JPH115828A - Resin composition for copper-clad laminate, copper foil with resin, multilayer copper-clad laminate and multilayer printed wiring board - Google Patents
Resin composition for copper-clad laminate, copper foil with resin, multilayer copper-clad laminate and multilayer printed wiring boardInfo
- Publication number
- JPH115828A JPH115828A JP17656597A JP17656597A JPH115828A JP H115828 A JPH115828 A JP H115828A JP 17656597 A JP17656597 A JP 17656597A JP 17656597 A JP17656597 A JP 17656597A JP H115828 A JPH115828 A JP H115828A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- copper
- clad laminate
- resin composition
- epoxy resin
- 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.)
- Pending
Links
Landscapes
- Epoxy Resins (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性に優れた多
層プリント配線板およびその製造に好適な銅張積層板用
樹脂組成物、樹脂付き銅箔及び多層銅張積層板に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer printed wiring board having excellent heat resistance, a resin composition for a copper-clad laminate suitable for the production thereof, a resin-coated copper foil, and a multilayer copper-clad laminate.
【０００２】[0002]
【従来の技術】従来から電子産業で使用されているプリ
ント配線板用積層板は、ガラスクロス、クラフト紙、ガ
ラス不織布等にフェノール樹脂、エポキシ樹脂等の熱硬
化性樹脂を含浸し、半硬化状態としたプリプレグと、そ
の片面または両面に銅箔を張り合わせて積層することに
より製造される場合が多い。また上記銅張積層板の両面
に回路形成を行って内層材を作成し、さらにプリプレグ
を介して銅箔を両面に張り合わせ、外層の銅箔をエッチ
ングして回路を形成した多層プリント配線板も製造され
ている。2. Description of the Related Art A laminated board for a printed wiring board conventionally used in the electronics industry is obtained by impregnating a glass cloth, kraft paper, glass nonwoven fabric, etc. with a thermosetting resin such as a phenolic resin or an epoxy resin, and in a semi-cured state. In many cases, the prepreg is manufactured by laminating a prepreg and a copper foil on one or both sides thereof. Circuits are also formed on both sides of the copper-clad laminate to create an inner layer material, a copper foil is laminated on both sides via a prepreg, and the outer layer copper foil is etched to form a multilayer printed wiring board. Have been.
【０００３】近年になって、プリント配線板の高密度化
に伴い、プリント配線板の表面に、微細な非貫通穴いわ
ゆるバイアホールを設けることが一般化している。この
ときにバイアホールを形成する方法としては、レーザー
光線やプラズマ加工により行われる。このときにガラス
繊維のような無機成分を含有するプリプレグを絶縁層と
して使用するとレーザー光線やプラズマによる加工性が
悪いので、無機成分を含有しない樹脂のみを絶縁層とし
て使用する場合が多い。この場合は樹脂層として、液状
の樹脂を直接内層回路上に塗布したものや、半硬化状態
の熱硬化性樹脂からなる樹詣フィルムや銅箔の片面に樹
脂を塗布し、半硬化させた樹脂等が用いられる。それら
を介して外層用銅箔が回路形成されたプリント配線板
（内層材）に積層され、外層銅箔の回路形成やバイアホ
ール形成を行い、多層プリント配線板に加工される。In recent years, with the increase in density of printed wiring boards, it has become common to provide fine non-through holes, so-called via holes, on the surface of the printed wiring board. At this time, a via hole is formed by laser beam or plasma processing. At this time, if a prepreg containing an inorganic component such as glass fiber is used as the insulating layer, workability by laser light or plasma is poor. Therefore, only a resin containing no inorganic component is often used as the insulating layer. In this case, as a resin layer, a resin in which a liquid resin is applied directly on the inner layer circuit, or a resin in which a resin is applied to one side of a thermosetting resin or a copper foil in a semi-cured state and the resin is semi-cured Are used. The copper foil for the outer layer is laminated on the printed wiring board (inner layer material) on which the circuit is formed via these, the circuit formation of the outer layer copper foil and the formation of the via hole are performed, and the copper foil is processed into a multilayer printed wiring board.
【０００４】しかし、このような多層プリント配線板加
工時に、液状の樹脂を直接内層回路上に塗布する方法の
場合は、樹脂を精度よく塗工する困難さや、回路をメッ
キにより作成する際に研磨等に手間がかかるといった問
題がある。また樹脂フィルムを用いる場合は、プラスチ
ックスフィルムに樹脂組成物を塗布することにより製造
されるが、使用後に破棄されるプラスチックスフィルム
のコストがかかるといった問題があり、樹脂付き銅箔と
して使用する方法がより一般的である。また樹脂成分と
しては、エポキシ樹脂が使用される場合が多い。However, when such a method is used in which a liquid resin is applied directly onto an inner layer circuit at the time of processing a multilayer printed wiring board, it is difficult to apply the resin with high precision, and polishing is required when the circuit is formed by plating. There is a problem that it takes time and the like. When a resin film is used, it is manufactured by applying a resin composition to a plastic film, but there is a problem that the cost of the plastic film discarded after use is high, and a method of using the resin-coated copper foil is used. Is more common. As the resin component, an epoxy resin is often used.
【０００５】本発明者らは、エポキシ樹脂とポリビニル
アセタール樹脂、ウレタン樹脂等からなる樹脂組成物を
銅箔に塗布した樹脂付き銅箔をすでに提案している（特
開平８−１３４４２５）。このような樹脂組成とするこ
とにより、半硬化状態での取り扱いの容易さやプレスに
より積層する際の樹脂流れの制御が格段に向上する。こ
のような方法により製造された積層板は、プリント配線
板用として、実用上満足できる耐熱性、電気特性、耐薬
品特性を有しているものの、エポキシ樹脂を主成分とし
ているために、高度な耐熱性は得られないといった問題
があった。高度な耐熱性が要求される揚合としては、デ
バイスを実装する際にワイヤボンディングを行う場合に
特に問題となる。このときにプリント配線板は高温下で
も高い弾性率を維持する必要があることから、高度の耐
熱性が必要とされているので従来のエポキシ樹脂系では
適応できない場合があった。The present inventors have already proposed a resin-coated copper foil in which a resin composition comprising an epoxy resin, a polyvinyl acetal resin, a urethane resin and the like is applied to a copper foil (Japanese Patent Application Laid-Open No. 8-134425). By using such a resin composition, the ease of handling in a semi-cured state and the control of resin flow when laminating by pressing are significantly improved. Laminated boards manufactured by such a method have high heat resistance, electrical properties, and chemical resistance properties that are practically satisfactory for printed wiring boards. There is a problem that heat resistance cannot be obtained. As a requirement for high heat resistance, there is a problem particularly when wire bonding is performed when mounting a device. At this time, since the printed wiring board needs to maintain a high elastic modulus even at a high temperature, a high degree of heat resistance is required.
【０００６】そこで、エポキシ樹脂をマレイミド化合物
で変性することが提案されている。これにより樹脂の耐
熱性は大輻に向上するが、硬化物は非常に脆くなり、機
械的な衝撃や熱的衝撃を受けた場合にクラックを生じる
ことがあり実用的ではなかった。またマレイミド樹脂を
ゴム類で変性して耐クラック性を改善する方法も提案さ
れているが、硬化物の耐熱性が非常に悪くなるので一般
的ではなかった。Accordingly, it has been proposed to modify an epoxy resin with a maleimide compound. Thereby, the heat resistance of the resin is greatly improved, but the cured product becomes very brittle, and may be cracked when subjected to a mechanical or thermal shock, which is not practical. Further, a method of improving the crack resistance by modifying a maleimide resin with rubbers has also been proposed, but it has not been common since the heat resistance of the cured product becomes extremely poor.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、上述
した従来技術の技術的課題を解決し、高度な耐熱性を有
し、かつ機械的な衝撃や熱的衝撃を受けた際にも極めて
高い耐クラック性を示す銅張積層板用樹脂組成物及びこ
れを用いた樹脂付き銅箔を提供することにある。また、
本発明の別の目的は、このように高度な耐熱性及び高い
耐クラック性を示す銅張積層板用樹脂組成物および樹脂
付き銅箔を用いた多層銅張積層板及び多層プリント配線
板を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned technical problems of the prior art, to have high heat resistance, and to be capable of receiving a mechanical shock or a thermal shock. An object of the present invention is to provide a resin composition for a copper-clad laminate having extremely high crack resistance and a resin-coated copper foil using the same. Also,
Another object of the present invention is to provide a resin composition for a copper-clad laminate exhibiting such high heat resistance and high crack resistance, and a multilayer copper-clad laminate and a multilayer printed wiring board using a resin-coated copper foil. Is to do.
【０００８】[0008]
【課題を解決するための手段】本発明者等は、上記課題
を解決するために種々検討した結果、銅張積層板用樹脂
組成物として、エポキシ樹脂およびその硬化剤からなる
エポキシ樹脂配合物、マレイミド化合物及び水酸基およ
び水酸基以外のエポキシ樹脂またはマレイミド化合物と
重合可能な官能基を有するポリビニルアセタール樹脂を
採用することにより、上述した従来技術の技術的課題を
解決することができる本発明を完成するに至った。The present inventors have conducted various studies to solve the above problems, and as a result, as a resin composition for a copper-clad laminate, an epoxy resin compound comprising an epoxy resin and a curing agent thereof, By adopting a maleimide compound and a hydroxyl group and an epoxy resin other than the hydroxyl group or a polyvinyl acetal resin having a functional group capable of polymerizing with the maleimide compound, the present invention which can solve the above-mentioned technical problems of the prior art is completed. Reached.
【０００９】すなわち本発明の銅張積層板用樹脂組成物
は、以下の成分 １）エポキシ樹脂およびその硬化剤からなるエポキシ樹
脂配合物、 ２）マレイミド化合物、および ３）水酸基および水酸基以外のエポキシ樹脂またはマレ
イミド化合物と重合可能な官能基を有するポリビニルア
セタール樹脂 を含有することを特徴とするものである。尚、前記エポ
キシ樹脂配合物には、硬化促進剤を含んでいても良い。
また、本発明の樹脂付き銅箔は、多層プリント配線板用
の層間絶縁樹脂成分として、本発明の前記銅張積層板用
樹脂組成物を銅箔の片面に塗工して得られるものであ
る。That is, the resin composition for a copper-clad laminate of the present invention comprises the following components: 1) an epoxy resin compound comprising an epoxy resin and a curing agent thereof; 2) a maleimide compound; and 3) a hydroxyl group and an epoxy resin other than a hydroxyl group. Or, it is characterized by containing a polyvinyl acetal resin having a functional group capable of polymerizing with a maleimide compound. The epoxy resin composition may contain a curing accelerator.
The resin-coated copper foil of the present invention is obtained by applying the resin composition for a copper-clad laminate of the present invention to one surface of a copper foil as an interlayer insulating resin component for a multilayer printed wiring board. .
【００１０】さらに、本発明の多層銅張積層板は、絶縁
基材層と該絶縁基材層の片面又は両面に形成された内層
回路と、該内層回路の外側に絶縁樹脂層を介して形成さ
れた外層回路用銅箔からなる多層銅張積層板であって、
前記内層回路と前記外層回路用銅箔間に存在する前記絶
縁樹脂層を本発明の前記銅張積層板用樹脂組成物で形成
したことを特徴とするものである。Further, the multilayer copper-clad laminate of the present invention comprises an insulating base layer, an inner layer circuit formed on one or both sides of the insulating base layer, and an insulating resin layer formed outside the inner layer circuit. A multilayer copper-clad laminate comprising a copper foil for an outer layer circuit,
The insulating resin layer present between the inner layer circuit and the outer layer copper foil is formed of the resin composition for a copper-clad laminate of the present invention.
【００１１】またさらに、本発明の多層プリント配線板
は、絶縁基材層と該絶縁基材層の片面又は両面に形成さ
れた内層回路と、該内層回路の外側に絶縁樹脂層を介し
て形成された外層回路とからなる多層プリント配線板で
あって、前記内層回路と前記外層回路間に存在する前記
絶縁樹脂層を本発明の前記銅張積層板用樹脂組成物で形
成したことを特徴とするものである。Further, the multilayer printed wiring board according to the present invention comprises an insulating base layer, an inner layer circuit formed on one or both sides of the insulating base layer, and an insulating resin layer formed outside the inner layer circuit. A multilayer printed wiring board comprising an outer layer circuit, wherein the insulating resin layer present between the inner layer circuit and the outer layer circuit is formed of the resin composition for a copper-clad laminate of the present invention. Is what you do.
【００１２】[0012]
【発明の実施の形態】以下、本発明の銅張積層板用樹脂
組成物についてさらに詳細に説明する。本発明の銅張積
層板用樹脂組成物では、使用されるエポキシ樹脂および
その硬化剤のうち、エポキシ樹脂としては電気、電子材
料に使用される品種であれば特に制限なく使用できる。
例示すると、ビスフェノールＡ型エポキシ樹脂、ビスフ
ェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹
詣、クレゾールノボラック型エポキシ樹脂、テトラブロ
モビスフェノール樹脂及びグリシジルアミン型エポキシ
樹脂等である。またエポキシ樹脂の硬化剤としては、樹
脂付き銅箔として使用されることが前提であるので、ジ
シアンジアミド、イミダゾール類、芳香族アミン類、フ
ェノールノボラック樹脂及びクレゾールノボラック樹脂
等の室温で活性が低く、加熱により硬化するいわゆる潜
在性硬化剤が好適である。このときにエポキシ樹脂とそ
の硬化剤との反応を促進する硬化促進剤も好ましく使用
できる。硬化促進剤としては、３級アミン類、イミダゾ
ール類が使用できるが、イミダゾール類は上記マレイミ
ド化合物の硬化促進剤とも作用するので、さらに好適で
ある。尚、前記エポキシ樹脂配合物は、エポキシ樹脂お
よびその硬化剤からなるが、硬化促進剤を含んでいても
良い。エポキシ樹脂配合物の含有率は樹脂組成物の総量
１００重量部に対して４０〜８０重量部であることが望
ましい。４０重量部未満では接着性が低下し、また８０
重量部を越えると耐熱性向上効果が期待できない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the resin composition for a copper-clad laminate of the present invention will be described in more detail. In the resin composition for a copper-clad laminate of the present invention, among the epoxy resin used and its curing agent, the epoxy resin can be used without any particular limitation as long as it is a type used for electric and electronic materials.
Examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, tetrabromobisphenol resin and glycidylamine type epoxy resin. As a curing agent for the epoxy resin, it is presumed that the resin is used as a copper foil with a resin, so that dicyandiamide, imidazoles, aromatic amines, phenol novolak resins, cresol novolak resins, and the like have low activity at room temperature and are heated. A so-called latent curing agent that cures with the aid of a curing agent is preferred. At this time, a curing accelerator that promotes the reaction between the epoxy resin and its curing agent can also be preferably used. As the curing accelerator, tertiary amines and imidazoles can be used, but imidazoles are more preferable because they act also as a curing accelerator for the maleimide compound. The epoxy resin composition comprises an epoxy resin and a curing agent thereof, but may contain a curing accelerator. The content of the epoxy resin compound is desirably 40 to 80 parts by weight based on 100 parts by weight of the total amount of the resin composition. If the amount is less than 40 parts by weight, the adhesiveness decreases, and
Exceeding the parts by weight cannot improve the heat resistance.
【００１３】マレイミド化合物としてはＮ，Ｎ’−
（４，４−ジフェニルメタン）ビスマレイミド、ビス
（３−エチル−５メチル−４−マレイミドフェニ）メタ
ン、２，２ビス［４−（４−マレイミドフェノキシ）フ
ェニル］プロパン等の化合物が好適である。このときに
マレイミド化合物の含有率は樹脂組成物の総量１００重
量部に対して１０〜５０重量部であることが望ましい。
１０重量部未満であれば耐熱性を確保することが不十分
となり、また５０重量部を越えると硬化物が非常に脆く
なり、耐クラック性が非常に悪くなる。As the maleimide compound, N, N'-
Compounds such as (4,4-diphenylmethane) bismaleimide, bis (3-ethyl-5methyl-4-maleimidophenyl) methane, and 2,2bis [4- (4-maleimidophenoxy) phenyl] propane are preferred. At this time, the content of the maleimide compound is preferably 10 to 50 parts by weight based on 100 parts by weight of the total amount of the resin composition.
If the amount is less than 10 parts by weight, it becomes insufficient to secure heat resistance, and if it exceeds 50 parts by weight, the cured product becomes very brittle and the crack resistance becomes extremely poor.
【００１４】水酸基および水酸基以外のエポキシ樹脂ま
たはマレイミド化合物と重合可能な官能基を有するポリ
ビニルアセタール樹脂を使用することにより、硬化物の
クラック性を大幅に向上でき、かつエポキシ樹脂または
マレイミド化合物と架橋することにより高度な耐熱性を
維持することができる。一般的なポリビニルアセタール
樹脂は、反応性の官能基としては水酸基のみを含有して
いるので、エポキシ樹脂やビスマレイミド化合物と架橋
させることは非常に困難であり、エポキシ樹脂やビスマ
レイミド化合物と併用した場合には、その硬化物の耐熱
性を低下させ、高度な耐熱性を維持することは困難であ
った。本発明に示される水酸基および水酸基以外のエポ
キシ樹脂またはマレイミド化合物と重合可能な官能基を
有するビニルアセタール樹脂を使用することにより、こ
の問題は回避される。水酸基および水酸基以外のエポキ
シ樹脂またはマレイミド化合物と重合可能な官能基を有
するポリビニルアセタール樹脂としては、ポリビニルア
セタール樹脂にカルボキシル基、アミノ基、不飽和二重
結合を導入することにより得られる。例えば、ポリビニ
ルアルコールとアルデヒド類からポリビニルアセタール
樹脂を合成する際に、原料としてマレイン酸やアクリル
酸を共重合させたポリ酢酸ビニルを加水分解することに
より得られるポリビニルアルコールを用いることによ
り、カルボキシル基を含有するポリビニルアセタール樹
脂が合成できる。また、アルデヒド類の一部を、クロト
ンアルデヒド等の不飽和二重結合を有する化合物とする
ことにより不飽和二重結合を有するポリビニルアセター
ル樹脂が得られる。ポリビニルアセタール樹脂の分子量
は特に限定されないが重合度１０００〜３０００程度の
ものを使用することが望ましい。重合度１０００未満で
あれば、樹脂としての強靭性が乏しく、硬化物のクラッ
クを防止することが困難になり、重合度３０００を越え
ると、エポキシ樹脂との相溶性が悪くなる。水酸基以外
の官能基の量は特に限定されないが、ポリビニルアセタ
ール樹脂１分子あたり１個以上の水酸基以外の官能基を
導入することが望ましい。１個未満であればエポキシ樹
脂やビスマレイミド化合物との重合が不十分となる。水
酸基以外のエポキシ樹脂またはマレイミド化合物と重合
可能な官能基を有するポリビニルアセタール樹脂の使用
量としては、樹脂組成物の総量１００重量部に対して５
〜３０重量部であることが望ましい。５重量部未満であ
れば耐クラック性を改良する効果が発現せず、３０重量
部を越えると硬化物の耐熱性が悪くなる。By using a polyvinyl acetal resin having a functional group capable of polymerizing with a hydroxyl group and an epoxy resin other than the hydroxyl group or a maleimide compound, the cracking property of the cured product can be greatly improved, and the cured product can be crosslinked with the epoxy resin or the maleimide compound. Thereby, high heat resistance can be maintained. Since a general polyvinyl acetal resin contains only a hydroxyl group as a reactive functional group, it is very difficult to cross-link with an epoxy resin or a bismaleimide compound. In such a case, it was difficult to reduce the heat resistance of the cured product and maintain a high degree of heat resistance. This problem can be avoided by using a hydroxyl group and a vinyl acetal resin having a functional group capable of polymerizing with an epoxy resin or a maleimide compound other than the hydroxyl group as shown in the present invention. The polyvinyl acetal resin having a hydroxyl group and a functional group polymerizable with an epoxy resin other than the hydroxyl group or a maleimide compound can be obtained by introducing a carboxyl group, an amino group, and an unsaturated double bond into the polyvinyl acetal resin. For example, when synthesizing a polyvinyl acetal resin from polyvinyl alcohol and aldehydes, by using a polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate obtained by copolymerizing maleic acid or acrylic acid as a raw material, a carboxyl group can be formed. The contained polyvinyl acetal resin can be synthesized. Further, a polyvinyl acetal resin having an unsaturated double bond can be obtained by using a compound having an unsaturated double bond such as crotonaldehyde as a part of aldehydes. The molecular weight of the polyvinyl acetal resin is not particularly limited, but it is desirable to use a resin having a degree of polymerization of about 1,000 to 3,000. If the degree of polymerization is less than 1,000, the toughness of the resin is poor, and it is difficult to prevent cracks in the cured product. If the degree of polymerization exceeds 3,000, the compatibility with the epoxy resin becomes poor. The amount of the functional group other than the hydroxyl group is not particularly limited, but it is desirable to introduce one or more functional groups other than the hydroxyl group per polyvinyl acetal resin molecule. If it is less than one, polymerization with an epoxy resin or a bismaleimide compound will be insufficient. The amount of the polyvinyl acetal resin having a functional group that can be polymerized with an epoxy resin or a maleimide compound other than a hydroxyl group is 5 parts by weight based on 100 parts by weight of the total amount of the resin composition.
Desirably, the amount is 30 parts by weight. If it is less than 5 parts by weight, the effect of improving crack resistance will not be exhibited, and if it exceeds 30 parts by weight, the heat resistance of the cured product will deteriorate.
【００１５】本発明の趣旨を逸脱しない範囲で、上記必
須成分以外の樹脂成分、例えば熱硬化性ポリイミド樹
脂、ウレタン樹脂、フェノール樹脂、フェノキシ樹脂等
を添加することもできる。これらの樹脂の添加により、
耐炎性の向上、樹脂流動性の改良等に効果がある。A resin component other than the above essential components, for example, a thermosetting polyimide resin, a urethane resin, a phenol resin, a phenoxy resin and the like can be added without departing from the spirit of the present invention. By adding these resins,
It is effective for improving flame resistance and improving resin fluidity.
【００１６】上記のようにして得られた耐熱性及び耐ク
ラック性に優れた本発明の前記樹脂組成物を、多層プリ
ント配線板用の層間絶縁樹脂成分として、銅箔の片面に
塗工することにより本発明の樹脂付き銅箔とすることが
できる。The above-mentioned resin composition of the present invention having excellent heat resistance and crack resistance obtained as described above is coated on one surface of a copper foil as an interlayer insulating resin component for a multilayer printed wiring board. Thus, the resin-coated copper foil of the present invention can be obtained.
【００１７】さらに、絶縁基材層と該絶縁基材層の片面
又は両面に形成された内層回路と、該内層回路の外側に
絶縁樹脂層を介して形成された外層回路用銅箔からなる
多層銅張積層板において、前記内層回路と前記外層回路
用銅箔間に存在する前記絶縁樹脂層を上記のようにして
得られた耐熱性及び耐クラック性に優れた本発明の前記
樹脂組成物で形成することにより、本発明の多層銅張積
層板とすることができる。Furthermore, a multilayer comprising an insulating base layer, an inner layer circuit formed on one or both sides of the insulating base layer, and a copper foil for an outer layer circuit formed outside the inner layer circuit via an insulating resin layer. In the copper-clad laminate, the resin composition of the present invention having excellent heat resistance and crack resistance obtained as described above, wherein the insulating resin layer present between the inner layer circuit and the outer layer circuit copper foil is obtained. By forming, the multilayer copper-clad laminate of the present invention can be obtained.
【００１８】またさらに、絶縁基材層と該絶縁基材層の
片面又は両面に形成された内層回路と、該内層回路の外
側に絶縁樹脂層を介して形成された外層回路とからなる
多層プリント配線板において、前記内層回路と前記外層
回路間に存在する前記絶縁樹脂層を上記のようにして得
られた耐熱性及び耐クラック性に優れた本発明の前記樹
脂組成物で形成することにより、本発明の多層プリント
配線板とすることができる。Furthermore, a multilayer printed circuit comprising an insulating base layer, an inner layer circuit formed on one or both sides of the insulating base layer, and an outer layer circuit formed outside the inner layer circuit via an insulating resin layer. In the wiring board, by forming the insulating resin layer present between the inner layer circuit and the outer layer circuit with the resin composition of the present invention having excellent heat resistance and crack resistance obtained as described above, The multilayer printed wiring board of the present invention can be obtained.
【００１９】[0019]
【実施例】以下に、実施例及び比較例に基づき本発明を
詳細に説明する。実施例１ １−１）エポキシ樹脂 ビスフェノールＡ型エポキシ樹脂エポミックＲ−１４０
（三井石油化学製、商品名）及びｏ−クレゾールノボラ
ック型エポキシ樹脂エポトートＹＤＣＮ−７０４（東都
化成製、商品名）を重量比１００：１００で混合して得
た。 １−２）エポキシ樹脂硬化剤 ミレックスＸＬ−２２５（三井東圧化学製、商品名）を
上記エポキシ樹詣に等量配合した。 １−３）エポキシ樹脂硬化促進剤 キュアゾール２ＰΖ（四国化成工業製、商品名）を上記
エポキシ樹脂に対して１重量部添加した。The present invention will be described below in detail based on examples and comparative examples. Example 1 1-1) Epoxy resin bisphenol A type epoxy resin Epomic R-140
(Trade name, manufactured by Mitsui Petrochemical Co., Ltd.) and o-cresol novolak type epoxy resin epototo YDCN-704 (trade name, manufactured by Toto Kasei) were mixed at a weight ratio of 100: 100. 1-2) Epoxy resin curing agent Mirex XL-225 (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.) was mixed in an equal amount to the above epoxy resin . 1-3) 1 part by weight of an epoxy resin curing accelerator Curesol 2P (trade name, manufactured by Shikoku Chemicals) was added to the epoxy resin.
【００２０】上記エポキシ樹脂、エポキシ樹脂硬化剤、
エポキシ樹脂促進剤をジメチルホルムアミドに溶解して
５０％溶液とした、エポキシ樹脂配合物を準備した。 ２）ビスマレイミド化合物 Ｎ，Ｎ´−（４，４−ジフェニルメタン）ビスマレイミ
ドを用いた。 ３）水酸基及び水酸基以外のエポキシ樹脂またはマレイ
ミド化合物と重合可能な官能基を有するポリビニルアセ
タール樹脂 原料ポリビニルアルコールの重合度２４００、アセター
ル化度８０、アセトアルデヒド／ブチルアルデヒド＝５
０／５０（モル比）、水酸基濃度１７重量％、カルボキ
シル基濃度１重量％のカルボキシル基変性ポリビニルア
セタール樹脂を用いた。これらの成分を以下の表１に示
される比率で配合した。The above epoxy resin, epoxy resin curing agent,
An epoxy resin formulation was prepared in which the epoxy resin accelerator was dissolved in dimethylformamide to make a 50% solution. 2) Bismaleimide compound N, N '-(4,4-diphenylmethane) bismaleimide was used. 3) Hydroxyl and non-hydroxyl epoxy resin or male
Poly (vinylacetate) having functional group capable of polymerizing with amide compound
Tar resin raw material polyvinyl alcohol polymerization degree 2400, acetalization degree 80, acetaldehyde / butyraldehyde = 5
A carboxyl group-modified polyvinyl acetal resin having a 0/50 (molar ratio), a hydroxyl group concentration of 17% by weight and a carboxyl group concentration of 1% by weight was used. These components were blended in the ratios shown in Table 1 below.
【００２１】[0021]
【表１】 上記樹脂組成物を１８μｍ電解銅箔の粗化面に塗布し
て、風乾後、１２０℃で５分間加熱して、半硬化状態の
樹脂層を有する樹脂付き銅箔を得た。このときの樹脂層
の厚さは１００〜１０５μｍであった。この樹脂付き銅
箔を常圧にて２００℃４時間加熱し、冷却後銅箔をエッ
チングにより除去し、硬化樹脂フィルムを得た。また、
上記樹脂付き銅箔を用いて、所定の回路が形成されたＦ
Ｒ−４内層材（コア厚さ０．５ｍｍ、銅箔厚さ３５μ
ｍ）の両面に樹脂付き銅箔の樹脂層が内層材と接するよ
うに重ねて、圧力２０ｋｇｆ／ｃｍ2 、温度２００℃に
て４時間の熱プレスを行い、４層の銅箔層を有する多層
銅張積層板を得た。次いで、上記多層銅張積層板の外層
の銅箔を公知のエッチング方法でエッチングして回路を
形成し、４層の多層プリント配線板を製造した。[Table 1] The resin composition was applied to a roughened surface of an 18 μm electrolytic copper foil, air-dried, and heated at 120 ° C. for 5 minutes to obtain a resin-coated copper foil having a resin layer in a semi-cured state. At this time, the thickness of the resin layer was 100 to 105 μm. The copper foil with resin was heated at 200 ° C. for 4 hours under normal pressure, and after cooling, the copper foil was removed by etching to obtain a cured resin film. Also,
Using the above copper foil with resin, F
R-4 inner layer material (core thickness 0.5mm, copper foil thickness 35μ)
m) A resin layer of copper foil with resin is superimposed on both sides so as to be in contact with the inner layer material, and hot-pressed at a pressure of 20 kgf / cm 2 and a temperature of 200 ° C. for 4 hours to perform a multilayer having four copper foil layers A copper-clad laminate was obtained. Next, the outer layer copper foil of the multilayer copper-clad laminate was etched by a known etching method to form a circuit, and a four-layer multilayer printed wiring board was manufactured.
【００２２】実施例２ 実施例１に用いた水酸基および水酸基以外のエポキシ樹
脂またはマレイミド化合物と重合可能な官能基を有する
ポリビニルアセタール樹脂として、原料ポリビニルアル
コールの重合度２４００、アセタール化度８０、アセト
アルデヒド／クロトンアルデヒド＝５Ｏ／５０（モル
比）、水酸基濃度１８重量％の不飽和二重結合変性のポ
リビニルアセタール樹脂に変更した以外は実施例１と同
様の方法により樹脂付き銅箔、硬化樹脂フィルム、多層
銅張積層板、多層プリント配線板を得た。 Example 2 The polyvinyl acetal resin having a hydroxyl group and a functional group capable of polymerizing with the epoxy resin or maleimide compound other than the hydroxyl group used in Example 1 was prepared using a raw material polyvinyl alcohol having a degree of polymerization of 2400, a degree of acetalization of 80, Copper foil with resin, cured resin film, multilayer by the same method as in Example 1 except that the crotonaldehyde was changed to an unsaturated double bond-modified polyvinyl acetal resin having a crotonaldehyde ratio of 50/50 (molar ratio) and a hydroxyl group concentration of 18% by weight. A copper-clad laminate and a multilayer printed wiring board were obtained.
【００２３】実施例３ 実施例１で使用した樹脂と同一の樹脂を用いて、各樹脂
の配合比を以下の表２に示される比率に変更した以外は
実施例１と同じ方法により樹脂付き銅箔、硬化樹脂フィ
ルム、多層銅張積層板及び多層プリント配線板を得た。 Example 3 The same resin as used in Example 1 was used, except that the compounding ratio of each resin was changed to the ratio shown in Table 2 below, and the same method as in Example 1 was repeated. A foil, a cured resin film, a multilayer copper-clad laminate, and a multilayer printed wiring board were obtained.
【００２４】[0024]
【表２】 実施例４ 実施例１で使用したエポキシ樹脂配合物を以下に変更し
た以外は実施例１と同じ方法により樹脂付き銅箔、硬化
樹脂フィルム、多層銅張積層板及び多層プリント配線板
を得た。[Table 2] Example 4 A copper foil with resin, a cured resin film, a multilayer copper-clad laminate, and a multilayer printed wiring board were obtained in the same manner as in Example 1, except that the epoxy resin composition used in Example 1 was changed as follows.
【００２５】１−１）エポキシ樹脂 ビスフェノールＡ型エポキシ樹脂エポミックＲ−１４０
（三井石油化学製 商品名）、ノボラック型エポキシ樹
脂ＥＰＰＮ−２０１（日本化薬製、商品名）を重量比３
０：７０で混合 １−２）エポキシ樹脂硬化剤 ミレックスＸＬ−２２５（三井東圧化学製、商品名）上
記エポキシ樹脂に等量配合 １−３）エポキシ樹脂硬化促進剤 キュアゾール２ＰＺ（四国化成工業製、商品名）上記エ
ポキシ樹脂に対して１重量部添加 上記エポキシ樹脂、エポキシ樹脂硬化剤、エポキシ樹脂
促進剤をジメチルホルムアミドに溶解して５０％溶液と
した。1-1) Epoxy resin Bisphenol A type epoxy resin EPOMIC R-140
(Mitsui Petrochemical's trade name), Novolak type epoxy resin EPPN-201 (Nippon Kayaku, trade name) 3
1-2) Epoxy resin hardener MILEX XL-225 (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.) Equivalent blending with the above epoxy resin 1-3) Epoxy resin hardening accelerator Curesol 2PZ (Shikoku Chemical Industry Co., Ltd.) (Trade name) 1 part by weight added to the above epoxy resin The above epoxy resin, epoxy resin curing agent and epoxy resin accelerator were dissolved in dimethylformamide to make a 50% solution.
【００２６】比較例１ 実施例１で使用した樹脂と同一のエポキシ樹脂、ポリビ
ニルアセタール樹脂を用い、ビスマレイミド化合物を使
用せずに各樹脂の配合を以下の表３に示される比率に変
更した以外は実施例１と同じ方法により、樹脂付き銅
箔、硬化樹脂フィルム、多層銅張積層板及び多層プリン
ト配線板を得た。 Comparative Example 1 The same epoxy resin and polyvinyl acetal resin as those used in Example 1 were used, and the ratio of each resin was changed to the ratio shown in Table 3 below without using a bismaleimide compound. In the same manner as in Example 1, a copper foil with resin, a cured resin film, a multilayer copper-clad laminate, and a multilayer printed wiring board were obtained.
【００２７】[0027]
【表３】 [Table 3]
【００２８】比較例２ 実施例１で使用した樹脂と同一エポキシ樹脂及びビスマ
レイミド化合物を用い、水酸基および水酸基以外のエポ
キシ樹脂またはマレイミド化合物と重合可能な官能基を
有するボリビニルアセタール樹脂を使用せずに各樹脂の
配合を以下の表４に示される比率に変更した以外は実施
例１と同じ方法により樹脂付き銅箔、硬化樹脂フィル
ム、多層銅張積層板及び多層プリント配線板を得た。 Comparative Example 2 Using the same epoxy resin and bismaleimide compound as the resin used in Example 1, without using a hydroxyl group and a non-hydroxyl epoxy resin or a polyvinyl acetal resin having a functional group polymerizable with the maleimide compound. A copper foil with resin, a cured resin film, a multilayer copper-clad laminate, and a multilayer printed wiring board were obtained in the same manner as in Example 1 except that the proportions of the respective resins were changed to the ratios shown in Table 4 below.
【００２９】[0029]
【表４】 [Table 4]
【００３０】比較例３ 実施例１で使用した水酸基および水酸基以外のエポキシ
樹脂またはマレイミド化合物と重合可能な官能基を有す
るポリビニルアセタール樹脂を以下に変更した以外は実
施例１と同じ方法により樹脂付き銅箔、硬化樹脂フィル
ム及び多層プリント配線板を得た。 Comparative Example 3 The same procedure as in Example 1 was repeated except that the hydroxyl group and the polyvinyl acetal resin having a functional group polymerizable with the epoxy resin or maleimide compound other than the hydroxyl group used in Example 1 were changed as follows. A foil, a cured resin film and a multilayer printed wiring board were obtained.
【００３１】ポリビニルアセタール樹脂 原料ポリビニルアルコールの重合度２４００、アセター
ル化度８０、アセトアルデヒド／ブチルアルデヒド＝５
０／５０（モル比）、水酸基濃度１７重量％の水酸基以
外の反応性官能基を有しないポリビニルアセタール樹脂 以上の実施例１〜４および比較例１〜３で作成した樹脂
フィルム、多層銅張積層板を用いて次の特性について評
価を行った。 Polyvinyl acetal resin raw material Polyvinyl alcohol polymerization degree 2400, acetalization degree 80, acetaldehyde / butyraldehyde = 5
0/50 (molar ratio), polyvinyl acetal resin having a hydroxyl group concentration of 17% by weight and having no reactive functional group other than hydroxyl groups The resin films prepared in Examples 1 to 4 and Comparative Examples 1 to 3 above, multilayer copper-clad laminates The following characteristics were evaluated using the plate.
【００３２】半硬化樹脂フィルム： （１）動的粘弾性測定装置によるＴｇ（ガラス転移温
度）測定多層プリント配線板： （１）外層銅箔にランドを形成し、金線のワイヤボンデ
ィングを行った後に、引張り試験により密着強度を測定 （２）外層銅箔にエッチングによる幅１００μｍの銅回
路およびバイアホール径１５０μｍ、ランド径３５０μ
ｍのバイアホールを形成した後に、−６５℃（３０分）
から＋１２５℃（３０分）×３００サイクルの熱衝撃試
験を行い、樹脂クラックの有無を断面観察により評価 （３）２６０℃、１０秒オイル浸漬から自然空冷×１０
０サイクルのオイルディップ耐熱性試験 上記試験で得られた結果を以下の表５及び表６に示す。 Semi-cured resin film: (1) Tg (glass transition temperature) measurement by dynamic viscoelasticity measuring device Multilayer printed wiring board: (1) Land was formed on outer layer copper foil, and gold wire was wire-bonded. Thereafter, the adhesion strength is measured by a tensile test. (2) A copper circuit having a width of 100 μm, a via hole diameter of 150 μm, and a land diameter of 350 μm are etched on the outer copper foil.
After forming via holes of m, the temperature is -65 ° C (30 minutes).
To + 125 ° C (30 minutes) × 300 cycles of thermal shock test, and the presence or absence of resin cracks was evaluated by cross-sectional observation.
0-Cycle Oil Dip Heat Resistance Test The results obtained in the above test are shown in Tables 5 and 6 below.
【００３３】本発明の樹脂付き銅箔は樹脂層の耐熱性が
高く、これを用いて製造された多層プリント配線板はワ
イヤボンディングによる金線の密着性も高い。さらに、
耐熱性、耐熱衝撃性も良好である。The resin-coated copper foil of the present invention has a high heat resistance of the resin layer, and the multilayer printed wiring board manufactured using the resin layer has high adhesion of the gold wire by wire bonding. further,
Good heat resistance and thermal shock resistance.
【００３４】[0034]
【表５】 [Table 5]
【００３５】[0035]
【表６】 [Table 6]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０５Ｋ 3/46 Ｈ０５Ｋ 3/46 Ｔ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI H05K 3/46 H05K 3/46 T
Claims (7)
脂配合物、 ２）マレイミド化合物、および ３）水酸基および水酸基以外のエポキシ樹脂またはマレ
イミド化合物と重合可能な官能基を有するポリビニルア
セタール樹脂 を含むことを特徴とする銅張積層板用樹脂組成物。1. The following components: 1) an epoxy resin blend comprising an epoxy resin and a curing agent thereof; 2) a maleimide compound; and 3) a polyvinyl having a hydroxyl group and a functional group capable of polymerizing with an epoxy resin other than the hydroxyl group or a maleimide compound. A resin composition for a copper-clad laminate, comprising an acetal resin.
し、エポキシ樹脂配合物４０〜８０重量部、マレイミド
化合物１０〜５０重量部、水酸基および水酸基以外のエ
ポキシ樹脂またはマレイミド化合物と重合可能な官能基
を有するポリビニルアセタール樹脂５〜３０重量部から
なることを特徴とする請求項１に記載の銅張積層板用樹
脂組成物。2. An epoxy resin compound of 40 to 80 parts by weight, a maleimide compound of 10 to 50 parts by weight, a hydroxyl group and a functional group capable of polymerizing with an epoxy resin other than the hydroxyl group or a maleimide compound, based on 100 parts by weight of the resin composition. The resin composition for a copper-clad laminate according to claim 1, comprising 5 to 30 parts by weight of a polyvinyl acetal resin having a group.
をさらに含むことを特徴とする請求項１または２に記載
の銅張積層板用樹脂組成物。3. The resin composition for a copper clad laminate according to claim 1, further comprising a curing accelerator in the epoxy resin composition.
にカルボキシル基、アミノ基または不飽和二重結合を導
入したものであることを特徴とする請求項１、２または
３に記載の銅張積層板用樹脂組成物。4. The copper clad laminate according to claim 1, wherein the polyvinyl acetal resin has a carboxyl group, an amino group or an unsaturated double bond introduced into a molecule. Resin composition.
分として請求項１から４のいずれかに記載の樹脂組成物
を銅箔の片面に塗工して得られることを特徴とする樹脂
付き銅箔。5. A resin-coated copper obtained by coating the resin composition according to claim 1 on one surface of a copper foil as an interlayer insulating resin component for a multilayer printed wiring board. Foil.
面に形成された内層回路と、該内層回路の外側に絶縁樹
脂層を介して形成された外層回路用銅箔からなる多層銅
張り積層板であって、前記内層回路と前記外層回路用銅
箔間に存在する前記絶縁樹脂層を請求項１から４のいず
れかに記載の樹脂組成物で形成したことを特徴とする前
記多層銅張り積層板。6. A multilayer comprising an insulating base layer, an inner layer circuit formed on one or both sides of the insulating base layer, and a copper foil for an outer layer circuit formed outside the inner layer circuit via an insulating resin layer. A copper-clad laminate, wherein the insulating resin layer present between the inner layer circuit and the outer layer circuit copper foil is formed of the resin composition according to any one of claims 1 to 4. Multi-layer copper-clad laminate.
面に形成された内層回路と、該内層回路の外側に絶縁樹
脂層を介して形成された外層回路とからなる多層プリン
ト配線板であって、前記内層回路と前記外層回路間に存
在する前記絶縁樹脂層を請求項１から４のいずれかに記
載の樹脂組成物で形成したことを特徴とする前記多層プ
リント配線板。7. A multilayer printed wiring comprising an insulating base layer, an inner layer circuit formed on one or both sides of the insulating base layer, and an outer layer circuit formed outside the inner layer circuit via an insulating resin layer. The multilayer printed wiring board, wherein the insulating resin layer present between the inner circuit and the outer circuit is formed of the resin composition according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17656597A JPH115828A (en) | 1997-06-17 | 1997-06-17 | Resin composition for copper-clad laminate, copper foil with resin, multilayer copper-clad laminate and multilayer printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17656597A JPH115828A (en) | 1997-06-17 | 1997-06-17 | Resin composition for copper-clad laminate, copper foil with resin, multilayer copper-clad laminate and multilayer printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH115828A true JPH115828A (en) | 1999-01-12 |
Family
ID=16015801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17656597A Pending JPH115828A (en) | 1997-06-17 | 1997-06-17 | Resin composition for copper-clad laminate, copper foil with resin, multilayer copper-clad laminate and multilayer printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH115828A (en) |
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| WO2001031985A1 (en) * | 1999-10-28 | 2001-05-03 | Hitachi Chemical Co., Ltd. | Insulating agent for multilayer printed wiring board, insulating agent with metal foil and multilayer printed wiring board |
| WO2002046264A1 (en) * | 2000-12-08 | 2002-06-13 | Mitsui Mining & Smelting Co.,Ltd. | Resin compound for forming interlayer insulating layer of printed wiring board, resin sheet and copper foil with resin for forming insulating layer using the resin compound, and copper-clad laminate using them |
| US6652962B1 (en) | 1998-05-29 | 2003-11-25 | Mitsui Mining & Smelting Co. Ltd. | Resin-coated composite foil, production and use thereof |
| KR100491754B1 (en) * | 2002-09-11 | 2005-05-27 | 주식회사 엘지화학 | Resin coated copper composition for substrate of build-up preinted circuit board |
| JP2007254710A (en) * | 2005-11-29 | 2007-10-04 | Ajinomoto Co Inc | Resin composition for interlayer insulation layer of multi-layer printed circuit board |
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| JP2009173017A (en) * | 2007-12-28 | 2009-08-06 | Mitsui Mining & Smelting Co Ltd | Resin-coated copper foil and process for producing resin-coated copper foil |
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| JP2012126914A (en) * | 2005-11-29 | 2012-07-05 | Ajinomoto Co Inc | Resin composition for interlayer insulating layer of multi-layer printed wiring board |
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-
1997
- 1997-06-17 JP JP17656597A patent/JPH115828A/en active Pending
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| WO2001031985A1 (en) * | 1999-10-28 | 2001-05-03 | Hitachi Chemical Co., Ltd. | Insulating agent for multilayer printed wiring board, insulating agent with metal foil and multilayer printed wiring board |
| WO2002046264A1 (en) * | 2000-12-08 | 2002-06-13 | Mitsui Mining & Smelting Co.,Ltd. | Resin compound for forming interlayer insulating layer of printed wiring board, resin sheet and copper foil with resin for forming insulating layer using the resin compound, and copper-clad laminate using them |
| US6716530B2 (en) | 2000-12-08 | 2004-04-06 | Mitsui Mining & Smelting Co., Ltd. | Resin compound for fabricating interlayer dielectric of printed wiring board, resin sheet and resin applied-copper foil for forming insulation layer using the resin compound, and copper-clad laminate using them |
| CN1314726C (en) * | 2000-12-08 | 2007-05-09 | 三井金属鉱业株式会社 | Resin compound for forming interlayer insualting layer of printed wiring board, resin for forming insulating layer using resin compound |
| KR100491754B1 (en) * | 2002-09-11 | 2005-05-27 | 주식회사 엘지화학 | Resin coated copper composition for substrate of build-up preinted circuit board |
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