JPH09124767A - Insulating layer resin composition for multilayer printed wiring board - Google Patents
Insulating layer resin composition for multilayer printed wiring boardInfo
- Publication number
- JPH09124767A JPH09124767A JP28508695A JP28508695A JPH09124767A JP H09124767 A JPH09124767 A JP H09124767A JP 28508695 A JP28508695 A JP 28508695A JP 28508695 A JP28508695 A JP 28508695A JP H09124767 A JPH09124767 A JP H09124767A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- parts
- manufactured
- printed wiring
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、多層プリント配線
板およびその製造方法に関するものであり、特に、耐熱
性樹脂からなる樹脂絶縁層によって層間絶縁された多層
プリント配線板を形成するための絶縁層樹脂組成物に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer printed wiring board and a method for manufacturing the same, and particularly to an insulating layer for forming a multilayer printed wiring board which is interlayer-insulated by a resin insulating layer made of a heat resistant resin. It relates to a resin composition.
【０００２】[0002]
【従来の技術】近年、電子技術の進歩に伴い、大型コン
ピューターなどの電子機器に対する高密度化あるいは演
算機能の高速化が進めれている。その結果、プリント配
線板においても高密度化を目的として配線回路が多層に
形成された多層プリント配線板が脚光を浴びてきた。2. Description of the Related Art In recent years, with the progress of electronic technology, the density of electronic devices such as large computers and the speed of arithmetic functions have been increased. As a result, multilayer printed wiring boards, in which wiring circuits are formed in multiple layers for the purpose of increasing the density of printed wiring boards, have been spotlighted.
【０００３】従来、多層プリント配線板としては、例え
ば内装回路を接続し導通せしめた多層プリント配線板が
代表的なものであった。しかしながら、このような多層
プリント配線板は、複数の内装回路をスルーホールを介
して接続導通させたものであるため、配線回路が複雑に
なりすぎて高密度化あるいは高速化を実現することが困
難であった。Conventionally, as a multilayer printed wiring board, for example, a multilayer printed wiring board in which an internal circuit is connected and made conductive is typical. However, in such a multilayer printed wiring board, since a plurality of internal circuits are connected and conducted through through holes, the wiring circuit becomes too complicated, and it is difficult to realize high density or high speed. Met.
【０００４】このような問題点を克服することのできる
多層プリント配線板として、最近、導体回路と有機絶縁
膜とを交互にビルドアップした多層プリント配線板が開
発されている。この多層プリント配線板は、超高密度化
と高速化に適合したものであるが、欠点は有機絶縁膜上
に無電解めっき膜を信頼性よく形成させることが困難な
ことにあった。As a multilayer printed wiring board capable of overcoming such problems, a multilayer printed wiring board in which conductor circuits and organic insulating films are alternately built up has been developed recently. This multilayer printed wiring board is suitable for ultra-high density and high speed, but the drawback is that it is difficult to reliably form an electroless plated film on an organic insulating film.
【０００５】このため、かかる多層プリント配線板にお
いては、導体回路を、蒸着やスパッタリングなどのＰＶ
Ｄ法もしくは前記ＰＶＤ法と無電解めっき及び電解めっ
きとの併用法で形成していたが、このようなＰＶＤ法に
よる導体回路形成方法は生産性が劣り、コストが高い点
にあった。Therefore, in such a multilayer printed wiring board, the conductor circuit is formed by PV such as vapor deposition or sputtering.
Although it was formed by the D method or the combined method of the PVD method and the electroless plating and the electrolytic plating, such a conductor circuit forming method by the PVD method has poor productivity and high cost.
【０００６】最近、このような有機絶縁膜上に無電解め
っき膜を信頼性よく形成する方法として、樹脂絶縁層中
に酸化剤などに可溶な成分を混合し溶解除去することに
よって、無電解めっき膜に接する樹脂表面を荒らす方法
が提案されている。たとえば、特開昭６４−４７０９５
にあるように耐熱性の樹脂絶縁層をマトリックスとし
て、樹脂層中に酸化剤に可溶のエポキシ樹脂、ビスマレ
イミド・トリアジン樹脂、ポリエステル樹脂などの樹脂
と、酸化剤に不溶の樹脂や無機フィラーの混合により、
樹脂絶縁層の表面を酸化剤で荒らして無電解めっき膜形
成のアンカー効果を高めたものなどが提案されている。
また、特開昭６１−２７６８７５のように、耐熱性絶縁
樹脂分子内にジエン系ゴム成分などを組み込むことによ
り、無電解めっき膜との接着性を向上させる方法なども
提案されている。Recently, as a method for reliably forming an electroless plating film on such an organic insulating film, an electroless plating film is formed by mixing a component soluble in an oxidizer or the like in a resin insulating layer and dissolving it. A method for roughening the resin surface in contact with the plating film has been proposed. For example, Japanese Patent Laid-Open No. 64-47095
As described in (1), the heat-resistant resin insulation layer is used as a matrix, and the resin layer contains a resin such as an epoxy resin, a bismaleimide / triazine resin, or a polyester resin that is soluble in an oxidant, and a resin or an inorganic filler that is insoluble in the oxidant. By mixing,
It has been proposed that the surface of the resin insulating layer is roughened with an oxidizing agent to enhance the anchor effect of electroless plating film formation.
Further, as in JP-A-61-276875, there has been proposed a method of improving the adhesiveness to an electroless plating film by incorporating a diene rubber component in the heat resistant insulating resin molecule.
【０００７】しかしながら、これらの方法では耐熱性の
樹脂絶縁層に対して酸化剤などで溶解させる樹脂粒子や
ゴム成分などの樹脂改質剤自体の耐熱性が劣っているた
め、結果として形成された樹脂絶縁層の耐熱性を低下さ
せることが問題となっていた。However, according to these methods, the heat resistance of the resin modifier itself such as resin particles and rubber components dissolved in the heat-resistant resin insulating layer with an oxidizing agent or the like is inferior. There has been a problem of lowering the heat resistance of the resin insulating layer.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、前述のごと
き従来の多層プリント配線板の有する問題点を解消する
ために、耐熱性樹脂からなる樹脂絶縁層を形成すること
によって、高耐熱性で、かつ信頼性の高い多層プリント
配線板を容易にかつ安価に提供することである。SUMMARY OF THE INVENTION The present invention has a high heat resistance by forming a resin insulating layer made of a heat resistant resin in order to solve the problems of the conventional multilayer printed wiring board as described above. And to provide a highly reliable multilayer printed wiring board easily and at low cost.
【０００９】[0009]
【課題を解決するための手段】本発明において、上記課
題を達成するために、まず請求項１においては、多層プ
リント配線板の層間絶縁層樹脂として、感光性耐熱樹脂
成分としてビスフェノール型エポキシ化合物と不飽和モ
ノカルボン酸との反応物と飽和または不飽和多塩基酸無
水物とを反応せしめて得られる紫外線硬化性樹脂（Ａ）
と、光重合開始剤（Ｂ）と、希釈剤（Ｃ）と、一分子中
に３個以上のエポキシ基を有する２種類のエポキシ化合
物からなる熱硬化性成分を含んでなり、該エポキシ化合
物の一つが脂環式エポキシ類化合物であり、もう一つが
芳香族環を含む構造のエポキシ類化合物（Ｄ）と、から
なることを特徴とする、希アルカリ溶液に現像可能な光
硬化性および熱硬化性の多層プリント配線板用絶縁層樹
脂組成物としたものである。In order to achieve the above object in the present invention, first, in claim 1, as an interlayer insulating layer resin of a multilayer printed wiring board, a bisphenol type epoxy compound is used as a photosensitive heat resistant resin component. UV curable resin (A) obtained by reacting a reaction product with an unsaturated monocarboxylic acid and a saturated or unsaturated polybasic acid anhydride
A photopolymerization initiator (B), a diluent (C), and a thermosetting component composed of two kinds of epoxy compounds having three or more epoxy groups in one molecule. One comprising an alicyclic epoxy compound and the other comprising an epoxy compound having a structure containing an aromatic ring (D); And an insulating layer resin composition for a multilayer printed wiring board.
【００１０】また、請求項２においては、前記脂環式エ
ポキシ類化合物と芳香族環を含むエポキシ類化合物の配
合比を４：１〜１：１（重量比）としたものである。In the second aspect, the compounding ratio of the alicyclic epoxy compound and the epoxy compound containing an aromatic ring is 4: 1 to 1: 1 (weight ratio).
【００１１】さらにまた、請求項３においては、前記脂
環式エポキシ類化合物が（化１）に示す構造を有するこ
とを特徴とする多層プリント配線板用絶縁層樹脂組成物
としたものである。Further, in the third aspect of the present invention, there is provided an insulating layer resin composition for a multilayer printed wiring board, wherein the alicyclic epoxy compound has a structure shown in (Chemical Formula 1).
【００１２】以下、本発明をさらに詳細に説明する。本
発明の感光性耐熱樹脂成分である、ビスフェノール型エ
ポキシ化合物と不飽和モノカルボン酸との反応物と、飽
和または不飽和多塩基酸無水物とを反応せしめて得られ
る紫外線硬化性樹脂（Ａ）において、ビスフェノール成
分の具体例としては、ビス（４−ヒドロキシフェニル）
ケトン、ビス（４−ヒドロキシ−３，５−ジメチルフェ
ニル）ケトン、ビス（４−ヒドロキシ−３，５−ジクロ
ロフェニル）ケトン、ビス（４−ヒドロキシフェニル）
スルホン、ビス（４−ヒドロキシ−３，５−ジメチルフ
ェニル）スルホン、ビス（４−ヒドロキシ−３，５−ジ
クロロフェニル）スルホン、ビス（４−ヒドロキシフェ
ニル）メタン、ビス（４−ヒドロキシ−３，５−ジメチ
ルフェニル）メタン、ビス（４−ヒドロキシ−３，５−
ジクロロフェニル）メタン、ビス（４−ヒドロキシフェ
ニル）ヘキサフルオロプロパン、ビス（４−ヒドロキシ
−３，５−ジメチルフェニル）ヘキサフルオロプロパ
ン、ビス（４−ヒドロキシ−３，５−ジクロロフェニ
ル）ヘキサフルオロプロパン、ビス（４−ヒドロキシフ
ェニル）ジメチルシラン、ビス（４−ヒドロキシ−３，
５−ジメチルフェニル）ジメチルシラン、ビス（４−ヒ
ドロキシ−３，５−ジクロロフェニル）ジメチルシラ
ン、ビス（４−ヒドロキシフェニル）メタン、ビス（４
−ヒドロキシ−３，５−ジクロロフェニル）メタン、ビ
ス（４−ヒドロキシ−３，５−ジブロモフェニル）メタ
ン、２，２−ビス（４−ヒドロキシフェニル）プロパ
ン、２，２−ビス（４−ヒドロキシ−３，５−ジメチル
フェニル）プロパン、２，２−ビス（４−ヒドロキシ−
３，５−ジクロロフェニル）プロパン、２，２−ビス
（４−ヒドロキシ−３−メチルフェニル）プロパン、
２，２−ビス（４−ヒドロキシ−３−クロロフェニル）
プロパン、ビス（４−ヒドロキシフェニル）エーテル、
ビス（４−ヒドロキシ−３，５−ジメチルフェニル）エ
ーテル、ビス（４−ヒドロキシ−３，５−ジクロロフェ
ニル）エーテル等が挙げられる。The present invention will be described in more detail below. UV curable resin (A) obtained by reacting a reaction product of a bisphenol type epoxy compound and an unsaturated monocarboxylic acid, which is a photosensitive heat-resistant resin component of the present invention, with a saturated or unsaturated polybasic acid anhydride In the above, as a specific example of the bisphenol component, bis (4-hydroxyphenyl)
Ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl)
Sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-). Dimethylphenyl) methane, bis (4-hydroxy-3,5-
Dichlorophenyl) methane, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis ( 4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,
5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4
-Hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-Dimethylphenyl) propane, 2,2-bis (4-hydroxy-)
3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
2,2-bis (4-hydroxy-3-chlorophenyl)
Propane, bis (4-hydroxyphenyl) ether,
Examples thereof include bis (4-hydroxy-3,5-dimethylphenyl) ether and bis (4-hydroxy-3,5-dichlorophenyl) ether.
【００１３】また、不飽和モノカルボン酸の具体例とし
ては、例えば、アクリル酸、メタクリル酸、ケイ皮酸等
が挙げられる。Specific examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid and cinnamic acid.
【００１４】また、飽和または不飽和多塩基酸無水物の
具体例としては、例えば、無水マレイン酸、無水コハク
酸、無水イタコン酸、無水フタル酸、無水テトラヒドロ
フタル酸、無水へキサヒドロフタル酸、メチルへキサヒ
ドロ無水フタル酸、無水エンドメチレンテトラヒドロフ
タル酸、無水メチルエンドメチレンテトラヒドロフタル
酸、無水クロレンド酸、メチルテトラヒドロ無水フタル
酸などの二塩基性酸無水物；無水トリメリット酸、無水
ピロメリット酸、ベンゾフェノンテトラカルボン酸二無
水物などの芳香族多価カルボン酸無水物；その他これに
付随する例えば５−（２，５−ジオキソテトラヒドロフ
リル）−３−メチル−３−シクロヘキセン−１，２−ジ
カルボン酸無水物のような多価カルボン酸無水物誘導体
などが使用できる。Specific examples of the saturated or unsaturated polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like. Dibasic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride; trimellitic anhydride, pyromellitic anhydride, Aromatic polyvalent carboxylic acid anhydrides such as benzophenone tetracarboxylic acid dianhydride; and other incidental compounds such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Polyvalent carboxylic acid anhydride derivative such as acid anhydride can be used
【００１５】更に、本発明の樹脂組成物を構成する光重
合開始剤（Ｂ）としては、例えば、アセトフェノン、
２，２−ジエトキシアセトフェノン、ｐ−ジメチルアセ
卜フェノン、ｐ−ジメチルアミノプロピオフェノン、ジ
クロロアセトフェノン、トリクロロアセトフェノン、ｐ
−ｔｅｒｔ−ブチルアセトフェノン等のアセトフェノン
類や、ベンゾフェノン、２−クロロベンゾフェノン、
ｐ，ｐ’−ビスジメチルアミノベンゾフェノン等のベン
ゾフェノン類や、ベンゾイン、ベンゾインメチルエーテ
ル、ベンゾインイソプロピルエーテル、ベンゾインイソ
ブチルエーテル、等のベンゾインエーテル類や、ベンジ
ルジメチルケタール、チオキサンソン、２−クロロチオ
キサンソン、２，４−ジエチルチオキサンソン、２−メ
チルチオキサンソン、２−イソプロピルチオキサンソン
等のイオウ化合物や、２−エチルアントラキノン、オク
タメチルアントラキノン、１，２−ベンズアントラキノ
ン、２，３−ジフェニルアントラキノン等のアントラキ
ノン類や、アゾビスイソブチルニトリル、ベンゾイルパ
ーオキサイド、クメンパーオキシド等の有機過酸化物
や、２−メルカプ卜ベンゾイミダゾール、２−メルカプ
トベンゾオキサゾール、２−メルカプトベンゾチアゾー
ル等のチオール化合物等が挙げられる。これらの化合物
は、２種以上を組み合わせて使用することもできる。ま
た、それ自体では光重合開始剤として作用しないが、上
記の化合物と組み合わせて用いることによリ、光重合開
始剤の能力を増大させ得るような化合物を添加すること
もできる。そのような化合物としては、例えば、ベンゾ
フエノンと組み合わせて使用すると効果のあるトリエタ
ノールアミン等の第三級アミンを挙げることができる。Further, as the photopolymerization initiator (B) constituting the resin composition of the present invention, for example, acetophenone,
2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p
Acetophenones such as -tert-butylacetophenone, benzophenone, 2-chlorobenzophenone,
Benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2 , 4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and other sulfur compounds, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone Anthraquinones, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole , 2-mercaptobenzothiazole and other thiol compounds. These compounds may be used in combination of two or more. In addition, a compound which does not act as a photopolymerization initiator by itself, but can be used in combination with the above compound, can increase the ability of the photopolymerization initiator. Examples of such compounds include tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.
【００１６】また、本発明における樹脂組成物の溶液の
調製に適した希釈剤（Ｃ）としては、通常の汎用溶剤、
例えば、メチルエチルケトン、メチルイソブチルケト
ン、メチルセロソルブ、エチルセロソルブ、ブチルセロ
ソルブ、ブチルセロソルブアセテート、ブチルカルビト
ール、テトラリン、ジメチルホルムアミド、ノルマルメ
チルピロリドン等が挙げられる。Further, as the diluent (C) suitable for preparing the solution of the resin composition in the present invention, a usual general-purpose solvent,
Examples thereof include methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, butyl carbitol, tetralin, dimethylformamide, and normal methylpyrrolidone.
【００１７】本発明における熱硬化性成分である２種類
のエポキシ化合物（Ｄ）としては、一つが脂環式エポキ
シ類化合物であり、もう一つが芳香族環を含む構造のエ
ポキシ類化合物からなることが望ましい。芳香族環を含
む構造のエポキシ類化合物の具体例としては、フェノー
ルノボラック型エポキシ樹脂、クレゾールノボラック型
エポキシ樹脂、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、ビスフェノールＳ型エポ
キシ樹脂、ビフェニル型エポキシ樹脂、脂環式エポキシ
樹脂等のエポキシ樹脂や、フェニルグリシジルエーテ
ル、ｐ−ブチルフェノールグリシジルエーテル、トリグ
リシジルイソシアヌレート、ジグリシジルイソシアヌレ
ート、アリルグリシジルエーテル、グリシジルメタクリ
レート等のエポキシ基を少なくとも３個以上有する化合
物等が挙げられる。また、脂環式エポキシ類化合物の具
体例としては、シクロヘキセンオキシドの各種誘導体や
前記芳香族エポキシ類の水素添加化合物や、請求項３に
示す構造のエポキシ化合物などが挙げられる。As the two kinds of epoxy compounds (D) which are thermosetting components in the present invention, one is an alicyclic epoxy compound and the other is an epoxy compound having a structure containing an aromatic ring. Is desirable. Specific examples of the epoxy compound having a structure containing an aromatic ring include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin. , Epoxy resins such as alicyclic epoxy resins, compounds having at least three epoxy groups such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate, etc. Is mentioned. Specific examples of the alicyclic epoxy compounds include various derivatives of cyclohexene oxide, hydrogenated compounds of the aromatic epoxies, epoxy compounds having the structure shown in claim 3, and the like.
【００１８】上記２種類のエポキシ化合物の配合比とし
ては、脂環式エポキシ類化合物と芳香族環を含む構造の
エポキシ類化合物の配合比が、４：１〜１：１（重量
比）であることが好ましく、さらには、２．５：１〜
１．５：１（重量比）であることが特に好ましい。脂環
式エポキシ類化合物と芳香族環を含む構造のエポキシ類
化合物の配合比が上記の範囲外であると、ガラス転移温
度（Ｔｇ）が極端に下がり耐熱性が低下したり、また、
めっき接着強度（ピール強度）が低下して無電解めっき
膜を信頼性よく形成することが困難になる可能性があ
る。As the compounding ratio of the above-mentioned two kinds of epoxy compounds, the compounding ratio of the alicyclic epoxy compound and the epoxy compound having a structure containing an aromatic ring is 4: 1 to 1: 1 (weight ratio). Preferably, further, 2.5: 1-
It is particularly preferable that the ratio is 1.5: 1 (weight ratio). When the compounding ratio of the alicyclic epoxy compound and the epoxy compound having a structure containing an aromatic ring is out of the above range, the glass transition temperature (Tg) is extremely lowered and the heat resistance is lowered.
The plating adhesion strength (peel strength) may decrease, and it may be difficult to reliably form an electroless plating film.
【００１９】また、上記感光性樹脂組成物中には、必要
に応じて、例えば、フッソ樹脂やポリイミド樹脂、ベン
ゾグアナミン樹脂などの有機質充填剤、あるいはシリカ
やタルク、アルミナ、クレー、炭酸カルシウム、酸化チ
タン、硫酸バリウムなどの無機質充填剤を配合すること
ができる。In the above-mentioned photosensitive resin composition, if necessary, for example, an organic filler such as a fluorine resin, a polyimide resin or a benzoguanamine resin, or silica, talc, alumina, clay, calcium carbonate or titanium oxide. Inorganic fillers such as barium sulfate can be added.
【００２０】さらに、上記感光性樹脂組成物中には、必
要に応じて、エポキシ基硬化促進剤、熱重合禁止剤、可
塑剤、レベリング剤、消泡剤、紫外線吸収剤、難燃化剤
等の添加剤や着色用顔料等を添加することが可能であ
る。Further, in the above-mentioned photosensitive resin composition, if necessary, an epoxy group curing accelerator, a thermal polymerization inhibitor, a plasticizer, a leveling agent, a defoaming agent, an ultraviolet absorber, a flame retardant, etc. It is possible to add such additives and coloring pigments.
【００２１】[0021]
【発明の実施の形態】次に多層プリント配線板の製造方
法について具体的に説明する。本発明は、まず導体回路
を形成した基板上に、上記の感光性樹脂絶縁層を形成す
ることにより始まる。本発明に使用する基板としては、
例えばプラスチック基板、セラミック基板、金属基板、
フィルム基板などを使用することができ、具体的にはガ
ラスエポキシ基板、ビスマレイミドートリアジン基板、
低温焼成セラミック基板、窒化アルミニウム基板、アル
ミニウム基板、鉄基板、ポリイミドフィルム基板などを
使用することができる。BEST MODE FOR CARRYING OUT THE INVENTION Next, a method for manufacturing a multilayer printed wiring board will be specifically described. The present invention begins by forming the above-mentioned photosensitive resin insulating layer on a substrate on which a conductor circuit is formed. As the substrate used in the present invention,
For example, plastic substrate, ceramic substrate, metal substrate,
A film substrate or the like can be used, and specifically, a glass epoxy substrate, a bismaleimide-triazine substrate,
A low temperature fired ceramic substrate, an aluminum nitride substrate, an aluminum substrate, an iron substrate, a polyimide film substrate or the like can be used.
【００２２】導体回路を形成した基板に前記樹脂絶縁層
を形成する方法としては、例えば上記感光性樹脂組成物
を、例えばローラーコート法、ディップコート法、スプ
レーコート法、スピナーコート法、カーテンコート法、
スクリーン印刷法などの各種手段により塗布する方法、
あるいは前記混合液をフィルム状に加工した樹脂フィル
ムを貼付する方法を適用することができる。また、本発
明における前記樹脂絶縁層の好適な厚さは通常２０〜１
００μｍ程度であるが、特に高い絶縁性が要求される場
合にはそれ以上に厚くすることもできる。As a method of forming the resin insulating layer on the substrate on which a conductor circuit is formed, for example, the above-mentioned photosensitive resin composition is applied by, for example, a roller coating method, a dip coating method, a spray coating method, a spinner coating method, a curtain coating method. ,
A method of applying by various means such as a screen printing method,
Alternatively, a method of applying a resin film obtained by processing the mixed solution into a film can be applied. The suitable thickness of the resin insulation layer in the present invention is usually 20 to 1
Although it is about 00 μm, it can be made thicker if a particularly high insulating property is required.
【００２３】上記感光性樹脂組成物を塗布、乾燥させた
後、次いで、このようにして得られた被膜の上にネガフ
ィルムをあて、活性光線を照射して露光部を硬化させ、
更に弱アルカリ水溶液を用いて未露光部を溶出する。本
発明における光による硬化に適したものとしては、超高
圧水銀ランプ、高圧水銀ランプあるいはメタルハライド
ランプ等のランプから発振される光が挙げられる。ま
た、本発明で述べるアルカリ性溶液としては炭酸ナトリ
ウム水溶液、炭酸水素ナトリウム水溶液、ジエタノール
アミン水溶液、トリエタノールアミン水溶液、水酸化ア
ンモニウム水溶液、水酸化ナトリウム水溶液などがあげ
られる。なかでも炭酸ナトリウム水溶液は適度なアルカ
リ性を有し、作業環境的にも水酸化ナトリウムなどの強
アルカリと違って安全であり特に好ましい。After coating and drying the above-mentioned photosensitive resin composition, a negative film is then placed on the thus-obtained coating film and irradiated with actinic rays to cure the exposed portion,
Further, the unexposed portion is eluted with a weak alkaline aqueous solution. Suitable for curing by light in the present invention is light emitted from a lamp such as an ultra-high pressure mercury lamp, a high pressure mercury lamp or a metal halide lamp. Examples of the alkaline solution described in the present invention include sodium carbonate aqueous solution, sodium hydrogen carbonate aqueous solution, diethanolamine aqueous solution, triethanolamine aqueous solution, ammonium hydroxide aqueous solution, and sodium hydroxide aqueous solution. Among them, the sodium carbonate aqueous solution is suitable because it has a proper alkalinity and is safe in terms of working environment unlike a strong alkali such as sodium hydroxide.
【００２４】アルカリ現像後、耐アルカリ性を向上させ
るために、加熱してエポキシ硬化処理を施すことが望ま
しい。本発明の樹脂組成物においては、加熱処埋を行う
ことによリ、強アルカリ水に対する耐久性が著しく向上
するばかリでなく、ガラス、銅等の金属に対する密着
性、耐熱性、表面硬度等の諸性質も向上する。After the alkali development, it is desirable to heat and apply an epoxy curing treatment in order to improve the alkali resistance. In the resin composition of the present invention, by performing heat treatment, not only the durability to strong alkaline water is significantly improved, but also glass, adhesion to metals such as copper, heat resistance, surface hardness, etc. The various properties of are also improved.
【００２５】本発明の多層プリント配線板は、前記樹脂
絶縁層の表面を酸、あるいは酸化剤を用いて粗面化処理
した後、無電解めっき及び電解めっきを施すことによ
り、導体回路を形成することにより製造される。この無
電解めっきの方法としては、例えば無電解銅めっき、無
電解ニッケルめっき、無電解金めっき、無電解銀めっ
き、無電解錫めっきのいずれか少なくとも一種であるこ
とが好適である。なお、前記無電解めっきを施した上に
さらに異なる種類の無電解めっきあるいは電解めっきを
行ったり、はんだをコートしたりすることもできる。In the multilayer printed wiring board of the present invention, a conductor circuit is formed by subjecting the surface of the resin insulating layer to surface roughening treatment using an acid or an oxidizing agent, and then subjecting it to electroless plating and electrolytic plating. It is manufactured by The electroless plating method is preferably at least one of electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, and electroless tin plating. In addition, it is also possible to further perform different types of electroless plating or electrolytic plating after applying the electroless plating, or to coat with solder.
【００２６】なお、本発明によれば、従来知られたプリ
ント配線板について行われている種々の方法で導体回路
を形成することができ、例えば基板に無電解めっき及び
電解めっきを施してから回路をエッチングする方法や無
電解めっきを施す際に直接回路を形成する方法などを適
用することができる。According to the present invention, a conductor circuit can be formed by various methods that have been carried out for a conventionally known printed wiring board. For example, a circuit is formed by subjecting a substrate to electroless plating and electrolytic plating. It is possible to apply a method of etching the substrate or a method of directly forming a circuit when performing electroless plating.
【００２７】本発明の樹脂組成物により絶縁層を形成す
ることにより、無電解めっき膜を信頼性よく形成させた
多層プリント基板配線板を容易にかつ安価に提供するこ
とができる。By forming an insulating layer from the resin composition of the present invention, it is possible to easily and inexpensively provide a multilayer printed wiring board having an electroless plated film formed thereon with high reliability.
【００２８】[0028]
【実施例】以下、本発明の多層プリント配線板を製造す
る実施例について説明する。 〈実施例１〉ビスフェノールＡ型エポキシアクリレート
（リポキシＶＲ−９０、昭和高分子社製）と無水フタル
酸を反応せしめて得られる酸価約１６５（ｍｇＫＯＨ／
ｇ）の紫外線硬化性樹脂４０重量部、脂環式エポキシ樹
脂ＥＨＰＥ−３１５０（ダイセル化学社製）２０重量
部、芳香環を含むエポキシ樹脂ＥＯＣＮ−４４００（日
本化薬製）５重量部、シリカゲル微粉末サイリシア７７
０（富士シリシア化学製、平均粒径５μｍ）１０重量
部、分散剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．５重量
部、消泡剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．５重量
部、光重合開始剤ダロキュアー４２６５（チバガイギー
社製）４重量部を混合し、エチルセルソルブアセテート
２０重量部を添加して撹拌した後、３本ロールで混練し
感光性絶縁樹脂溶液を得た。EXAMPLES Examples for manufacturing the multilayer printed wiring board of the present invention will be described below. <Example 1> An acid value of about 165 (mgKOH / mgKOH /, obtained by reacting bisphenol A type epoxy acrylate (lipoxy VR-90, manufactured by Showa High Polymer Co., Ltd.) with phthalic anhydride.
g) UV curable resin 40 parts by weight, alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries) 20 parts by weight, aromatic ring-containing epoxy resin EOCN-4400 (manufactured by Nippon Kayaku) 5 parts by weight, fine silica gel Powder Sylysia 77
0 (manufactured by Fuji Silysia Chemical Ltd., average particle size 5 μm) 10 parts by weight, dispersant (manufactured by BYK-CHEMIE) 0.5 part by weight, defoamer (manufactured by BYK-CHEMIE) 0.5 parts by weight, photopolymerization initiation 4 parts by weight of the agent Darocur 4265 (manufactured by Ciba Geigy) was mixed, 20 parts by weight of ethyl cellosolve acetate was added and stirred, and then kneaded with a three-roll to obtain a photosensitive insulating resin solution.
【００２９】次に、この感光性絶縁樹脂溶液をスロット
コータを用いて、脱脂洗浄した銅張りガラスエポキシ基
板に約５０μｍの厚さに塗布して乾燥したのち、フォト
マスクを介して２０００ｍＪ／ｃｍ2 で密着露光し、炭
酸ナトリウムの１％水溶液にて３０℃でｌ分間現像し、
未露光部を除去した。その後、乾燥オーブンを用いて、
１８０℃で３時間加熱硬化処理を行い、樹脂絶縁層を形
成した。Next, this photosensitive insulating resin solution was applied to a degreased and washed copper-clad glass epoxy substrate to a thickness of about 50 μm using a slot coater and dried, and then 2000 mJ / cm 2 through a photomask. Contact exposure with and develop with 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute,
The unexposed part was removed. Then, using a drying oven,
Heat curing treatment was performed at 180 ° C. for 3 hours to form a resin insulating layer.
【００３０】上記樹脂絶縁層を形成した基板を、膨潤液
（シプレイ社製）に５０℃で１５分、過マンガン酸カリ
ウム／水酸化ナトリウムの混合溶液に７０℃で５分間浸
漬して樹脂絶縁層の表面を粗面化し、その後中和溶液
（シプレイ社製）に浸漬して水洗した。The substrate on which the resin insulating layer is formed is immersed in a swelling solution (made by Shipley) at 50 ° C. for 15 minutes, and in a mixed solution of potassium permanganate / sodium hydroxide at 70 ° C. for 5 minutes to immerse the resin insulating layer. Was roughened, then immersed in a neutralizing solution (made by Shipley) and washed with water.
【００３１】次に、樹脂絶縁層の表面が粗面化された基
板にパラジウム触媒（シプレイ社製）層を形成し、アク
セラレータ（シプレイ社製）により表面を活性化させた
後、無電解めっき液（シプレイ社製）に３０分間浸漬し
て、更に電解めっき液（硫酸銅）に１Ａ／ｄｍの電流を
流しながら２時間浸漬して厚さ２５μｍの銅めっきを施
し、プリント配線板を得た。Next, a palladium catalyst (manufactured by Shipley) is formed on a substrate having a resin insulating layer whose surface is roughened, and the surface is activated by an accelerator (manufactured by Shipley), followed by electroless plating solution. (Manufactured by Shipley Co., Ltd.) for 30 minutes and further immersed in an electrolytic plating solution (copper sulfate) for 2 hours while applying a current of 1 A / dm to perform copper plating with a thickness of 25 μm to obtain a printed wiring board.
【００３２】〈実施例２〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０、昭和高分子社製）
と無水フタル酸を反応せしめて得られる酸価約１６５
（ｍｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、脂
環式エポキシ樹脂ＥＨＰＥ−３１５０（ダイセル化学社
製）１７．５重量部、芳香環を含むエポキシ樹脂ＥＯＣ
Ｎ−４４００（日本化薬社製）７．５重量部、シリカゲ
ル微粉末サイリシア７７０（富士シリシア化学製、平均
粒径５μｍ）１０重量部、分散剤（ＢＹＫ−ＣＨＥＭＩ
Ｅ社製）０．５重量部、消泡剤（ＢＹＫ−ＣＨＥＭＩＥ
社製）０．５重量部、光重合開始剤ダロキュアー４２６
５（チバガイギー社製）４重量部を混合し、その混合物
に対して２０重量部のエチルセルソルブアセテートを添
加して撹拌した後、３本ロールで混練し感光性絶縁樹脂
溶液を得た。この感光性絶縁樹脂溶液を用い、以下感光
性絶縁樹脂溶液の塗布以降電解銅めっきまで、実施例１
と同様の方法で処理を行い、プリント配線板を得た。<Example 2> Bisphenol A type epoxy acrylate (lipoxy VR-90, manufactured by Showa High Polymer Co., Ltd.)
Acid value obtained by reacting phthalic anhydride with 165
(MgKOH / g) UV curable resin 40 parts by weight, alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) 17.5 parts by weight, epoxy resin EOC containing aromatic ring
N-4400 (manufactured by Nippon Kayaku Co., Ltd.) 7.5 parts by weight, silica gel fine powder Sylysia 770 (manufactured by Fuji Silysia Chemical Ltd., average particle size 5 μm) 10 parts by weight, dispersant (BYK-CHEMI).
E company) 0.5 part by weight, antifoaming agent (BYK-CHEMIE
0.5 parts by weight, Darocur 426 photopolymerization initiator
5 parts (manufactured by Ciba Geigy) were mixed, 20 parts by weight of ethyl cellosolve acetate was added to the mixture, and the mixture was stirred and then kneaded with three rolls to obtain a photosensitive insulating resin solution. Using this photosensitive insulating resin solution, hereinafter, from the application of the photosensitive insulating resin solution to the electrolytic copper plating, Example 1
By the same method as above, a printed wiring board was obtained.
【００３３】〈実施例３〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０、昭和高分子社製）
と無水フタル酸を反応せしめて得られる酸価約１６５
（ｍｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、脂
環式エポキシ樹脂ＥＨＰＥ−３１５０（ダイセル化学社
製）１５重量部、芳香環を含むエポキシ樹脂ＥＣＯＮ−
４４００（日本化薬社製）１０重量部、シリカゲル微粉
末サイリシア７７０（富士シリシア化学製、平均粒径５
μｍ）１０重量部、分散剤（ＢＹＫ−ＣＨＥＭＩＥ社
製）０．５重量部、消泡剤（ＢＹＫ−ＣＨＥＭＩＥ社
製）０．５重量部、光重合開始剤ダロキュアー４２６５
（チバガイギー社製）４重量部を混合し、その混合物に
対して２０重量部のエチルセルソルブアセテートを添加
して撹拌した後、３本ロールで混練し感光性絶縁樹脂溶
液を得た。この感光性絶縁樹脂溶液を用い、以下感光性
絶縁樹脂溶液の塗布以降電解銅めっきまで、実施例１と
同様の方法で処理を行い、プリント配線板を得た。<Example 3> Bisphenol A type epoxy acrylate (lipoxy VR-90, manufactured by Showa High Polymer Co., Ltd.)
Acid value obtained by reacting phthalic anhydride with 165
(MgKOH / g) UV curable resin 40 parts by weight, alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) 15 parts by weight, epoxy resin ECON- containing aromatic ring
4400 (Nippon Kayaku Co., Ltd.) 10 parts by weight, silica gel fine powder Sylysia 770 (Fuji Silysia Chemical, average particle size 5)
μm) 10 parts by weight, dispersant (manufactured by BYK-CHEMIE) 0.5 parts by weight, defoamer (manufactured by BYK-CHEMIE) 0.5 parts by weight, photoinitiator Darocur 4265
4 parts by weight (manufactured by Ciba Geigy) were mixed, 20 parts by weight of ethyl cellosolve acetate was added to the mixture, and the mixture was stirred and then kneaded with a three-roll to obtain a photosensitive insulating resin solution. Using this photosensitive insulating resin solution, the following processes from the application of the photosensitive insulating resin solution to the electrolytic copper plating were carried out in the same manner as in Example 1 to obtain a printed wiring board.
【００３４】〈実施例４〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０、昭和高分子社製）
と無水フタル酸を反応せしめて得られる酸価約１６５
（ｍｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、脂
環式エポキシ樹脂ＥＨＰＥ−３１５０（ダイセル化学社
製）１７．５重量部、芳香環を含むエポキシ樹脂ＨＰ７
２００Ｈ（大日本インキ社製）７．５重量部、シリカゲ
ル微粉末サイリシア７７０（富士シリシア化学製、平均
粒径５μｍ）１０重量部、分散剤（ＢＹＫ−ＣＨＥＭＩ
Ｅ社製）０．５重量部、消泡剤（ＢＹＫ−ＣＨＥＭＩＥ
社製）０．５重量部、光重合開始剤ダロキュアー４２６
５（チバガイギー社製）４重量部を混合し、その混合物
に対して２０重量部のエチルセルソルブアセテートを添
加して撹拌した後、３本ロールで混練し感光性絶縁樹脂
溶液を得た。この感光性絶縁樹脂溶液を用い、以下感光
性絶縁樹脂溶液の塗布以降電解銅めっきまで、実施例１
と同様の方法で処理を行い、プリント配線板を得た。<Example 4> Bisphenol A type epoxy acrylate (lipoxy VR-90, manufactured by Showa High Polymer Co., Ltd.)
Acid value obtained by reacting phthalic anhydride with 165
(MgKOH / g) UV curable resin 40 parts by weight, alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) 17.5 parts by weight, epoxy resin HP7 containing aromatic ring
200H (manufactured by Dainippon Ink and Chemicals, Inc.) 7.5 parts by weight, silica gel fine powder Sylysia 770 (manufactured by Fuji Silysia Chemical Ltd., average particle size 5 μm) 10 parts by weight, dispersant (BYK-CHEMI).
E company) 0.5 part by weight, antifoaming agent (BYK-CHEMIE
0.5 parts by weight, Darocur 426 photopolymerization initiator
5 parts (manufactured by Ciba Geigy) were mixed, 20 parts by weight of ethyl cellosolve acetate was added to the mixture, and the mixture was stirred and then kneaded with three rolls to obtain a photosensitive insulating resin solution. Using this photosensitive insulating resin solution, hereinafter, from the application of the photosensitive insulating resin solution to the electrolytic copper plating, Example 1
By the same method as above, a printed wiring board was obtained.
【００３５】〈実施例５〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０、昭和高分子社製）
と無水フタル酸を反応せしめて得られる酸価約１６５
（ｍｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、脂
環式エポキシ樹脂ＥＨＰＥ−３１５０（ダイセル化学社
製）１５重量部、芳香環を含むエポキシ樹脂ＨＰ７２０
０Ｈ（大日本インキ社製）１５重量部、シリカゲル微粉
末サイリシア７７０（富士シリシア化学製、平均粒径５
μｍ）１０重量部、分散剤（ＢＹＫ−ＣＨＥＭＩＥ社
製）０．５重量部、消泡剤（ＢＹＫ−ＣＨＥＭＩＥ社
製）０．５重量部、光重合開始剤ダロキュアー４２６５
（チバガイギー社製）４重量部を混合し、その混合物に
対して２０重量部のエチルセルソルブアセテートを添加
して撹拌した後、３本ロールで混練し感光性絶縁樹脂溶
液を得た。この感光性絶縁樹脂溶液を用い、以下感光性
絶縁樹脂溶液の塗布以降電解銅めっきまで、実施例１と
同様の方法で処理を行い、プリント配線板を得た。Example 5 Bisphenol A Epoxy Acrylate (Lipoxy VR-90, Showa High Polymer Co., Ltd.)
Acid value obtained by reacting phthalic anhydride with 165
(MgKOH / g) UV curable resin 40 parts by weight, alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) 15 parts by weight, epoxy resin HP720 containing aromatic ring
15 parts by weight of OH (manufactured by Dainippon Ink and Chemicals, Inc.), silica gel fine powder Sylysia 770 (manufactured by Fuji Silysia Chemical, average particle size 5)
μm) 10 parts by weight, dispersant (manufactured by BYK-CHEMIE) 0.5 parts by weight, defoamer (manufactured by BYK-CHEMIE) 0.5 parts by weight, photoinitiator Darocur 4265
4 parts by weight (manufactured by Ciba Geigy) were mixed, 20 parts by weight of ethyl cellosolve acetate was added to the mixture, and the mixture was stirred and then kneaded with a three-roll to obtain a photosensitive insulating resin solution. Using this photosensitive insulating resin solution, the following processes from the application of the photosensitive insulating resin solution to the electrolytic copper plating were carried out in the same manner as in Example 1 to obtain a printed wiring board.
【００３６】〈実施例６〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０、昭和高分子社製）
と無水フタル酸を反応せしめて得られる酸価約１６５
（ｍｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、脂
環式エポキシ樹脂ＥＨＰＥ−３１５０（ダイセル化学社
製）１２．５重量部、芳香環を含むエポキシ樹脂ＨＰ７
２００Ｈ（大日本インキ社製）１２．５重量部、シリカ
ゲル微粉末サイリシア７７０（富士シリシア化学製、平
均粒径５μｍ）１０重量部、分散剤（ＢＹＫ−ＣＨＥＭ
ＩＥ社製）０．５重量部、消泡剤（ＢＹＫ−ＣＨＥＭＩ
Ｅ社製）０．５重量部、光重合開始剤ダロキュアー４２
６５（チバガイギー社製）４重量部を混合し、その混合
物に対して２０重量部のエチルセルソルブアセテートを
添加して撹拌した後、３本ロールで混練し感光性絶縁樹
脂溶液を得た。この感光性絶縁樹脂溶液を用い、以下感
光性絶縁樹脂溶液の塗布以降電解銅めっきまで、実施例
１と同様の方法で処理を行い、プリント配線板を得た。<Example 6> Bisphenol A type epoxy acrylate (lipoxy VR-90, manufactured by Showa High Polymer Co., Ltd.)
Acid value obtained by reacting phthalic anhydride with 165
(MgKOH / g) UV curable resin 40 parts by weight, alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) 12.5 parts by weight, aromatic ring-containing epoxy resin HP7
200H (manufactured by Dainippon Ink and Chemicals, Inc.) 12.5 parts by weight, silica gel fine powder Sylysia 770 (manufactured by Fuji Silysia Chemical Ltd., average particle size 5 μm) 10 parts by weight, dispersant (BYK-CHEM)
IE, 0.5 parts by weight, antifoaming agent (BYK-CHEMI)
(Manufactured by Company E) 0.5 part by weight, photopolymerization initiator Darocur 42
4 parts by weight of 65 (manufactured by Ciba Geigy) were mixed, 20 parts by weight of ethyl cellosolve acetate was added to the mixture, and the mixture was stirred and then kneaded with three rolls to obtain a photosensitive insulating resin solution. Using this photosensitive insulating resin solution, the following processes from the application of the photosensitive insulating resin solution to the electrolytic copper plating were carried out in the same manner as in Example 1 to obtain a printed wiring board.
【００３７】〈実施例７〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０、昭和高分子社製）
と無水フタル酸を反応せしめて得られる酸価約１６５
（ｍｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、脂
環式エポキシ樹脂ＥＨＰＥ−３１５０（ダイセル化学社
製）１５重量部、芳香環を含むエポキシ樹脂ＭＹ−９５
１２（旭チバ社製）１０重量部、シリカゲル微粉末サイ
リシア７７０（富士シリシア化学製、平均粒径５μｍ）
１０重量部、分散剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．
５重量部、消泡剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．５
重量部、光重合開始剤ダロキュアー４２６５（チバガイ
ギー社製）４重量部を混合し、その混合物に対して２０
重量部のエチルセルソルブアセテートを添加して撹拌し
た後、３本ロールで混練し感光性絶縁樹脂溶液を得た。
この感光性絶縁樹脂溶液を用い、以下感光性絶縁樹脂溶
液の塗布以降電解銅めっきまで、実施例１と同様の方法
で処理を行い、プリント配線板を得た。<Example 7> Bisphenol A type epoxy acrylate (lipoxy VR-90, manufactured by Showa High Polymer Co., Ltd.)
Acid value obtained by reacting phthalic anhydride with 165
(MgKOH / g) UV curable resin 40 parts by weight, alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) 15 parts by weight, epoxy resin MY-95 containing aromatic ring
12 (manufactured by Asahi Ciba) 10 parts by weight, silica gel fine powder Sylysia 770 (manufactured by Fuji Silysia Chemical, average particle size 5 μm)
10 parts by weight, dispersant (manufactured by BYK-CHEMIE) 0.
5 parts by weight, antifoaming agent (manufactured by BYK-CHEMIE) 0.5
By weight, 4 parts by weight of a photopolymerization initiator Darocur 4265 (manufactured by Ciba Geigy) are mixed, and the mixture is mixed with 20 parts by weight.
A part by weight of ethyl cellosolve acetate was added and stirred, and then kneaded with a three-roll to obtain a photosensitive insulating resin solution.
Using this photosensitive insulating resin solution, the following processes from the application of the photosensitive insulating resin solution to the electrolytic copper plating were carried out in the same manner as in Example 1 to obtain a printed wiring board.
【００３８】〈実施例８〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０昭和高分子社製）と
無水フタル酸を反応せしめて得られる酸価約１６５（ｍ
ｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、脂環式
エポキシ樹脂ＥＨＰＥ−３１５０（ダイセル化学社製）
２０重量部、芳香環を含むエポキシ樹脂ＭＹ−９５１２
（旭チバ社製）５重量部、シリカゲル微粉末サイリシア
７７０（富士シリシア化学製、平均粒径５μｍ）１０重
量部、分散剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．５重量
部、消泡剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．５重量
部、光重合開始剤ダロキュアー４２６５（チバガイギー
社製）４重量部を混合し、その混合物に対して２０重量
部のエチルセルソルブアセテートを添加して撹拌した
後、３本ロールで混練し感光性絶縁樹脂溶液を得た。こ
の感光性絶縁樹脂溶液を用い、以下感光性絶縁樹脂溶液
の塗布以降電解銅めっきまで、実施例１と同様の方法で
処理を行い、プリント配線板を得た。Example 8 An acid value of about 165 (m) obtained by reacting bisphenol A type epoxy acrylate (lipoxy VR-90 manufactured by Showa High Polymer Co., Ltd.) with phthalic anhydride.
40 parts by weight of UV curable resin (gKOH / g), alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.)
20 parts by weight, epoxy resin MY-9512 containing aromatic ring
(Asahi Ciba) 5 parts by weight, silica gel fine powder Sylysia 770 (manufactured by Fuji Silysia Chemical Ltd., average particle size 5 μm) 10 parts by weight, dispersant (manufactured by BYK-CHEMIE) 0.5 parts by weight, defoamer (BYK). -CHEMIE) 0.5 parts by weight and 4 parts by weight of a photopolymerization initiator Darocur 4265 (manufactured by Ciba Geigy) are mixed, and 20 parts by weight of ethyl cellosolve acetate is added to the mixture and stirred, The mixture was kneaded with three rolls to obtain a photosensitive insulating resin solution. Using this photosensitive insulating resin solution, the following processes from the application of the photosensitive insulating resin solution to the electrolytic copper plating were carried out in the same manner as in Example 1 to obtain a printed wiring board.
【００３９】〈比較例１〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０、昭和高分子社製）
と無水フタル酸を反応せしめて得られる酸価約１６５
（ｍｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、脂
環式エポキシ樹脂ＥＨＰＥ−３１５０（ダイセル化学社
製）２５重量部、シリカゲル微粉末サイリシア７７０
（富士シリシア化学製、平均粒径５μｍ）１０重量部、
分散剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．５重量部、消
泡剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．５重量部、光重
合開始剤ダロキュアー４２６５（チバガイギー社製）４
重量部を混合し、その混合物に対して２０重量部のエチ
ルセルソルブアセテートを添加して撹拌した後、３本ロ
ールで混練し感光性絶縁樹脂溶液を得た。この感光性絶
縁樹脂溶液を用い、以下感光性絶縁樹脂溶液の塗布以降
電解銅めっきまで、実施例１と同様の方法で処理を行
い、プリント配線板を得た。<Comparative Example 1> Bisphenol A type epoxy acrylate (lipoxy VR-90, manufactured by Showa High Polymer Co., Ltd.)
Acid value obtained by reacting phthalic anhydride with 165
(MgKOH / g) UV curable resin 40 parts by weight, alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) 25 parts by weight, silica gel fine powder Sylysia 770
(Fuji Silysia Chemical, average particle size 5 μm) 10 parts by weight,
0.5 parts by weight of a dispersant (manufactured by BYK-CHEMIE), 0.5 part by weight of an antifoaming agent (manufactured by BYK-CHEMIE), a photopolymerization initiator Darocur 4265 (manufactured by Ciba Geigy) 4
20 parts by weight of ethyl cellosolve acetate was added to the mixture, stirred, and then kneaded with a three-roll mill to obtain a photosensitive insulating resin solution. Using this photosensitive insulating resin solution, the following processes from the application of the photosensitive insulating resin solution to the electrolytic copper plating were carried out in the same manner as in Example 1 to obtain a printed wiring board.
【００４０】〈比較例２〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０、昭和高分子社製）
と無水フタル酸を反応せしめて得られる酸価約１６５
（ｍｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、芳
香環を含むエポキシ樹脂ＥＣＯＮ−４４００（日本化薬
社製）２５重量部、シリカゲル微粉末サイリシア７７０
（富士シリシア化学製、平均粒径５μｍ）１０重量部、
分散剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．５重量部、消
泡剤（ＢＹＫ−ＣＨＥＭＩＥ社製）０．５重量部、光重
合開始剤ダロキュアー４２６５（チバガイギー社製）４
重量部を混合し、その混合物に対して２０重量部のエチ
ルセルソルブアセテートを添加して撹拌した後、３本ロ
ールで混練し感光性絶縁樹脂溶液を得た。この感光性絶
縁樹脂溶液を用い、以下感光性絶縁樹脂溶液の塗布以降
電解銅めっきまで、実施例１と同様の方法で処理を行
い、プリント配線板を得た。<Comparative Example 2> Bisphenol A type epoxy acrylate (lipoxy VR-90, manufactured by Showa High Polymer Co., Ltd.)
Acid value obtained by reacting phthalic anhydride with 165
(MgKOH / g) UV curable resin 40 parts by weight, aromatic ring-containing epoxy resin ECON-4400 (manufactured by Nippon Kayaku Co., Ltd.) 25 parts by weight, silica gel fine powder Sylysia 770
(Fuji Silysia Chemical, average particle size 5 μm) 10 parts by weight,
0.5 parts by weight of a dispersant (manufactured by BYK-CHEMIE), 0.5 part by weight of an antifoaming agent (manufactured by BYK-CHEMIE), a photopolymerization initiator Darocur 4265 (manufactured by Ciba Geigy) 4
20 parts by weight of ethyl cellosolve acetate was added to the mixture, stirred, and then kneaded with a three-roll mill to obtain a photosensitive insulating resin solution. Using this photosensitive insulating resin solution, the following processes from the application of the photosensitive insulating resin solution to the electrolytic copper plating were carried out in the same manner as in Example 1 to obtain a printed wiring board.
【００４１】〈比較例３〉ビスフェノールＡ型エポキシ
アクリレート（リポキシＶＲ−９０、昭和高分子社製）
と無水フタル酸を反応せしめて得られる酸価約１６５
（ｍｇＫＯＨ／ｇ）の紫外線硬化性樹脂４０重量部、芳
香環を含むエポキシ樹脂（大日本インキ社製）２５重量
部、シリカゲル微粉末サイリシア７７０（富士シリシア
化学製、平均粒径５μｍ）１０重量部、分散剤（ＢＹＫ
−ＣＨＥＭＩＥ社製）０．５重量部、消泡剤（ＢＹＫ−
ＣＨＥＭＩＥ社製）０．５重量部、光重合開始剤ダロキ
ュアー４２６５（チバガイギー社製）４重量部を混合
し、その混合物に対して２０重量部のエチルセルソルブ
アセテートを添加して撹拌した後、３本ロールで混練し
感光性絶縁樹脂溶液を得た。この感光性絶縁樹脂溶液を
用い、以下感光性絶縁樹脂溶液の塗布以降電解銅めっき
まで、実施例１と同様の方法で処理を行い、プリント配
線板を得た。<Comparative Example 3> Bisphenol A type epoxy acrylate (lipoxy VR-90, manufactured by Showa High Polymer Co., Ltd.)
Acid value obtained by reacting phthalic anhydride with 165
40 parts by weight of (mgKOH / g) UV curable resin, 25 parts by weight of an epoxy resin containing an aromatic ring (manufactured by Dainippon Ink and Chemicals, Inc.), 10 parts by weight of silica gel fine powder Sylysia 770 (manufactured by Fuji Silysia Chemical, average particle size 5 μm). , Dispersant (BYK
-CHEMIE, 0.5 parts by weight, antifoaming agent (BYK-
CHEMIE Co., Ltd.) 0.5 parts by weight and photopolymerization initiator Darocur 4265 (Ciba Geigy Co., Ltd.) 4 parts by weight are mixed, and 20 parts by weight of ethyl cellosolve acetate is added to the mixture and stirred, and then 3 The mixture was kneaded with this roll to obtain a photosensitive insulating resin solution. Using this photosensitive insulating resin solution, the following processes from the application of the photosensitive insulating resin solution to the electrolytic copper plating were carried out in the same manner as in Example 1 to obtain a printed wiring board.
【００４２】上述したようにして製造されたプリント配
線板の絶縁樹脂層と銅めっき層との接着強度をＪＩＳ−
Ｃ−６４８１の方法で測定したところ、ピール強度は
（表１）に示す結果となった。また、ガラス転移温度の
測定も同時に行ったがいずれも良好な結果を得た。The adhesive strength between the insulating resin layer and the copper plating layer of the printed wiring board manufactured as described above is determined by JIS-
When the peel strength was measured by the method of C-6481, the results are shown in (Table 1). The glass transition temperature was also measured at the same time, and good results were obtained in each case.
【００４３】[0043]
【表１】 [Table 1]
【００４４】上記（表１）から明らかなように、実施例
１〜８は目的の諸物性、すなわち耐熱性かつ無電解めっ
き接着性の優れた特性を達成できたが、比較例１では、
耐熱性の値は十分なものの、めっきピール強度が低く、
無電解めっき膜を信頼性よく形成させることが困難であ
った。また比較例２及び比較例３では、逆に無電解めっ
き膜は信頼性よく形成させることができるもののガラス
転移温度が低く、十分な耐熱性を得られるに至らなかっ
た。As is clear from the above (Table 1), Examples 1 to 8 were able to achieve the desired physical properties, that is, excellent heat resistance and electroless plating adhesion, but in Comparative Example 1,
Although the value of heat resistance is sufficient, the plating peel strength is low,
It was difficult to form the electroless plated film with high reliability. On the contrary, in Comparative Examples 2 and 3, the electroless plated film could be formed with high reliability, but the glass transition temperature was low, and sufficient heat resistance could not be obtained.
【００４５】以上の結果より、本発明の樹脂組成物は、
耐熱性かつ無電解めっき接着性の優れたアルカリ現像型
感光性樹脂絶縁膜を提供できることが判明した。From the above results, the resin composition of the present invention is
It has been found that an alkali-developable photosensitive resin insulation film having excellent heat resistance and adhesiveness to electroless plating can be provided.
【００４６】[0046]
【発明の効果】本発明の感光性樹脂組成物により樹脂絶
縁層を形成することにより、高耐熱性、かつ接着性の優
れた導体回路を有する高信頼性の多層プリント配線板を
容易にかつ安価に提供できる。EFFECT OF THE INVENTION By forming a resin insulating layer from the photosensitive resin composition of the present invention, a highly reliable multilayer printed wiring board having a conductor circuit with high heat resistance and excellent adhesiveness can be easily and inexpensively produced. Can be provided to.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 63/10 ＮＪＷ Ｃ０８Ｌ 63/10 ＮＪＷ Ｇ０３Ｆ 7/032 ５０１ Ｇ０３Ｆ 7/032 ５０１ Ｈ０５Ｋ 3/46 Ｈ０５Ｋ 3/46 Ｔ (72)発明者 松本 陽美 東京都台東区台東１丁目５番１号 凸版印 刷株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08L 63/10 NJW C08L 63/10 NJW G03F 7/032 501 G03F 7/032 501 H05K 3/46 H05K 3/46 T (72) Inventor Yoshimi Matsumoto 1-5-1 Taito, Taito-ku, Tokyo Inside Toppan Printing Co., Ltd.
Claims (3)
型エポキシ化合物と不飽和モノカルボン酸との反応物と
飽和または不飽和多塩基酸無水物とを反応せしめて得ら
れる紫外線硬化性樹脂（Ａ）と、光重合開始剤（Ｂ）
と、希釈剤（Ｃ）と、一分子中に３個以上のエポキシ基
を有する２種類のエポキシ化合物からなる熱硬化性成分
を含んでなり、該エポキシ化合物の一つが脂環式エポキ
シ類化合物であり、もう一つが芳香族環を含む構造のエ
ポキシ類化合物（Ｄ）と、からなることを特徴とする希
アルカリ溶液に現像可能な光硬化性および熱硬化性の多
層プリント配線板用絶縁層樹脂組成物。1. An ultraviolet curable resin (A) obtained by reacting a reaction product of a bisphenol type epoxy compound and an unsaturated monocarboxylic acid as a photosensitive heat resistant resin component with a saturated or unsaturated polybasic acid anhydride. , Photopolymerization initiator (B)
And a diluent (C), and a thermosetting component composed of two kinds of epoxy compounds having three or more epoxy groups in one molecule, one of the epoxy compounds being an alicyclic epoxy compound. And another is an epoxy compound (D) having a structure containing an aromatic ring, and a photocurable and thermosetting insulating layer resin for a multilayer printed wiring board, which is developable in a dilute alkaline solution. Composition.
含むエポキシ類化合物の配合比が４：１〜１：１（重量
比）であることを特徴とする請求項１記載の多層プリン
ト配線板用絶縁層樹脂組成物。2. The multilayer print according to claim 1, wherein the compounding ratio of the alicyclic epoxy compound and the epoxy compound containing an aromatic ring is 4: 1 to 1: 1 (weight ratio). Insulating layer resin composition for wiring boards.
に記載の多層プリント配線板用絶縁層樹脂組成物。3. The alicyclic epoxy compound according to claim 1, 3. A structure as set forth in claim 1, wherein:
The insulating layer resin composition for a multilayer printed wiring board as described in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28508695A JP3841858B2 (en) | 1995-11-01 | 1995-11-01 | Insulating layer resin composition for multilayer printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28508695A JP3841858B2 (en) | 1995-11-01 | 1995-11-01 | Insulating layer resin composition for multilayer printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09124767A true JPH09124767A (en) | 1997-05-13 |
| JP3841858B2 JP3841858B2 (en) | 2006-11-08 |
Family
ID=17686963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28508695A Expired - Fee Related JP3841858B2 (en) | 1995-11-01 | 1995-11-01 | Insulating layer resin composition for multilayer printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3841858B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0943935A2 (en) * | 1998-03-20 | 1999-09-22 | Nippon Telegraph and Telephone Corporation | Optical waveguide and method for production thereof |
| JP2000212248A (en) * | 1999-01-21 | 2000-08-02 | Toppan Printing Co Ltd | Insulating resin composition for multilayered printed- wiring board and multilayered printed-wiring board |
| JP2001228605A (en) * | 2000-02-16 | 2001-08-24 | Shin Etsu Chem Co Ltd | Thermosetting photosensitive material |
| WO2005019298A1 (en) * | 2003-08-25 | 2005-03-03 | Daicel Chemical Industries, Ltd. | Thermosetting epoxy resin composition and transparent material |
| US7781543B2 (en) | 2002-09-05 | 2010-08-24 | Daicel Chemical Industries, Ltd. | Curable alicyclic diepoxy resin composition |
| US7786224B2 (en) * | 2001-03-23 | 2010-08-31 | Daicel Chemical Industries, Ltd | Liquid composition of alicyclic diepoxide, curing agent and/or curing accelerator |
-
1995
- 1995-11-01 JP JP28508695A patent/JP3841858B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0943935A2 (en) * | 1998-03-20 | 1999-09-22 | Nippon Telegraph and Telephone Corporation | Optical waveguide and method for production thereof |
| EP0943935A3 (en) * | 1998-03-20 | 2001-01-31 | Nippon Telegraph and Telephone Corporation | Optical waveguide and method for production thereof |
| JP2000212248A (en) * | 1999-01-21 | 2000-08-02 | Toppan Printing Co Ltd | Insulating resin composition for multilayered printed- wiring board and multilayered printed-wiring board |
| JP2001228605A (en) * | 2000-02-16 | 2001-08-24 | Shin Etsu Chem Co Ltd | Thermosetting photosensitive material |
| US7786224B2 (en) * | 2001-03-23 | 2010-08-31 | Daicel Chemical Industries, Ltd | Liquid composition of alicyclic diepoxide, curing agent and/or curing accelerator |
| US7781543B2 (en) | 2002-09-05 | 2010-08-24 | Daicel Chemical Industries, Ltd. | Curable alicyclic diepoxy resin composition |
| WO2005019298A1 (en) * | 2003-08-25 | 2005-03-03 | Daicel Chemical Industries, Ltd. | Thermosetting epoxy resin composition and transparent material |
| CN100445311C (en) * | 2003-08-25 | 2008-12-24 | 大赛璐化学工业株式会社 | Thermosetting epoxy resin composition and transparent material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3841858B2 (en) | 2006-11-08 |
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