on the surface of the insulating resin. For this reason, the insulating resin is required to have a high adhesive force with the electroless copper plating and a flexibility that can withstand thermal stress. In contrast, crosslinked acrylonitrile butadiene rubber particles whose primary average particle diameter is maintained at about 0.01 to 0.1 μm are effective. However, the crosslinked acrylonitrile butadiene rubber particles having a primary average particle size of about 0.01 to 0.1 μm are dispersed even if the crosslinked acrylonitrile butadiene rubber particles alone can be maintained in the primary particle size state by using an appropriate solvent. In general, it swells, aggregates or dissolves depending on the type of solvent contained in the partner resin. For this reason, the partner resin that disperses the crosslinked acrylonitrile butadiene rubber particles is a solvent-free or solvent-free resin that does not contain a solvent, and its use is limited.
[0003]
[Problems to be solved by the invention]
The present invention is a method of uniformly dispersing the above-mentioned crosslinked acrylonitrile butadiene rubber particles having a primary average particle size of about 0.01 to 0.1 μm in a primary particle size state without swelling or dissolving even when an organic solvent is used. The problem was to propose.
[0004]
[Means for Solving the Problems]
The present invention relates to a method for producing an adhesive which essentially includes a crosslinked acrylonitrile butadiene rubber particle and a surface tension reducing agent as an adhesive composition, wherein the crosslinked acrylonitrile butadiene rubber particle and the surface tension reducing agent are first mixed. It is the manufacturing method of the adhesive agent for electroless plating characterized.
In the present invention, it is preferable that at least one of a copolymer resin of ethyl acrylate and ethylhexyl acrylate or at least one of dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone is used as the surface tension reducing agent. It is a manufacturing method of the adhesive agent for plating.
Furthermore, the present invention is a preferable method for producing an electroless plating adhesive when a surface tension reducing agent is blended in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the adhesive composition excluding the organic solvent.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The crosslinked acrylonitrile butadiene rubber particles used in the present invention are fine high molecular weight crosslinked rubber particles having a primary particle diameter of about 0.01 to 0.1 μm and crosslinked with acrylonitrile butadiene rubber in an emulsion state after emulsion polymerization. Alternatively, any unmodified acrylonitrile butadiene rubber can be used. In addition, the solvent for dispersing the acrylonitrile butadiene rubber particles is not particularly limited, but a low polarity solvent is preferable because it can be maintained in a primary particle size state.
[0006]
The first group that can be used as the resin component constituting the adhesive composition used in the present invention includes alicyclic epoxy resins such as epoxy resins, brominated epoxy resins, rubber-modified epoxy resins, rubber-dispersed epoxy resins, etc. Or the bisphenol-A type | system | group epoxy resin and the acid modification thing of these epoxy resins are mentioned. In particular, when photocuring is performed by light irradiation, modified products of these epoxy resins and unsaturated acids are preferred. Examples of the unsaturated acid include maleic anhydride, tetrahydrophthalic anhydride, itaconic anhydride, acrylic acid, methacrylic acid and the like. These can be obtained by reacting the unsaturated carboxylic acid in an amount equal to or less than the equivalent of the epoxy group of the epoxy resin. When the epoxy resin itself is used, an image can be formed by removing an unreacted portion using a solvent such as cyclohexanone or butyl carbitol after photocuring. By using an appropriate carboxylic acid-modified product as an epoxy resin, it is possible to apply inexpensive and widespread processes such as an alkaline aqueous solution and an aqueous developer as a developer. At this time, if an acid compound having an unsaturated group is used, the photoreactivity of the curable composition can be further increased, which is particularly useful.
[0007]
The second group that can be used as other resin components includes phenolic resins, alkylphenol resins, novolac phenol resins, acid-modified novolac phenol resins, bisphenol A, resins having a phenolic hydroxyl group such as tetrabromobisphenol A. is there. These can be used alone or as a mixture or a modified product. These materials do not limit whether or not they contain a solvent, and further do not limit the solvent to be used.
[0008]
As a surface tension reducing agent necessary for uniformly dispersing the crosslinked acrylonitrile butadiene rubber particles used in the present invention in a state of a primary average particle size, a copolymer resin of acrylate and ethyl hexyl or dimethylsilcon , Methyl phenyl silicone, and methyl hydrogen silicone can be used. Modaflow (trade name, manufactured by Monsanto Co., Ltd.) is easily available as a copolymer resin of ethyl acrylate and ethylhexyl acrylate. Examples of dimethyl silicone that can be easily obtained include SH-193 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) and KF96 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). As those easily available, there are SH-510 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) and KF50 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, examples of easily available methyl hydrogen silicone include SH-1107 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) and KF99 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). The blending amount of these surface tension reducing agents is preferably 0.1 to 20 parts by weight of the surface tension reducing agent with respect to 100 parts by weight of the adhesive composition excluding the organic solvent. When the surface tension reducing agent is less than 0.1 part by weight, it is difficult to disperse the acrylonitrile butadiene rubber particles with an average primary particle size. On the other hand, when the surface tension reducing agent is 20 parts by weight or more, decomposition and deterioration mainly on the high temperature side tend to occur.
[0009]
In addition, when an inorganic filler such as fine powder silica, aluminum hydroxide, silica, zirconium silicate, calcium carbonate, talc, barium sulfate is mixed in the adhesive composition of the present invention, the adhesive layer is reinforced and chemically treated. Since it is easy to form roughened unevenness when roughened, it is preferable from the viewpoint of improving adhesive strength with plated copper. The adhesive composition of the present invention is usually diluted with a solvent, which is coated on a suitable substrate, dried after the solvent is formed to form a coating film, and then cured. Alternatively, as described above, a coating film may be formed in advance on another base material and transferred and laminated on another base material. Examples of the substrate include a glass substrate, a plastic substrate, a metal substrate, an insulating substrate, a laminate, and a printed wiring board, and any substrate that can hold a coating film can be used. In particular, when a laminated substrate or a printed wiring board is used, a new insulating layer can be formed on the already formed wiring board, so that it can be used as an insulating material for build-up wiring boards. Hereinafter, the present invention will be described specifically by way of examples.
[0010]
【Example】
Example 1
(1) Methyl ethyl ketone solution (XER-91SK15, trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.) having a solid content of 15% by weight of particulate crosslinked acrylonitrile butadiene rubber was weighed and stirred.
(2) 0.4 parts by weight of Modaflow (manufactured by Monsanto Co., Ltd.), a copolymer resin of ethyl acrylate and ethylhexyl acrylate, was weighed and gradually added to the solution of (1).
(3) A solution obtained by dissolving 60 wt% of an epoxy resin (Epicoat 1004, manufactured by Yuka Shell Epoxy Co., Ltd., trade name), which is one of the adhesive compositions, in cyclohexanone is further added with a solid content of 80 parts by weight and stirred. did.
(4) 0.88 parts by weight of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.), which is an epoxy resin curing accelerator, was added and stirred for 30 minutes.
(5) After coating and drying the varnish of the adhesive composition obtained above on a glass epoxy substrate (LE-67, manufactured by Hitachi Chemical Co., Ltd., trade name) to a film thickness of 30 μm, 160 ° C. For 60 minutes.
(6) The substrate with the adhesive layer provided on the glass epoxy substrate was cast with an epoxy resin, and the cross-sectional observation of the dispersion state of the crosslinked acrylonitrile butadiene rubber in the cross section of the adhesive layer was performed with a scanning electron microscope.
[0011]
(Example 2)
In Example 1, Modaflow of the surface tension reducing agent was replaced with SH-193 (dimethyl silicone, manufactured by Toray Dow Corning Silicone Co., Ltd., trade name) or KF96 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), The same method was used.
[0012]
(Example 3)
(1) Methyl ethyl ketone solution (XER-91SK15, trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.) having a solid content of 15% by weight of particulate crosslinked acrylonitrile butadiene rubber was weighed and stirred.
(2) 0.4 parts by weight of Modaflow (manufactured by Monsanto Co., Ltd.), a copolymer resin of ethyl acrylate and ethylhexyl acrylate, was weighed and gradually added to the solution of (1).
(3) A master batch solution prepared by previously kneading 80 parts by weight of solid acid content epoxy resin (R-5259, manufactured by Nippon Kayaku Co., Ltd., trade name) and 15 parts by weight of aluminum hydroxide in a bead mill. Added into the above solution.
(4) 5 parts by weight of Irgacure 651 (trade name, manufactured by Ciba Geigy Co., Ltd.) as a photoinitiator was added and stirred for 30 minutes.
(5) Unnecessary portions of copper foil using MCL-E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a copper-clad glass cloth epoxy resin laminate with 18 μm double-side roughened copper foil attached to both sides. Was removed by etching to form a first circuit (shown in FIG. 1- (a)). The varnish produced by the above method was applied to one side of the substrate using a roll coater and dried at 80 ° C. for 10 minutes to form an insulating layer having a thickness of 50 μm (shown in FIG. 1- (b)).
(6) An ultraviolet ray with an exposure amount of 300 mJ / cm 2 is irradiated through a photomask in which a shielding portion is formed in a portion to be a via hole (shown in FIG. 1- (c)), and an unexposed portion is Via-holes were formed by spraying at 30 ° C. for 1 minute with a developer containing 10% by volume of 2-butoxyethoxyethanol and 8 g / l of sodium borate.
(7) Post-exposure was performed by irradiating the insulating layer with ultraviolet rays 2 J / cm 2 .
(8) Heating was performed after 150 hours at 150 ° C.
(9) In order to chemically roughen the adhesive layer, an aqueous solution of KMnO 4 : 60 g / l, NaOH: 40 g / l is prepared as a roughening solution, heated to 50 ° C. and immersed for 5 minutes. After the KMnO 4 immersion treatment, it was neutralized by immersion in an aqueous solution of SnCl 2 : 30 g / l and HCl: 300 ml / l at room temperature for 5 minutes to form a roughened uneven shape.
(10) to form a second circuit to the first surface of the insulating layer, firstly, HS-202B (manufactured by Hitachi Chemical Co., Ltd., trade name) is an electroless plating catalyst containing PdCl 2, the room temperature Soaked in water for 10 minutes, immersed in L-59 plating solution (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is electroless copper plating, for 30 minutes at 70 ° C., and further subjected to copper sulfate electrolytic plating. A conductor layer having a thickness of 20 μm was formed on the surface of the adhesive layer (FIG. 1- (d)). Next, an etching resist is formed to remove unnecessary portions of the plated conductor, and etching is performed. Thereafter, the etching resist is removed, and a second circuit including a via hole connected to the first circuit is formed. (Shown in FIG. 1- (e)).
(11) Further, in order to make a multilayer, the surface of the second circuit conductor is placed in an aqueous solution of sodium chlorite: 50 g / l, NaOH: 20 g / l, trisodium phosphate: 10 g / l at 85 ° C. for 20 minutes. It was immersed, washed with water, and dried at 80 ° C. for 20 minutes to form copper oxide irregularities on the surface of the second circuit conductor.
(12) Steps (2) to (7) were repeated to produce a 6-layer multilayer wiring board.
[0013]
(Comparative Example 1)
In Example 1, an adhesive composition varnish was prepared without using Modaflow (manufactured by Monsanto Co., Ltd.), a copolymer resin of ethyl acrylate and ethyl hexyl acrylate. Others were performed in the same manner as in Example 1.
[0014]
(Comparative Example 2)
In Example 3, an adhesive composition varnish was prepared without using Modaflow (manufactured by Monsanto Co., Ltd.), a copolymer resin of ethyl acrylate and ethyl hexyl acrylate. Others were performed in the same manner as in Example 3. Table 1 shows the characteristics of the samples and multilayer wiring boards produced by the above method.
The via resolution having a diameter of 0.10 mm is obtained by using a metal microscope and a scanning electron microscope to form a via hole forming portion of the substrate exposed and developed using a photomask having a via hole diameter of 0.10 mm. The resin residue at the bottom and the via hole shape were observed, and those having no resin residue at the bottom of the via hole and forming via holes free from peeling or dents were evaluated as good, and the others were evaluated as defective. The peel strength was determined in accordance with JIS C6481, and the adhesive strength when the plated copper was peeled off at a 10 mm width in the 90-degree direction.
[0015]
[Table 1]
In Examples 1 and 2, in which the crosslinked acrylonitrile butadiene rubber particles and the surface tension reducing agent were first mixed, the dispersibility of the crosslinked acrylonitrile butadiene rubber particles was far superior to Comparative Example 1 in which no surface tension reducing agent was used. ing. And the peeling strength of the copper plating of the multilayer wiring board of Example 3 produced using the method shows 3 times the adhesiveness compared with the comparative example 2 which does not use the method.
[0017]
【The invention's effect】
The adhesive obtained by the method for producing an electroless plating adhesive of the present invention has excellent dispersibility of the crosslinked acrylonitrile butadiene rubber particles, and aggregates are not seen, so that peel strength is not deteriorated without deteriorating the resolution of vias. Can be increased.
[Brief description of the drawings]
FIGS. 1A to 1E are cross-sectional views of steps for explaining a method for manufacturing a multilayer wiring board according to the present invention.
[Explanation of symbols]
1. First circuit layer2. 2. Insulating substrate Insulating layer 4. Via hole 5. Second circuit layer 6. Copper plating layer
Claims (2)
架橋したアクリロニトリルブタジエンゴム粒子と、アクリル酸エチルとアクリル酸エチルへキシルとの共重合樹脂またはジメチルシリコーン、メチルフェニルシリコーン、メチルハイドロジェンシリコーンの少なくとも１種から選択される表面張力低下剤とを最初に混合させ、
得られた混合物に、その後に樹脂成分を、次に樹脂成分の硬化促進剤または光開始剤を順次混合させることを特徴とする無電解めっき用接着剤の製造方法。 As an adhesive composition, in a method for producing an adhesive that essentially includes crosslinked acrylonitrile butadiene rubber particles, a surface tension reducing agent, a resin component, and a curing accelerator or photoinitiator for the resin component,
First, a crosslinked acrylonitrile butadiene rubber particle and a copolymer resin of ethyl acrylate and ethyl hexyl or a surface tension reducing agent selected from at least one of dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone are used. Mix,
A method for producing an adhesive for electroless plating, wherein a resin component is subsequently mixed with the resulting mixture, followed by a curing accelerator or a photoinitiator of the resin component .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35026897A JP4211070B2 (en) | 1997-12-19 | 1997-12-19 | Method for producing an electroless plating adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35026897A JP4211070B2 (en) | 1997-12-19 | 1997-12-19 | Method for producing an electroless plating adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11181379A JPH11181379A (en) | 1999-07-06 |
| JP4211070B2 true JP4211070B2 (en) | 2009-01-21 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35026897A Expired - Fee Related JP4211070B2 (en) | 1997-12-19 | 1997-12-19 | Method for producing an electroless plating adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4211070B2 (en) |
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1997
- 1997-12-19 JP JP35026897A patent/JP4211070B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH11181379A (en) | 1999-07-06 |
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