JP2006193583A - Adhesive composition, multi-layered printed circuit board using the adhesive composition and method for producing multi-layered printed circuit board - Google Patents
Adhesive composition, multi-layered printed circuit board using the adhesive composition and method for producing multi-layered printed circuit board Download PDFInfo
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本発明は，接着剤組成物，この接着剤組成物を用いてなる多層プリント配線板及び多層プリント配線板の製造方法に関する。 The present invention relates to an adhesive composition, a multilayer printed wiring board using the adhesive composition, and a method for producing the multilayer printed wiring board.
多層プリント配線板は，複数の基板を接着一体化して製造され，基板の接着には，エポキシ樹脂等の熱硬化性樹脂を含む熱硬化性樹脂組成物（接着剤組成物）をガラス布等の基材に含浸乾燥して得られるプリプレグが用いられている。プリプレグに含浸乾燥された熱硬化性樹脂組成物（接着剤組成物）は，接着一体化するときのプレス工程において一旦溶融流動化し，基板に形成された導体回路間の凹みを埋めるようにされている。 A multilayer printed wiring board is manufactured by bonding and integrating a plurality of substrates. For bonding substrates, a thermosetting resin composition (adhesive composition) containing a thermosetting resin such as an epoxy resin is used for glass cloth or the like. A prepreg obtained by impregnating and drying a substrate is used. The thermosetting resin composition (adhesive composition) impregnated and dried in the prepreg is once melted and fluidized in the pressing process when the adhesive is integrated, and the recesses between the conductor circuits formed on the substrate are filled. Yes.
最近，チップキャリア，ピングリッドアレイ，ボールグリッドアレイ等，半導体素子を搭載するために用いられるパッケージ（以下単にパッケージという）を、多層プリント配線板を製造する手法により製造するようになっている（例えば、特許文献１参照）。 Recently, packages used for mounting semiconductor elements such as chip carriers, pin grid arrays, and ball grid arrays (hereinafter simply referred to as packages) have been manufactured by a technique for manufacturing a multilayer printed wiring board (for example, , See Patent Document 1).
例えば，ピングリッドアレイは，図１に示すように，半導体素子搭載部１を有する下基板２ａ並びに半導体素子を納めるキャビティー３となる窓穴４ｂ，４ｃ及び４ｄを形成した上基板２ｂ，２ｃ及び２ｄを接着一体化し，これに，電気的接続及び取り付け用導体ピン５を挿通した多層プリント配線板である。上基板の内の一枚，例えば２ｂには，半導体素子からのワイヤをボンディングするためのボンディングパッド６が通常設けられ，また，最上部に位置する上基板２ｄの表面を除き，下基板２ａ並びに上基板２ｄ及び２ｃには導体回路７が設けられている。なお，図１には，上基板を３枚とした例を示したが，上基板の枚数はこれに限られるものではない。 For example, as shown in FIG. 1, the pin grid array includes a lower substrate 2a having a semiconductor element mounting portion 1 and upper substrates 2b, 2c formed with window holes 4b, 4c and 4d serving as cavities 3 for housing semiconductor elements. This is a multilayer printed wiring board in which 2d is bonded and integrated, and electrical connection and mounting conductor pins 5 are inserted through it. One of the upper substrates, for example, 2b, is usually provided with a bonding pad 6 for bonding a wire from a semiconductor element, and the lower substrate 2a and the upper substrate 2d except for the surface of the upper substrate 2d located at the top. Conductor circuits 7 are provided on the upper substrates 2d and 2c. Although FIG. 1 shows an example in which three upper substrates are used, the number of upper substrates is not limited to this.
このように窓穴を設けた上基板２ｂ，２ｃ及び２ｄを接着一体化するときに従来の多層プリント配線板の製造に用いられていたものと同様のプリプレグを用いると，プレス工程において一旦溶融流動化した熱硬化性樹脂組成物（接着剤組成物）８がキャビティー３内にはみ出し，図２に示すように，ボンディングパッド６がはみ出した熱硬化性樹脂組成物（接着剤組成物）８に覆われることがあった。ボンディングパッド６がはみ出した熱硬化性樹脂組成物（接着剤組成物）８により覆われると，半導体素子からのワイヤをボンディングすることが困難になるので好ましくない。そこで，通常の多層プリント配線板の製造に用いられているプリプレグよりも熱硬化性樹脂組成物（接着剤組成物）の硬化を進めて，プレス成形時の樹脂フローを小さくしたプリプレグが開発されている。
しかしながら，熱硬化性樹脂組成物（接着剤組成物）の硬化条件は，樹脂組成や溶剤の種類，量等により変化するため樹脂フローを適正に調整することが困難であり，また，プレス成形時の樹脂フローを小さくしたプリプレグは，樹脂フローが小さいために導体回路間の凹みを充分に埋めることができないことがあるためボイドが残り，さらに，熱硬化性樹脂組成物（接着剤組成物）の硬化が進んでいるため，基板との接着性も悪くなるという欠点を有していた。 However, the curing conditions of the thermosetting resin composition (adhesive composition) vary depending on the resin composition, the type and amount of solvent, etc., and it is difficult to adjust the resin flow properly. The prepreg with a small resin flow has a small resin flow and may not be able to sufficiently fill the dents between the conductor circuits, leaving voids. In addition, the thermosetting resin composition (adhesive composition) Since the curing has progressed, the adhesiveness to the substrate is also deteriorated.
本発明は，以上のような実状に鑑みてなされたもので，樹脂フローの調整が容易な接着剤組成物，この接着剤組成物を用いることによりキャビティー内への樹脂のはみ出しが小さい多層プリント配線板，及び，その製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an adhesive composition in which the resin flow can be easily adjusted, and a multi-layer print in which the resin does not protrude into the cavity by using this adhesive composition. It aims at providing a wiring board and its manufacturing method.
本発明は、次のものに関する。
（１）熱硬化性樹脂，ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子及び主鎖の構造単位の一部が架橋したエラストマーを含有する接着剤組成物。
（２）少なくとも２つ以上の基板と基板間に存在する接着剤組成物からなる多層プリント配線板において、接着剤組成物が項（１）に記載の接着剤組成物である多層プリント配線板。
（３）少なくとも２つ以上の基板を接着してなる多層プリント配線板の製造方法において、項（１）に記載の接着剤組成物をワニスとし，このワニスを基板の接着面に塗布し，乾燥した後、加熱加圧することを特徴とする多層プリント配線板の製造方法。
The present invention relates to the following.
(1) An adhesive composition containing a thermosetting resin, core-shell type polymer particles having a core portion made of a rubber-like polymer, and an elastomer in which a part of the structural unit of the main chain is crosslinked.
(2) A multilayer printed wiring board comprising an adhesive composition present between at least two substrates and the substrate, wherein the adhesive composition is the adhesive composition according to item (1).
(3) In a method for producing a multilayer printed wiring board obtained by adhering at least two or more substrates, the adhesive composition according to item (1) is used as a varnish, and the varnish is applied to an adhesive surface of the substrate and dried. After that, a method for producing a multilayer printed wiring board, characterized by heating and pressing.
樹脂フローの調整が容易な接着剤組成物，この接着剤組成物を用いることによりキャビティー内への樹脂のはみ出しが小さい多層プリント配線板，及びその製造方法を提供することが可能となった。 It has become possible to provide an adhesive composition that allows easy adjustment of the resin flow, a multilayer printed wiring board in which the resin does not protrude into the cavity, and a method for producing the same by using this adhesive composition.
以下、本発明の好適な実施形態について詳細に説明する。
本発明の接着剤組成物は、熱硬化性樹脂，ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子及び主鎖の構造単位の一部が架橋したエラストマーを含有している。
Hereinafter, preferred embodiments of the present invention will be described in detail.
The adhesive composition of the present invention contains a thermosetting resin, core-shell type polymer particles having a core portion made of a rubber-like polymer, and an elastomer in which a part of the structural unit of the main chain is crosslinked.
ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子は，プレス成形時に溶融流動することなく，接着剤組成物の熱硬化性樹脂中に散在し，いわゆる海島型分散構造をとることができ，接着剤組成物の熱硬化性樹脂中に散在することにより，溶融した熱硬化性樹脂の流動を抑制することにより、例えばパッケージなどのキャビティー内への接着剤組成物のはみ出しを抑制することができる。また，主鎖の構造単位の一部が架橋したエラストマーも，プレス成形時に溶融流動することなく，接着剤組成物の熱硬化性樹脂中に粒子として散在し，いわゆる海島型分散構造をとることができ，接着剤組成物の熱硬化性樹脂中に散在する粒子により，溶融した熱硬化性樹脂の流動を抑制することにより、例えばパッケージなどのキャビティー内への接着剤組成物のはみ出しを抑制することができる。 The core-shell type polymer particles having a core portion made of a rubber-like polymer are dispersed in the thermosetting resin of the adhesive composition without being melt-flowed during press molding, and can take a so-called sea-island type dispersion structure. By suppressing the flow of the molten thermosetting resin by being scattered in the thermosetting resin of the adhesive composition, for example, the protrusion of the adhesive composition into the cavity of the package or the like is suppressed. Can do. In addition, an elastomer in which a part of the structural unit of the main chain is crosslinked may be dispersed as particles in the thermosetting resin of the adhesive composition without being melt-flowed during press molding, and may have a so-called sea-island type dispersion structure. And by suppressing the flow of the molten thermosetting resin by particles scattered in the thermosetting resin of the adhesive composition, for example, the protrusion of the adhesive composition into a cavity such as a package is suppressed. be able to.
熱硬化性樹脂中に配合するゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子及び主鎖の構造単位の一部が架橋したエラストマーの量により溶融した熱硬化性樹脂の流動性を調整できることから，流動性の制御も容易であり，かつ，安定した品質とすることができる。そして，プレス成形時の樹脂フローを小さくするために、従来技術のように接着剤組成物の硬化を予め進めておく必要がないので，基板同士の接着性を損なうこともない。 The fluidity of the melted thermosetting resin is adjusted by the amount of the core-shell type polymer particles having a core portion composed of a rubber-like polymer blended in the thermosetting resin and the elastomer in which a part of the main chain structural unit is crosslinked. Therefore, fluidity can be easily controlled and stable quality can be achieved. And in order to make the resin flow at the time of press molding small, since it is not necessary to advance hardening of an adhesive composition beforehand like the prior art, the adhesiveness of board | substrates is not impaired.
ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子と、主鎖の構造単位の一部が架橋したエラストマーは併用する。ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子を単独で使用し，接着剤組成物のパッケージなどのキャビティー内へのはみ出しを小さくすると，熱硬化性樹脂の量が相対的に少なくなり，熱硬化性樹脂の相が連続しなくなるため，接着剤組成物の接着性が低下するおそれがある。また，主鎖の構造単位の一部が架橋したエラストマーを単独で使用し，接着剤組成物のはみ出しを小さくすると，熱硬化性樹脂の量が相対的に少なくなり，誘電率，誘電正接の上昇あるいは多層プリント配線板の耐熱性が低下するなどの問題が発生するおそれがある。 Core-shell type polymer particles having a core portion made of a rubber-like polymer and an elastomer in which a part of the main chain structural unit is crosslinked are used in combination. When core-shell type polymer particles having a core portion made of a rubbery polymer are used alone and the protrusion of the adhesive composition into a cavity such as a package is reduced, the amount of thermosetting resin is relatively small. Therefore, since the thermosetting resin phase is not continuous, the adhesiveness of the adhesive composition may be lowered. In addition, if an elastomer in which a part of the structural unit of the main chain is cross-linked is used alone, and the protrusion of the adhesive composition is reduced, the amount of the thermosetting resin is relatively reduced, and the dielectric constant and dielectric loss tangent are increased. Or there exists a possibility that the problem that the heat resistance of a multilayer printed wiring board falls may generate | occur | produce.
少なくとも２つ以上の基板と基板間に存在する接着剤組成物からなる多層プリント配線板において、本発明の接着剤組成物は，プリプレグ、接着フィルム、ワニスなどいずれの形態で、多層プリント配線板に使用してもかまわない。また多層プリント配線板の製造方法としては、基板表面に形成された導体回路間の凹部を十分に埋めること、すなわち回路充填性の点から本発明の接着剤組成物を有機溶剤に溶解分散させて、ワニス状にし、これを接着面となる基板表面に塗布乾燥して、その上に他の基板を重ね加熱加圧する方法が好ましい。なお基板表面にワニス状の接着剤組成物を塗布する方法としては、特に制限されないが、印刷法、ディップ法などが挙げられる。 In a multilayer printed wiring board comprising an adhesive composition present between at least two substrates and the substrate, the adhesive composition of the present invention is applied to the multilayer printed wiring board in any form such as a prepreg, an adhesive film, and a varnish. You can use it. As a method for producing a multilayer printed wiring board, the concave portions between the conductor circuits formed on the substrate surface are sufficiently filled, that is, the adhesive composition of the present invention is dissolved and dispersed in an organic solvent from the viewpoint of circuit filling properties. A method of forming a varnish, applying and drying the varnish on the substrate surface to be an adhesive surface, and stacking another substrate thereon and heating and pressing is preferable. The method for applying the varnish-like adhesive composition to the substrate surface is not particularly limited, and examples thereof include a printing method and a dipping method.
本発明において接着剤組成物に使用される熱硬化性樹脂としては，シアナート樹脂，構造中にベンゾオキサジン環を有する樹脂，エポキシ樹脂，ポリイミド樹脂，構造中にトリアジン環を有する樹脂，フェノール樹脂，不飽和ポリエステル樹脂等が挙げられる。これらの熱硬化性樹脂を２種類以上適宜組み合わせて使用することもできる。これらの熱硬化性樹脂には，必要な硬化剤又は硬化促進剤が用いられるが，硬化剤又は硬化促進剤としては，それぞれの熱硬化性樹脂について公知の硬化剤又は硬化促進剤を使用することができ，特に制限はない。 The thermosetting resin used in the adhesive composition in the present invention includes cyanate resin, resin having a benzoxazine ring in the structure, epoxy resin, polyimide resin, resin having a triazine ring in the structure, phenol resin, non-curable resin. Examples include saturated polyester resins. Two or more of these thermosetting resins can be used in appropriate combination. For these thermosetting resins, the necessary curing agents or accelerators are used. As the curing agent or accelerator, a known curing agent or accelerator for each thermosetting resin should be used. There are no particular restrictions.
本発明において使用されるゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子は，好適には，ゴム状ポリマーから成る軟質コア部が、そのコア部にグラフト結合した硬質ポリマーのシェル部によって取り囲まれた２層構造の複合材料である。そしてコア部がスチレン−ブタジエンゴム，水素化スチレン−ブタジエンゴム，アクリルゴム等のいずれかから成るものが好ましく，シェル部が熱硬化性樹脂への分散性の良いポリメチルメタクリレート，ポリ（メチルメタクリレート−スチレン），ポリ（メチルメタクリレート−グリシジルメタクリレート）等のいずれかから構成された２層構造の粒子（複合材料）であることが好ましく，その平均粒子径は，０．０１〜０．１μｍの微小粒子となっているものが好ましい。なお、市販品として、スチレン−ブタジエンゴム系コア−シェル型ゴム（呉羽化学工業株式会社製，パラロイドＥＸＬ−２６５５（商品名））などが挙げられる。 The core-shell type polymer particles having a core portion made of a rubber-like polymer used in the present invention preferably have a soft polymer portion made of a rubber-like polymer and a hard polymer shell portion grafted to the core portion. It is a composite material with a two-layer structure surrounded. The core portion is preferably made of styrene-butadiene rubber, hydrogenated styrene-butadiene rubber, acrylic rubber or the like, and the shell portion is polymethyl methacrylate, poly (methyl methacrylate-) having good dispersibility in a thermosetting resin. It is preferably a two-layered particle (composite material) composed of any of styrene), poly (methyl methacrylate-glycidyl methacrylate), etc., and the average particle diameter is 0.01-0.1 μm fine particles Is preferred. Examples of commercially available products include styrene-butadiene rubber-based core-shell type rubber (manufactured by Kureha Chemical Industry Co., Ltd., Paraloid EXL-2655 (trade name)).
本発明において使用される主鎖の構造単位の一部が架橋したエラストマーとしては，ポリウレタン系，アクリル系，ポリアミド系，酢酸ビニル系等のエラストマーの主鎖の構造単位の一部を架橋させたエラストマーを挙げることができる。また主鎖の構造単位の一部が架橋したエラストマーとしては，例えばアクリロニトリル、アクリル酸、アクリル酸エチル、アクリル酸ブチル、アクリル酸グリシジル、ブタジエンなどを共重合成分とするエラストマーが挙げられ、天然ゴム、スチレン−ブタジエンゴム、イソプレンゴム、ブチルゴム、アクリロニトリル−ブタジエンゴム、エチレン−プロピレン−ジエンゴム、アクリルゴム等を過酸化物などの架橋剤を用いて部分的に処理したり、あるいは含有する官能基同士を付加反応あるいは縮合反応させることによって得られる。また、これらに含有される不飽和結合と特定の官能基を有する化合物を共重合させて側鎖や末端に反応性官能基を導入することによって、接着剤組成物や多層プリント配線板中の分散状態や界面接着性を制御することもできる。なかでも，熱硬化性樹脂と海島構造を形成しやすく，さらに吸湿時の耐熱性に優れていることから，アクリロニトリル−ブタジエン共重合体エラストマーが好ましく用いられる。前記エラストマーの粒子径は，熱硬化性樹脂への分散性の観点から，０．５〜２．０μｍであるのが好ましい。なお、市販品として、架橋アクリロニトリル−ブタジエン共重合体エラストマー（アクリロニトリル含有量２０重量％，日本合成ゴム株式会社製，ＸＥＲ−９１（商品名）、帝国化学産業社製アクリロニトリル変性アクリルゴムＨＴＲ−８６０−３ＤＲ（アクリロニトリル含有量３０重量％）、ダイセル化学工業社製エポキシ化ポリブタジエンＰＢ−３６００などが挙げられる。 The elastomer in which a part of the structural unit of the main chain used in the present invention is crosslinked is an elastomer in which a part of the structural unit of the main chain of an elastomer such as polyurethane, acrylic, polyamide, or vinyl acetate is crosslinked. Can be mentioned. Examples of the elastomer in which a part of the structural unit of the main chain is crosslinked include, for example, an elastomer having a copolymerization component of acrylonitrile, acrylic acid, ethyl acrylate, butyl acrylate, glycidyl acrylate, butadiene, natural rubber, Styrene-butadiene rubber, isoprene rubber, butyl rubber, acrylonitrile-butadiene rubber, ethylene-propylene-diene rubber, acrylic rubber, etc. are partially treated with a crosslinking agent such as peroxide, or functional groups contained are added to each other. It can be obtained by reaction or condensation reaction. In addition, by dissociating unsaturated bonds contained in these compounds and compounds having specific functional groups and introducing reactive functional groups at the side chains and terminals, dispersion in adhesive compositions and multilayer printed wiring boards is achieved. The state and interfacial adhesion can also be controlled. Of these, an acrylonitrile-butadiene copolymer elastomer is preferably used because it easily forms a sea-island structure with a thermosetting resin and is excellent in heat resistance during moisture absorption. The particle diameter of the elastomer is preferably 0.5 to 2.0 μm from the viewpoint of dispersibility in a thermosetting resin. As commercially available products, crosslinked acrylonitrile-butadiene copolymer elastomer (acrylonitrile content 20% by weight, manufactured by Nippon Synthetic Rubber Co., Ltd., XER-91 (trade name), Teikoku Chemical Industry Co., Ltd. acrylonitrile modified acrylic rubber HTR-860- 3DR (acrylonitrile content 30% by weight), epoxidized polybutadiene PB-3600 manufactured by Daicel Chemical Industries, and the like.
熱硬化性樹脂，ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子及び主鎖の構造単位の一部が架橋したエラストマーの配合割合は，熱硬化性樹脂１００重量部に対して，ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子を５〜４０重量部とし、更に主鎖の構造単位の一部が架橋したエラストマーを１〜５重量部とするのが好ましい。 The blending ratio of the thermosetting resin, the core-shell type polymer particles having a core portion made of a rubbery polymer, and the elastomer in which a part of the structural unit of the main chain is crosslinked is based on 100 parts by weight of the thermosetting resin. It is preferable that the core-shell type polymer particles having a core portion made of a polymer are 5 to 40 parts by weight, and further the elastomer in which a part of the structural unit of the main chain is crosslinked is 1 to 5 parts by weight.
ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子の配合量が５重量部未満であると，樹脂のはみ出しを抑制する効果が小さい。また主鎖の構造単位の一部が架橋したエラストマーの配合量が１重量部未満であると，樹脂のはみ出しを小さくする効果が小さくなる。また，ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子の配合量が４０重量部を超える場合には，熱硬化性樹脂の量が相対的に少なくなり，熱硬化性樹脂の相が連続しなくなるため，接着性が劣る。また，主鎖の構造単位の一部が架橋したエラストマーの配合量が５重量部を超える場合には，誘電率，誘電正接の上昇及び多層プリント配線板の耐熱性が低下する。また熱硬化性樹脂１００重量部に対して，ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子を１０〜３０重量部とするのがより好ましい。更に熱硬化性樹脂１００重量部に対して，主鎖の構造単位の一部が架橋したエラストマーを２〜４重量部とするのがより好ましい。 When the blending amount of the core-shell type polymer particles having a core portion made of a rubbery polymer is less than 5 parts by weight, the effect of suppressing the protrusion of the resin is small. Further, when the amount of the elastomer in which a part of the structural unit of the main chain is crosslinked is less than 1 part by weight, the effect of reducing the protrusion of the resin is reduced. In addition, when the amount of the core-shell type polymer particles having a core portion made of a rubbery polymer exceeds 40 parts by weight, the amount of the thermosetting resin is relatively small, and the phase of the thermosetting resin is reduced. Adhesion is inferior because it is not continuous. Further, when the blending amount of the elastomer in which a part of the structural unit of the main chain is crossed exceeds 5 parts by weight, the dielectric constant and the dielectric loss tangent are increased and the heat resistance of the multilayer printed wiring board is decreased. More preferably, the core-shell type polymer particles having a core portion made of a rubber-like polymer are 10 to 30 parts by weight with respect to 100 parts by weight of the thermosetting resin. Furthermore, it is more preferable to use 2 to 4 parts by weight of an elastomer in which a part of the structural unit of the main chain is crosslinked with respect to 100 parts by weight of the thermosetting resin.
本発明の多層プリント配線板の製造方法において、本発明の接着剤組成物は有機溶剤に溶解分散させ，ワニスとして基板に塗布することにより使用されるのが好ましいが，ここで使用される有機溶剤としては，メチルエチルケトン，メチルエチルグリコール，メチルイソブチルケトン，メチルセルソルブ，ジメチルホルムアミド，ジメチルアセトアミド，アセトン，トルエン，メタノール等が挙げられ，これらは，単独で又は適宜２種類以上組み合わせて使用される。接着剤組成物とこれら有機溶剤との配合割合は，ワニスとして基板に塗布するときの作業性により選定される。ワニス塗布後の乾燥は指触乾燥とされるのが，基板同士の良好な接着を形成できる点から好ましい。 In the method for producing a multilayer printed wiring board of the present invention, the adhesive composition of the present invention is preferably used by dissolving and dispersing in an organic solvent and applying it to a substrate as a varnish. Examples thereof include methyl ethyl ketone, methyl ethyl glycol, methyl isobutyl ketone, methyl cellosolve, dimethylformamide, dimethylacetamide, acetone, toluene, methanol and the like, and these may be used alone or in appropriate combination of two or more. The blending ratio of the adhesive composition and these organic solvents is selected depending on the workability when the adhesive composition is applied to the substrate as a varnish. Drying after applying the varnish is preferably touch-drying because it can form good adhesion between the substrates.
なお，主として半導体搭載用のキャビティーを有する多層プリント配線板について説明したが，本発明の接着剤組成物及び本発明の製造方法はキャビティーを有さない通常の多層プリント配線板の製造にも適用できることはいうまでもない。 The multilayer printed wiring board having a cavity for mounting a semiconductor has been mainly described. However, the adhesive composition of the present invention and the manufacturing method of the present invention can also be used for manufacturing a normal multilayer printed wiring board having no cavity. Needless to say, this is applicable.
（実施例１）
熱硬化性樹脂として２，２−ビス（４−シアナトフェニル）プロパン（旭チバ株式会社製，Ａｒｏｃｙ Ｂ−１０（商品名））７７重量部と、ポリ（２，６−ジメチル−１，４フェニレン）エーテル（日本ジーイープラスチックス株式会社製，ノリルＰＫＮ４７５２（商品名））２０重量部及びＰ−（α−クミル）フェノール（サンテクノケミカル株式会社製，ＰＣＰ（商品名））１重量部をトルエン３０重量部に加熱溶解分散し，金属系反応触媒としてナフテン酸マンガン（マンガン含有量１０重量％，日本化学産業株式会社製を）０．０３重量部を添加後液温を１２０℃として反応させた。更に９０℃に冷却後シアネートエステル類化合物と反応性を有しない難燃剤として２，４，６−トリス（トリブロモフェノキシ）−１，３，５−トリアジン（第一工業製薬株式会社製，ＳＲ−２４５（商品名））１４重量部を投入し，次いでメチルエチルケトン３０重量部を投入撹拌して，更に４０℃以下に冷却後に前記Ｐ−（α−クミル）フェノール８重量部，金属系反応触媒としてナフテン酸亜鉛（亜鉛含有量８重量％，日本化学産業株式会社製）０．０１２５重量部，ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子としてスチレン−ブタジエンゴム系コア−シェル型ゴム（呉羽化学工業株式会社製，パラロイドＥＸＬ−２６５５（商品名））３０重量部，主鎖の構造単位の一部が架橋したエラストマーとして架橋アクリロニトリル−ブタジエン共重合体エラストマー（アクリロニトリル含有量２０重量％，日本合成ゴム株式会社製，ＸＥＲ−９１（商品名））４重量部を添加して、接着剤組成物ワニスを調製した。
Example 1
As a thermosetting resin, 77 parts by weight of 2,2-bis (4-cyanatophenyl) propane (Arocy B-10 (trade name) manufactured by Asahi Ciba Co., Ltd.) and poly (2,6-dimethyl-1,4) 30 parts of toluene by adding 20 parts by weight of phenylene) ether (manufactured by GE Plastics, Noryl PKN4752 (trade name)) and 1 part by weight of P- (α-cumyl) phenol (manufactured by Sun Techno Chemical Co., Ltd., PCP (trade name)) The mixture was dissolved by heating in parts by weight, and 0.03 part by weight of manganese naphthenate (manganese content: 10% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added as a metal-based reaction catalyst, followed by reaction at a liquid temperature of 120 ° C. Further, 2,4,6-tris (tribromophenoxy) -1,3,5-triazine (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., SR-) as a flame retardant having no reactivity with cyanate ester compounds after cooling to 90 ° C. 245 (trade name)), 14 parts by weight, and then 30 parts by weight of methyl ethyl ketone were added and stirred. After cooling to 40 ° C. or lower, 8 parts by weight of the P- (α-cumyl) phenol was added as a metal-based reaction catalyst, naphthene. Styrene-butadiene rubber-based core-shell type rubber as core-shell type polymer particles having 0.0125 parts by weight of zinc acid (
５００×３００ｍｍ，厚さ０．２ｍｍ，銅はく厚さ１２μｍの片面銅張積層板に導体回路を形成して下基板とした。また，５００×３００ｍｍ，厚さ０．１ｍｍ，銅はく厚さ１２μｍの片面銅張積層板に導体回路及び１５×１５ｍｍの窓穴を形成して上基板とした。次に，前記下基板に上基板を重ねたときの窓穴の位置をマスクし，前記で調整した接着剤組成物ワニスを印刷により，前記下基板の表面に導体回路の凹凸が現れないように塗布し，その後，８０℃で３０分間加熱して有機溶剤を揮発させ，厚さが５０μｍの接着剤組成物層を形成した。この接着剤組成物層の上に，前記上基板を重ね，温度２００℃，圧力３．０ＭＰａで加熱加圧することにより多層プリント配線板を作製した。 A conductor circuit was formed on a single-sided copper-clad laminate having a thickness of 500 × 300 mm, a thickness of 0.2 mm, and a copper foil thickness of 12 μm to form a lower substrate. In addition, a conductor circuit and a 15 × 15 mm window hole were formed on a single-sided copper clad laminate having a thickness of 500 × 300 mm, a thickness of 0.1 mm, and a copper foil thickness of 12 μm. Next, the position of the window hole when the upper substrate is overlaid on the lower substrate is masked, and the adhesive composition varnish adjusted as described above is printed so that the irregularities of the conductor circuit do not appear on the surface of the lower substrate. After coating, the organic solvent was volatilized by heating at 80 ° C. for 30 minutes to form an adhesive composition layer having a thickness of 50 μm. The upper substrate was overlaid on this adhesive composition layer, and a multilayer printed wiring board was produced by heating and pressing at a temperature of 200 ° C. and a pressure of 3.0 MPa.
（実施例２）
熱硬化性樹脂として熱硬化性ポリイミド樹脂（仏ローヌプーラン社製，ケルイミド６０１（商品名））４５重量部及びフェノールノボラック型エポキシ樹脂（ジャパンエポキシ株式会社製，エピコート１５４（商品名））４５重量部を、ジメチルアセトアミド６０重量部に加熱溶解分散し，３０℃以下に冷却後にジシアンジアミド１０重量部，ゴム状ポリマーから成るコア部を有するコア−シェル型ポリマー粒子としてスチレン−ブタジエンゴム系コア−シェル型ゴム（呉羽化学工業株式会社製，パラロイドＥＸＬ−２６５５（商品名））３０重量部，主鎖の構造単位の一部が架橋したエラストマーとして架橋アクリロニトリル−ブタジエン共重合体エラストマー（アクリロニトリル含有量２０重量％，日本合成ゴム株式会社製，ＸＥＲ−９１（商品名））４重量部を添加して接着剤組成物ワニスを調製した。以下，実施例１と同様にして多層プリント配線板を作製した。
(Example 2)
45 parts by weight of thermosetting polyimide resin (manufactured by Rhône-Poulenc, Kelimide 601 (trade name)) and 45 parts by weight of phenol novolac type epoxy resin (manufactured by Japan Epoxy Co., Ltd., Epicoat 154 (trade name)) Is dissolved and dispersed in 60 parts by weight of dimethylacetamide, cooled to 30 ° C. or lower, dicyandiamide 10 parts by weight, and core-shell type polymer particles having a core part composed of a rubber-like polymer. (Kureha Chemical Industries, Ltd., Paraloid EXL-2655 (trade name)) 30 parts by weight, a crosslinked acrylonitrile-butadiene copolymer elastomer (acrylonitrile content 20% by weight, as an elastomer in which a part of the main chain structural unit is crosslinked) Made by Nippon Synthetic Rubber Co., Ltd., XER-9 (Trade name)) 4 parts by weight was added to prepare an adhesive composition varnish. Thereafter, a multilayer printed wiring board was produced in the same manner as in Example 1.
（比較例１）
スチレン−ブタジエンゴム系コア−シェル型ゴム及び架橋アクリロニトリル−ブタジエン共重合体エラストマーを除いたほかは，実施例１と同様にして接着剤組成物ワニスを調整し，さらに多層プリント配線板を作製した。
(Comparative Example 1)
An adhesive composition varnish was prepared in the same manner as in Example 1 except that the styrene-butadiene rubber-based core-shell type rubber and the crosslinked acrylonitrile-butadiene copolymer elastomer were removed, and a multilayer printed wiring board was produced.
（比較例２）
スチレン−ブタジエンゴム系コア−シェル型ゴム及び架橋アクリロニトリル−ブタジエン共重合体エラストマーを除いたほかは，実施例２と同様にして接着剤組成物ワニスを調整し，さらに多層プリント配線板を作製した。
(Comparative Example 2)
An adhesive composition varnish was prepared in the same manner as in Example 2 except that the styrene-butadiene rubber-based core-shell type rubber and the crosslinked acrylonitrile-butadiene copolymer elastomer were removed, and a multilayer printed wiring board was produced.
（比較例３）
スチレン−ブタジエンゴム系コア−シェル型ゴムを除いたほかは，実施例１と同様にして接着剤組成物ワニスを調整し，さらに多層プリント配線板を作製した。
(Comparative Example 3)
An adhesive composition varnish was prepared in the same manner as in Example 1 except that the styrene-butadiene rubber-based core-shell type rubber was omitted, and a multilayer printed wiring board was produced.
（比較例４）
スチレン−ブタジエンゴム系コア−シェル型ゴムを除いたほかは，実施例２と同様にして接着剤組成物ワニスを調整し，さらに多層プリント配線板を作製した。
(Comparative Example 4)
An adhesive composition varnish was prepared in the same manner as in Example 2 except that the styrene-butadiene rubber-based core-shell type rubber was omitted, and a multilayer printed wiring board was produced.
実施例１及び２並びに比較例１，２，３，４で調整した接着剤組成物ワニスを真空脱溶剤して，２００℃で９０分間加熱して硬化させた。得られた硬化物について，ＪＩＳ Ｃ ６４８１に規定されるＴＭＡ法によりガラス転移点（Ｔｇ）を調べた。結果を表１に示した。 The adhesive composition varnishes prepared in Examples 1 and 2 and Comparative Examples 1, 2, 3, and 4 were subjected to vacuum desolvation and heated at 200 ° C. for 90 minutes to be cured. About the obtained hardened | cured material, the glass transition point (Tg) was investigated by the TMA method prescribed | regulated to JISC6481. The results are shown in Table 1.
また，実施例１及び２並びに比較例１，２，３，４で作製した多層プリント配線板について，樹脂のはみ出し長さ，ボイドの有無，接着部のピール強度を次のようにして調べた。結果を表１に示した。
（１）樹脂のはみ出し長さ：上基板の開口部（１５×１５ｍｍの窓穴）の壁から，はみ出した接着剤組成物の最大の長さをマイクロセクション法により測定した。
（２）ボイドの有無：下基板の導体回路上に形成した接着剤層表面を目視により観察した。
（３）接着部のピール強度：上基板と下基板とを９０度方向にクロックヘッドスピード５０ｍｍ／分で引きはがすのに要する荷重を測定した。
Further, for the multilayer printed wiring boards produced in Examples 1 and 2 and Comparative Examples 1, 2, 3, and 4, the protruding length of the resin, the presence or absence of voids, and the peel strength of the bonded portion were examined as follows. The results are shown in Table 1.
(1) Extrusion length of resin: The maximum length of the adhesive composition protruding from the wall of the opening (15 × 15 mm window hole) of the upper substrate was measured by the microsection method.
(2) Presence / absence of voids: The surface of the adhesive layer formed on the conductor circuit of the lower substrate was visually observed.
(3) Peel strength of the bonded portion: The load required to peel off the upper substrate and the lower substrate in the 90-degree direction at a clock head speed of 50 mm / min was measured.
表１に示したように、実施例１及び２とも、比較例１〜４と比べ、キャビティーに相当する開口部（１５×１５ｍｍの窓穴）の壁からの樹脂（接着剤組成物）のはみ出し長さは著しく小さい（４分の１以下）ことがわかる。また接着部のピール強度も良好であり、導体回路間のボイドも認められなかった。本発明によれば，キャビティー内への樹脂のはみ出しを小さくすることができて，さらに，基板間の接着性も良好とすることができる。さらに，導体回路間の凹みに接着剤組成物を塗布し，乾燥した後加熱加圧するので，導体回路間の凹みを充分に埋めることができ，ボイドのない接着性の良好な多層プリント配線板を製造することができる。 As shown in Table 1, in both Examples 1 and 2, compared with Comparative Examples 1 to 4, the resin (adhesive composition) from the wall of the opening (15 × 15 mm window hole) corresponding to the cavity was used. It can be seen that the overhang length is extremely small (1/4 or less). Also, the peel strength of the bonded part was good, and no voids were found between the conductor circuits. According to the present invention, the protrusion of the resin into the cavity can be reduced, and the adhesion between the substrates can be improved. In addition, since the adhesive composition is applied to the recesses between the conductor circuits, dried and heated and pressed, the recesses between the conductor circuits can be sufficiently filled, and a multilayer printed wiring board with good adhesion without voids can be obtained. Can be manufactured.
１ 半導体素子搭載部
２ａ 下基板
２ｂ，２ｃ，２ｄ 上基板
３ キャビティー
４ｂ，４ｃ，４ｄ 窓穴
５ 導体ピン
６ ボンディングパッド
７ 導体回路
８ 熱硬化樹脂組成物（接着剤組成物）
ＩＩ ピングリッドアレイの要部
DESCRIPTION OF SYMBOLS 1 Semiconductor element mounting part 2a Lower board | substrate 2b, 2c, 2d Upper board | substrate 3 Cavity 4b, 4c, 4d Window hole 5 Conductor pin 6 Bonding pad 7
II Main part of pin grid array
Claims (3)
In the manufacturing method of a multilayer printed wiring board formed by bonding at least two or more substrates, the adhesive composition according to claim 1 is used as a varnish, the varnish is applied to the bonding surface of the substrate, dried, and then heated. A method for producing a multilayer printed wiring board, characterized by applying pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005005092A JP2006193583A (en) | 2005-01-12 | 2005-01-12 | Adhesive composition, multi-layered printed circuit board using the adhesive composition and method for producing multi-layered printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005005092A JP2006193583A (en) | 2005-01-12 | 2005-01-12 | Adhesive composition, multi-layered printed circuit board using the adhesive composition and method for producing multi-layered printed circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006193583A true JP2006193583A (en) | 2006-07-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005005092A Pending JP2006193583A (en) | 2005-01-12 | 2005-01-12 | Adhesive composition, multi-layered printed circuit board using the adhesive composition and method for producing multi-layered printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2006193583A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010084083A (en) * | 2008-10-02 | 2010-04-15 | Yokohama Rubber Co Ltd:The | Epoxy resin composition |
| JP2010185034A (en) * | 2009-02-13 | 2010-08-26 | Yokohama Rubber Co Ltd:The | Structural adhesive composition |
-
2005
- 2005-01-12 JP JP2005005092A patent/JP2006193583A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010084083A (en) * | 2008-10-02 | 2010-04-15 | Yokohama Rubber Co Ltd:The | Epoxy resin composition |
| JP2010185034A (en) * | 2009-02-13 | 2010-08-26 | Yokohama Rubber Co Ltd:The | Structural adhesive composition |
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