JP4648508B2 - Resin composition and build-up wiring board using the same - Google Patents

Description

【００１１】
（式中、ＲはＨまたはＣ₁ 〜Ｃ₅ アルキルである）で示されるものが挙げられる。具体的には、Ｒがそれぞれ、ｎ−プロピルおよび水素である６−（４−ビニルベンジル−ｎ−プロピル）アミノ−１，３，５−トリアジン−２，４−ジチオールおよび６−（４−ビニルベンジル）アミノ−１，３，５−トリアジン−２，４−ジチオールがある。かかる化合物は銅配線と樹脂層との密着性を改良するために十分な量で用いられ、通常、エポキシ樹脂１００重量部に対して０．０１〜５重量部、好ましくは０．１〜５重量部の量で用いられる。これより多量であると、コストが嵩み、かつ、樹脂の物性が低くなることがあるからである。
【００１２】
本発明の組成物はビルドアップ配線基板のための絶縁樹脂として好適なエポキシ樹脂を含む。エポキシ樹脂としては、コア基板の曲げや基板上への部品の実装時に優れた耐クラック性、高い柔軟性および優れた信頼性を示すことができる組成物を提供することができるものである。エポキシ樹脂は好適には脂環式構造を有するエポキシである。特に好適な脂環式エポキシは、EHPE-3150(ダイセル化学) 等のシクロヘキサン骨格の多官能エポキシ樹脂、ERL-4299( ユニオンカーバイド社) 、セロキサイド2021 (ダイセル化学) 、CY-175( チバガイギー社) 、セロキサイド2080( ダイセル化学) 等の脂環式二官能エポキシ、エポリードGT300 等の脂環式三官能エポキシ、エポリードGT400 等の脂環式四官能エポキシおよびそれらの混合物である。
【００１３】
エポキシ硬化剤としてはフェノールノボラック樹脂および酸無水物が挙げられる。フェノールノボラック樹脂としては群栄化学製のPSM-4300があり、酸無水物としては新日本理化（株）より販売されるリカシッドHH、リカシッドTMEGがある。エポキシ硬化剤は、通常、エポキシ樹脂成分中に含まれるエポキシ基１当量に対してエポキシ硬化剤の活性水素当量として０．８〜１．１当量となるような配合比で含まれることが望ましい。このような量を用いるとエポキシ硬化物の物性が良好になるからである。
【００１４】
本発明の組成物は不飽和エチレン基を有するビニルもしくはアクリル化合物を含んでもよい。かかる化合物は、本発明に用いるトリアジンジチオールのエチレン基と重合反応を起こし、絶縁樹脂構造内にトリアジンチオール化合物を取り込む作用を有する。このような化合物としては、ジフェン酸エステルジアクリレート、ビスフェノールＡジエポキシアクリル酸付加物、ビスフェノールＦジエポキシアクリル酸付加物、トリメチロールプロパントリアクリレート、１，６−ヘキサンジオールジアクリレート、ペンタエリスリトールテトラアクリレート等の多官能アクリレートおよびこれらの多官能アクリレートに対応するメタクリレート類、アクリル酸メチル、メタクリル酸メチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、メタクリル酸メチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチルまたはジアリルフタレート等のモノマーもしくはオリゴマー等を挙げることができる。このような化合物は、使用されるときには、得られるエポキシ硬化物の物性を損なわない範囲の量で含まれ、通常、エポキシ樹脂１００重量部当たりに３０重量部以下の量で含まれる。
【００１５】
本発明の組成物はさらに不飽和エチレン基の重合を開始するための重合開始剤を含んでもよい。重合開始剤としてはα−アミノアルキルフェノンまたはその誘導体、ベンゾインエーテルまたはその誘導体、ケタールまたはその誘導体、アセトフェノンまたはその誘導体、ベンゾフェノンまたはその誘導体、チオキサントンまたはその誘導体、有機過酸化物、Ｎ−フェニルグリシン等の熱重合開始剤が挙げられる。重合開始剤は、通常、トリアジンジチオール化合物およびビニルもしくはアクリル化合物の合計量に対して１〜５重量％の量で使用される。
【００１６】
本発明の組成物は、一般に、ワニス状組成物として基板上に塗布、含浸される。ワニス状組成物とするのに、本発明の組成物は適当な溶媒を含むことができる。溶媒の例としては、エチレングリコールモノエーテルのようなエーテル類、シクロヘキサンのようなケトン類、アセテートのようなエステル類、トルエン、キシレン等の有機溶剤を挙げることができる。さらに、エポキシ化合物の硬化促進を目的として、トリフェニルホスフィンまたはイミダゾールなどの硬化促進剤を添加してもよい。このような硬化促進剤は、通常、エポキシ樹脂１００重量部に対して１〜１０重量部の量で添加することができる。また、必要に応じて、種々の添加剤、例えば、シリカ、アルミナ、アエロジルなどの体質顔料、フタロシアニンなどの着色顔料、シリコーンおよびフッ素系化合物からなる消泡剤、レベリング剤、酸化防止剤などを添加することができる。
【００１７】
さらに、難燃性が必要なときには、少量のリン系難燃剤を添加することもできる。このようなリン系難燃剤は、リン成分と窒素成分を共存させることで、窒素化合物がリン成分の分解および熱縮合を促進させ、ポリリン酸を生成し、そのポリリン酸がエポキシ樹脂の表面に皮膜を生成し、断熱効果、酸素遮断効果を生じ、その結果、燃焼を防止しようとするものである。本発明の組成物中に使用してよいリン成分としては、トリメチルホスフェート、トリフェニルホスフェート等のリン酸エステルが例示されるが、特にこれらに限定されるものではない。また、リン成分は本発明の組成物中に１０重量％以上存在すると吸水しやすくなるため好ましくない。
【００１８】
次に、図１にビルドアップ配線基板１０の断面図を示す。ビルドアップ配線基板１０はコア基板１の両面に多層化された配線回路層１２および１３を有しており、また、配線回路層１２および１３は、それぞれ、本発明の樹脂組成物に由来する絶縁膜２および銅配線３が交互に積み重ねられた構成を有している。さらに、基板１には、下層の配線回路１２および上層の配線回路１３を接続するために、絶縁性樹脂４で穴埋めされたスルーホール５が形成されている。図から理解されるように、配線回路の層間にビルドアップ用の絶縁膜（いわゆる層間絶縁膜）を形成する必要がある。ビルドアップ用の絶縁膜は、上層の配線回路との接続を行うビアホールを除いて、下層の配線回路の全面に形成されている。
【００１９】
ビルドアップ配線基板の製造方法
図１に示されるようなビルドアップ配線基板１０は以下の通りに製造される。
以下の説明は本発明の方法を例示するものであって、限定しようとするものではない。
（１）コア基板の作製
基板にスルーホール５を形成し、その基板の両面およびスルーホールの内壁に配線パターン３を形成し、さらにスルーホールの内部に絶縁性樹脂４を充填することにより、図２（Ａ）に示すように、両面に配線３を有する積層基板（コア基板１）を作製することができる。
【００２０】
（２）絶縁膜の作製
コア基板１の両面に、その全面を覆うようにして本発明の樹脂組成物を被覆する。被覆法としては、スクリーン印刷法、カーテンコート法、ロールコート法、スピンコート法等の方法で塗布しそして乾燥させて、所望の厚さ、例えば、３０〜６０μｍの皮膜を形成させる。次いで、皮膜を硬化させ、そして耐熱性を向上させるために、皮膜を適当な温度、例えば、１００〜２００℃で加熱する。その後に形成する上層の配線回路と接続すべき箇所、即ち、ビアホール部分に適当な露光量のレーザー光（炭酸ガスレーザ、エキシマレーザ、ＹＡＧレーザ等）を照射する。これにより、図２（Ｂ）に示すように、ビアホール６を備えた絶縁膜２が形成される。
【００２１】
（３）導体（銅）メッキ
続いて、上記の絶縁膜２の上に配線前駆体としての導体を全面に被覆する。この導体被覆工程は、例えば、無電解メッキ、電解メッキ等の常用のメッキ法を用いて行うことができる。また、このメッキ工程の前に、コア基板１を膨潤液、粗化液および中和液に順次浸漬し、絶縁膜２の表面に適当な微細凹凸を形成することが望ましい。絶縁膜２と導体メッキとの密着性がさらに向上するからである。
この工程により、図２（Ｃ）に示すように、コア基板１の両面に形成された絶縁膜２の表面に、導体メッキ層７が全面に形成される。
【００２２】
（４）配線の形成
導体メッキ層を所望の配線パターンに従ってエッチングする。このパターニング工程は、常用のエッチング法に従って行うことができる。これにより、図４（Ｄ）に示すように、導体配線３を備えたコア基板１を形成することができる。さらに、図示していないが、絶縁膜２の形成から導体配線３の形成までの一連の工程を繰り返すことにより、図１に示したような多層のビルドアップ配線基板１０が得られる。
【００２３】
次に、本発明をさらに具体的に説明するために実施例を示すとともに、本発明の効果を比較例との対比において示す。なお、本発明がこれらの実施例に限定されるものでないということは言うまでもない。
【００２４】
実施例１
シクロヘキサン骨格の脂環式エポキシ樹脂(EHPE-3150、ダイセル化学）６０重量部、セロキサイド2080（ダイセル化学）４０重量部、フェノールノボラック樹脂(PSM-4300 、群栄化学）６０重量部、２−メチル−４−エチル−イミダゾール（四国化成）４重量部、シリカ粉末３０重量部および６−（４−ビニルベンジル−ｎ−プロピル）アミノ−１，３，５−トリアジン−２，４−ジチオール５重量部をジオキサン１５０重量部中に溶解し、塗液を調製した。
調製した組成物を、銅箔基板上に５０μｍの厚さ（乾燥後の膜厚）にドクターブレード法により塗布し、次いで、１２０℃で２０分間加熱して乾燥し、さらに１７０℃で６０分間加熱して硬化させた後に室温まで放冷した。
次いで、このようにして得られた絶縁膜を有する基板を、前処理剤（シプレー製、コンディショナー、６５℃、１０分間）、酸化剤（スプレー製、プロモーター、７５℃、１０分間）、中和剤（シプレー製、ニュートライザー、６０℃、１０分間）に順次浸漬した。
次いで、樹脂膜上に無電解銅メッキおよび電解銅メッキをそれぞれ０．５μｍおよび３０μｍの厚さで施し、合計で約３０μｍの厚さの導体層を形成した。
樹脂膜と導体層との密着性を測定するために、上記の通りに得られた導体層のピール強度をＪＩＳの「プリント配線板用銅張積層板試験方法Ｃ６４８１」に準じて測定した。導体層の９０°ピール強度は１．０ｋｇ／ｃｍであった。
【００２５】
比較例１
シクロヘキサン骨格の脂環式エポキシ樹脂(EHPE-3150、ダイセル化学）６０重量部、セロキサイド2080（ダイセル化学）４０重量部、フェノールノボラック樹脂(PSM-4300 、群栄化学）６０重量部、２−メチル−４−エチル−イミダゾール（四国化成）４重量部、シリカ粉末３０重量部をジオキサン１５０重量部中に溶解し、塗液を調製した。
調製した組成物を、実施例１と同様に成膜し、上記の前処理剤、酸化剤および中和剤に順次浸漬した後に、無電解銅メッキおよび電解銅メッキをそれぞれ０．５μｍおよび３０μｍの厚さで施し、合計で約３０μｍの厚さの導体層を樹脂膜上に形成した。
実施例１と同一の試験法により測定して、導体層の９０°ピール強度は０．７５ｋｇ／ｃｍであった。
【００２６】
実施例２
比較例１で作製した塗液を銅箔基板上に乾燥後の膜厚が５０μｍとなるように塗布し、１００℃で１０分間乾燥した。次いで、実施例１で作製した塗液を乾燥後の膜厚が２μｍとなるように塗布し、１２０℃で２０分間加熱乾燥し、１７０℃で６０分間加熱して硬化させた後に室温まで放冷した。
この上に実施例１と同様にして３０μｍの厚さの導体層を形成し、導体層の９０°ピール強度を測定したところ、１．０ｋｇ／ｃｍであった。この結果は、銅導体層と接触する絶縁膜の表面層のみに本発明の樹脂組成物を用いたときにも、樹脂膜と導体層との密着性が向上することを示す。
【００２７】
実施例３
シクロヘキサン骨格の脂環式エポキシ樹脂(EHPE-3150、ダイセル化学）６０重量部、セロキサイド2080（ダイセル化学）４０重量部、フェノールノボラック樹脂(PSM-4300 、群栄化学）６０重量部、２−メチル−４−エチル−イミダゾール（四国化成）４重量部、シリカ粉末３０重量部、ビスフェノールＡ−ジエポキシ−アクリル酸付加物（大阪有機化学）３０重量部、Ｎ−フェニルグリシン０．６重量部および６−（４−ビニルベンジル−ｎ−プロピル）アミノ−１，３，５−トリアジン−２，４−ジチオール５重量部をジオキサン１８０重量部中に溶解し、塗液を調製した。
調製した組成物を、銅箔基板上に５０μｍの厚さ（乾燥後の膜厚）にドクターブレード法により塗布し、次いで、１２０℃で２０分間加熱して乾燥し、さらに１７０℃で６０分間加熱して硬化させた後に室温まで放冷した。
次いで、このようにして得られた絶縁膜を有する基板を、前処理剤（シプレー製、コンディショナー、６５℃、１０分間）、酸化剤（スプレー製、プロモーター、７５℃、１０分間）、中和剤（シプレー製、ニュートライザー、６０℃、１０分間）に順次浸漬した。
次いで、樹脂膜上に無電解銅メッキおよび電解銅メッキをそれぞれ０．５μｍおよび３０μｍの厚さで施し、合計で約３０μｍの厚さの導体層を形成した。
実施例１と同様に、導体層の９０°ピール強度を測定したところ、１．１ｋｇ／ｃｍであった。
【００２８】
本発明の樹脂組成物を使用することにより、樹脂と銅導体との密着性に優れたビルドアップ配線基板を提供することができる。
【図面の簡単な説明】
【図１】ビルドアップ配線基板の断面図を示す。
【図２】ビルドアップ配線基板の製造工程を示す断面図である。
【符号の説明】
１…コア基板
２…絶縁膜
３…配線パターン
４…絶縁性樹脂
５…スルーホール
６…ビアホール
７…導体メッキ層
１０…ビルドアップ配線基板
１２…配線回路
１３…配線回路[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition for producing a build-up wiring board, a build-up wiring board using the composition, and a method for producing the same.
[0002]
[Prior art]
Conventionally, a printed circuit board is generally used in order to incorporate an electronic component into an electronic device in a compact manner. In recent years, along with demands for downsizing, higher performance, and lower prices for electronic devices, miniaturization of printed wiring boards, multilayering, and high-density mounting of electronic components have rapidly progressed, and builds on printed wiring boards Studies on wiring boards having an up-multilayer wiring structure are being actively conducted. This wiring board includes a plurality of conductor wirings stacked on the board, and an insulating film (so-called interlayer insulating film) exists between the conductor wirings. In order to establish conduction between such a plurality of wirings, fine holes called via holes are formed in the insulating film. The via hole can be formed by a photolithography technique using a photosensitive resin, or can be formed by irradiating a laser.
[0003]
In general, a printed wiring board (build-up wiring board) having a build-up multilayer wiring structure is manufactured according to the following procedure. First, a double-sided wiring board having a wiring pattern and a through hole filled therein is prepared as a core substrate. An insulating film with via holes is formed by applying a photosensitive resin on both sides of the core substrate, exposing and developing, or by irradiating with a laser after forming a resin layer for the insulating film. To do. Next, a conductor plating layer is formed on the entire surface of the insulating film formed on both surfaces of the core substrate using a conventional plating method such as electroless plating or electroplating. Furthermore, a new conductor wiring is formed on the core substrate by etching the conductor plating layer according to a desired wiring pattern. Thereafter, if necessary, a series of steps from the formation of the insulating film to the formation of the conductor wiring is repeated, thereby obtaining a printed wiring board having a multilayer wiring structure with a high degree of circuit integration.
[0004]
There is a problem that the adhesiveness is low if the insulating resin layer of the build-up wiring board and the copper wiring as a conductor are left as they are. For this reason, as a conventional technique, an insulating resin is immersed in a swelling liquid, a roughening liquid, and a neutralizing liquid in order to form fine irregularities on the surface of the resin, and then electroless copper plating and electrolytic copper plating are sequentially formed thereon. Adhesion is obtained by giving an anchor effect by forming a copper film. However, the adhesion between the copper and the resin obtained by this physical anchor effect is less than 1 kg / cm in the 90 ° peel test according to JIS-C-6481 in the case of many resins. It is lower than the adhesion obtained between the insulating resin and the copper film. In general, in the industry, an adhesion of 1 kg / cm or more is required for a build-up wiring board.
[0005]
As a method for improving the adhesion between the copper wiring and the insulating resin, there is a chemical adhesion between copper and a constituent component in the resin in addition to the above-described physical anchor effect. As such components, various organic compounds have been proposed as known techniques at the molecular level. Among them, there is a report example that a heterocyclic compound having two or more thiol groups improves adhesion to copper. JP-A-5-158240 proposes compounds such as 1,3,5-trimercaptopyridine and 2,5-dimercapto-1,3,4-thiadiazole as compounds having excellent adhesion to copper. Yes. However, even though these compounds have excellent adhesion to copper, they have low adhesion to the resin when blended in the insulating resin, resulting in improved adhesion between the insulating resin film and the copper wiring. I can't.
[0006]
On the other hand, in JP-A-5-65466, 6-dibutylamino-1,3,5-triazine-2,4-dithiol, 6-phenyl is used as a copper damage prevention agent for preventing contamination due to copper migration. The use of compounds such as amino-1,3,5-triazine-2,4-dithiol has been proposed. The triazine thiol compound prevents migration of copper by chemically bonding to the metal by the action of forming a chelate with the metal. However, even if such a compound is used, high adhesion between the copper wiring and the insulating resin film cannot be obtained due to low adhesion between the compound and the resin.
[0007]
[Problems to be solved by the invention]
As described above, in the build-up wiring board, there is no insulating resin composition capable of obtaining sufficient adhesion between the insulating resin and the copper wiring. The present invention provides an insulating resin composition capable of obtaining high adhesion between an insulating resin and a copper wiring in a build-up wiring board, and also provides a build-up wiring board having high adhesion and a method for manufacturing the same. To do.
[0008]
[Means for Solving the Problems]
According to the present invention, there is provided a resin composition comprising an epoxy resin, an epoxy curing agent, and a triazine dithiol compound having an unsaturated ethylene group.
Further, an epoxy resin, an epoxy curing agent, a triazine dithiol compound having an unsaturated ethylene group, a vinyl or acrylic compound having an unsaturated ethylene group, and a polymerization initiator for initiating polymerization of the unsaturated ethylene group A composition is provided.
Further, in the above composition, a composition is provided wherein the epoxy curing agent is a phenol novolac type epoxy curing agent or acid anhydride.
Furthermore, the said composition WHEREIN: The resin composition whose triazine dithiol compound which has an unsaturated ethylene group is 0.01-5 weight part with respect to 100 weight part of epoxy resins is provided.
Furthermore, a substrate having a wiring pattern, an insulating resin layer obtained from the resin composition on the substrate, and a build-up wiring substrate having a copper wiring pattern on the insulating resin layer are provided.
Furthermore, applying a varnish of the above composition on a substrate having a wiring pattern, drying and curing the varnish to form an insulating resin layer, and forming the wiring pattern and the wiring pattern on the insulating resin layer. Forming a via hole for conducting electrical connection with the copper wiring layer, forming a copper wiring layer on the insulating resin layer, and etching the copper wiring layer with a desired pattern to form a wiring pattern A method for manufacturing a build-up wiring board is provided.
Furthermore, there is provided a method for manufacturing a build-up wiring board, in which the copper wiring layer is formed by subjecting the insulating resin layer to a roughening treatment, followed by electroless plating of copper and then electrolytic plating.
[0009]
The resin composition of the present invention contains a triazine dithiol compound having an unsaturated ethylene group (hereinafter, also simply referred to as “triazine dithiol compound”). Such a resin composition has high adhesion to copper wiring. This high adhesion is considered to be due to the dithiol group in this compound forming a chelate with copper and the unsaturated ethylene group being incorporated into the resin structure by reacting with the resin component. As the triazine dithiol compound having an unsaturated ethylene group, the following formula:
[Chemical 1]

[0011]
(Wherein R is H or C ₁ -C ₅ alkyl). Specifically, 6- (4-vinylbenzyl-n-propyl) amino-1,3,5-triazine-2,4-dithiol and 6- (4-vinyl, where R is n-propyl and hydrogen, respectively. Benzyl) amino-1,3,5-triazine-2,4-dithiol. Such a compound is used in an amount sufficient to improve the adhesion between the copper wiring and the resin layer, and is usually 0.01 to 5 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin. Used in parts quantity. If the amount is larger than this, the cost increases and the physical properties of the resin may be lowered.
[0012]
The composition of the present invention contains an epoxy resin suitable as an insulating resin for a build-up wiring board. The epoxy resin can provide a composition that can exhibit excellent crack resistance, high flexibility, and excellent reliability when the core substrate is bent or a component is mounted on the substrate. The epoxy resin is preferably an epoxy having an alicyclic structure. Particularly suitable cycloaliphatic epoxies are polyfunctional epoxy resins having a cyclohexane skeleton such as EHPE-3150 (Daicel Chemical), ERL-4299 (Union Carbide), Celoxide 2021 (Daicel Chemical), CY-175 (Ciba Geigy), An alicyclic bifunctional epoxy such as Celoxide 2080 (Daicel Chemical), an alicyclic trifunctional epoxy such as Epolide GT300, an alicyclic tetrafunctional epoxy such as Epolide GT400, and a mixture thereof.
[0013]
Examples of epoxy curing agents include phenol novolac resins and acid anhydrides. Phenol novolac resins include PSM-4300 manufactured by Gunei Chemical Co., and acid anhydrides include Ricacid HH and Ricacid TMEG sold by Shin Nippon Rika Co., Ltd. It is desirable that the epoxy curing agent is usually contained in a compounding ratio such that the active hydrogen equivalent of the epoxy curing agent is 0.8 to 1.1 equivalents with respect to 1 equivalent of the epoxy group contained in the epoxy resin component. This is because when such an amount is used, the physical properties of the epoxy cured product are improved.
[0014]
The composition of the present invention may comprise a vinyl or acrylic compound having an unsaturated ethylene group. Such a compound has a function of causing a polymerization reaction with the ethylene group of the triazine dithiol used in the present invention and incorporating the triazine thiol compound into the insulating resin structure. Such compounds include diphenic acid ester diacrylate, bisphenol A diepoxyacrylic acid adduct, bisphenol F diepoxyacrylic acid adduct, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate. And other polyfunctional acrylates and methacrylates corresponding to these polyfunctional acrylates, methyl acrylate, methyl methacrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, propyl methacrylate, n methacrylate -Monomers or oligomers such as butyl, isobutyl methacrylate or diallyl phthalate. When such a compound is used, it is contained in an amount that does not impair the physical properties of the resulting cured epoxy product, and is usually contained in an amount of 30 parts by weight or less per 100 parts by weight of the epoxy resin.
[0015]
The composition of the present invention may further contain a polymerization initiator for initiating polymerization of unsaturated ethylene groups. As polymerization initiators, α-aminoalkylphenone or derivatives thereof, benzoin ether or derivatives thereof, ketal or derivatives thereof, acetophenone or derivatives thereof, benzophenone or derivatives thereof, thioxanthone or derivatives thereof, organic peroxide, N-phenylglycine, etc. The following thermal polymerization initiators may be mentioned. The polymerization initiator is usually used in an amount of 1 to 5% by weight based on the total amount of the triazine dithiol compound and the vinyl or acrylic compound.
[0016]
The composition of the present invention is generally applied and impregnated on a substrate as a varnish-like composition. In order to obtain a varnish-like composition, the composition of the present invention may contain a suitable solvent. Examples of the solvent include ethers such as ethylene glycol monoether, ketones such as cyclohexane, esters such as acetate, and organic solvents such as toluene and xylene. Furthermore, for the purpose of accelerating the curing of the epoxy compound, a curing accelerator such as triphenylphosphine or imidazole may be added. Such a curing accelerator can be usually added in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin. In addition, various additives such as extender pigments such as silica, alumina and aerosil, colored pigments such as phthalocyanine, antifoaming agents composed of silicone and fluorine compounds, leveling agents and antioxidants are added as necessary. can do.
[0017]
Furthermore, when flame retardancy is required, a small amount of phosphorus-based flame retardant can be added. Such a phosphorus flame retardant coexists with a phosphorus component and a nitrogen component, so that the nitrogen compound promotes decomposition and thermal condensation of the phosphorus component to produce polyphosphoric acid, and the polyphosphoric acid is coated on the surface of the epoxy resin. This produces a heat insulation effect and an oxygen blocking effect, and as a result, attempts to prevent combustion. Examples of the phosphorus component that may be used in the composition of the present invention include phosphate esters such as trimethyl phosphate and triphenyl phosphate, but are not particularly limited thereto. Further, if the phosphorus component is present in the composition of the present invention in an amount of 10% by weight or more, it is not preferable because it easily absorbs water.
[0018]
Next, FIG. 1 shows a cross-sectional view of the build-up wiring board 10. The build-up wiring board 10 has multilayered wiring circuit layers 12 and 13 on both surfaces of the core substrate 1, and the wiring circuit layers 12 and 13 are respectively insulated from the resin composition of the present invention. The film 2 and the copper wiring 3 are alternately stacked. Furthermore, a through hole 5 filled with an insulating resin 4 is formed in the substrate 1 in order to connect the lower wiring circuit 12 and the upper wiring circuit 13. As understood from the drawing, it is necessary to form a build-up insulating film (so-called interlayer insulating film) between the layers of the wiring circuit. The build-up insulating film is formed on the entire surface of the lower wiring circuit except for the via hole for connection to the upper wiring circuit.
[0019]
Manufacturing method of build-up wiring board The build-up wiring board 10 as shown in FIG. 1 is manufactured as follows.
The following description is illustrative of the method of the present invention and is not intended to be limiting.
(1) Fabrication of a core substrate Through holes 5 are formed in a substrate, wiring patterns 3 are formed on both surfaces of the substrate and the inner walls of the through holes, and an insulating resin 4 is filled in the through holes. As shown in FIG. 2A, a laminated substrate (core substrate 1) having wirings 3 on both surfaces can be manufactured.
[0020]
(2) Production of Insulating Film The resin composition of the present invention is coated on both surfaces of the core substrate 1 so as to cover the entire surface. As a coating method, it is applied by a method such as a screen printing method, a curtain coating method, a roll coating method, or a spin coating method and dried to form a film having a desired thickness, for example, 30 to 60 μm. The film is then heated at a suitable temperature, for example, 100-200 ° C., in order to cure the film and improve heat resistance. Thereafter, a portion to be connected to the upper wiring circuit to be formed, that is, a via hole portion is irradiated with an appropriate exposure amount of laser light (a carbon dioxide laser, an excimer laser, a YAG laser, or the like). Thereby, as shown in FIG. 2B, the insulating film 2 including the via hole 6 is formed.
[0021]
(3) Conductor (copper) plating Subsequently, a conductor as a wiring precursor is coated on the entire surface of the insulating film 2. This conductor covering step can be performed using a conventional plating method such as electroless plating or electrolytic plating. Further, before this plating step, it is desirable to immerse the core substrate 1 in a swelling liquid, a roughening liquid and a neutralizing liquid in order to form appropriate fine irregularities on the surface of the insulating film 2. This is because the adhesion between the insulating film 2 and the conductor plating is further improved.
By this step, as shown in FIG. 2C, the conductor plating layer 7 is formed on the entire surface of the insulating film 2 formed on both surfaces of the core substrate 1.
[0022]
(4) Formation of wiring The conductor plating layer is etched according to a desired wiring pattern. This patterning step can be performed according to a conventional etching method. Thereby, as shown in FIG. 4D, the core substrate 1 including the conductor wiring 3 can be formed. Furthermore, although not shown in the drawing, a multilayer build-up wiring board 10 as shown in FIG. 1 is obtained by repeating a series of steps from the formation of the insulating film 2 to the formation of the conductor wiring 3.
[0023]
Next, in order to describe the present invention more specifically, examples are shown, and the effects of the present invention are shown in comparison with comparative examples. Needless to say, the present invention is not limited to these examples.
[0024]
Example 1
60 parts by weight of cyclohexane alicyclic epoxy resin (EHPE-3150, Daicel Chemical), 40 parts by weight of Celoxide 2080 (Daicel Chemical), 60 parts by weight of phenol novolac resin (PSM-4300, Gunei Chemical), 2-methyl- 4 parts by weight of 4-ethyl-imidazole (Shikoku Kasei), 30 parts by weight of silica powder and 5 parts by weight of 6- (4-vinylbenzyl-n-propyl) amino-1,3,5-triazine-2,4-dithiol Dissolved in 150 parts by weight of dioxane to prepare a coating solution.
The prepared composition was applied on a copper foil substrate to a thickness of 50 μm (film thickness after drying) by the doctor blade method, then dried by heating at 120 ° C. for 20 minutes, and further heated at 170 ° C. for 60 minutes. And then allowed to cool to room temperature.
Next, the substrate having the insulating film thus obtained was subjected to a pretreatment agent (manufactured by Shipley, conditioner, 65 ° C., 10 minutes), oxidizing agent (manufactured by spray, promoter, 75 ° C., 10 minutes), neutralizing agent. (Shipley, Neutriser, 60 ° C., 10 minutes) was sequentially immersed.
Next, electroless copper plating and electrolytic copper plating were applied on the resin film to a thickness of 0.5 μm and 30 μm, respectively, to form a conductor layer having a total thickness of about 30 μm.
In order to measure the adhesion between the resin film and the conductor layer, the peel strength of the conductor layer obtained as described above was measured in accordance with JIS "Copper Clad Laminate Test Method for Printed Wiring Board C6481". The 90 ° peel strength of the conductor layer was 1.0 kg / cm.
[0025]
Comparative Example 1
60 parts by weight of cyclohexane alicyclic epoxy resin (EHPE-3150, Daicel Chemical), 40 parts by weight of Celoxide 2080 (Daicel Chemical), 60 parts by weight of phenol novolac resin (PSM-4300, Gunei Chemical), 2-methyl- A coating solution was prepared by dissolving 4 parts by weight of 4-ethyl-imidazole (Shikoku Kasei) and 30 parts by weight of silica powder in 150 parts by weight of dioxane.
The prepared composition was formed into a film in the same manner as in Example 1 and immersed in the above pretreatment agent, oxidizing agent and neutralizing agent in turn, and then electroless copper plating and electrolytic copper plating were applied to 0.5 μm and 30 μm, respectively. A conductive layer having a total thickness of about 30 μm was formed on the resin film.
As measured by the same test method as in Example 1, the 90 ° peel strength of the conductor layer was 0.75 kg / cm.
[0026]
Example 2
The coating solution prepared in Comparative Example 1 was applied on a copper foil substrate so that the film thickness after drying was 50 μm, and dried at 100 ° C. for 10 minutes. Next, the coating liquid prepared in Example 1 was applied so that the film thickness after drying was 2 μm, dried by heating at 120 ° C. for 20 minutes, cured by heating at 170 ° C. for 60 minutes, and then allowed to cool to room temperature. did.
A conductor layer having a thickness of 30 μm was formed thereon in the same manner as in Example 1, and the 90 ° peel strength of the conductor layer was measured and found to be 1.0 kg / cm. This result shows that the adhesion between the resin film and the conductor layer is improved even when the resin composition of the present invention is used only for the surface layer of the insulating film in contact with the copper conductor layer.
[0027]
Example 3
60 parts by weight of cyclohexane alicyclic epoxy resin (EHPE-3150, Daicel Chemical), 40 parts by weight of Celoxide 2080 (Daicel Chemical), 60 parts by weight of phenol novolac resin (PSM-4300, Gunei Chemical), 2-methyl- 4-ethyl-imidazole (Shikoku Kasei) 4 parts by weight, silica powder 30 parts by weight, bisphenol A-diepoxy-acrylic acid adduct (Osaka Organic Chemical) 30 parts by weight, N-phenylglycine 0.6 part by weight and 6- ( 4-vinylbenzyl-n-propyl) amino-1,3,5-triazine-2,4-dithiol 5 parts by weight was dissolved in 180 parts by weight of dioxane to prepare a coating solution.
The prepared composition was applied on a copper foil substrate to a thickness of 50 μm (film thickness after drying) by the doctor blade method, then dried by heating at 120 ° C. for 20 minutes, and further heated at 170 ° C. for 60 minutes. And then allowed to cool to room temperature.
Next, the substrate having the insulating film thus obtained was subjected to a pretreatment agent (manufactured by Shipley, conditioner, 65 ° C., 10 minutes), oxidizing agent (manufactured by spray, promoter, 75 ° C., 10 minutes), neutralizing agent. (Shipley, Neutriser, 60 ° C., 10 minutes) was sequentially immersed.
Next, electroless copper plating and electrolytic copper plating were applied on the resin film to a thickness of 0.5 μm and 30 μm, respectively, to form a conductor layer having a total thickness of about 30 μm.
As with Example 1, the 90 ° peel strength of the conductor layer was measured and found to be 1.1 kg / cm.
[0028]
By using the resin composition of this invention, the buildup wiring board excellent in the adhesiveness of resin and a copper conductor can be provided.
[Brief description of the drawings]
FIG. 1 shows a cross-sectional view of a build-up wiring board.
FIG. 2 is a cross-sectional view showing a manufacturing process of a build-up wiring board.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Core substrate 2 ... Insulating film 3 ... Wiring pattern 4 ... Insulating resin 5 ... Through hole 6 ... Via hole 7 ... Conductor plating layer 10 ... Build-up wiring board 12 ... Wiring circuit 13 ... Wiring circuit

Claims (4)

Epoxy resin,
An epoxy curing agent,
A triazine dithiol compound having an unsaturated ethylene group represented by the following formula:

(Wherein, R is hydrogen or a C ₁ -C ₅ alkyl group). A substrate having a wiring pattern;
An epoxy resin, an epoxy curing agent, and a triazine dithiol compound having an unsaturated ethylene group, represented by the following formula, disposed above the substrate:

(Wherein, R is hydrogen or C ₁ -C ₅ alkyl group) and an insulating resin layer formed from a resin composition comprising,
A build-up wiring board comprising: a copper wiring pattern disposed above the insulating resin layer. On the substrate having the first wiring pattern, an epoxy resin, an epoxy curing agent, and a triazine dithiol compound having an unsaturated ethylene group represented by the following formula:

(Wherein, R is hydrogen or C ₁ -C ₅ alkyl group) a step of applying a varnish of the resin composition comprising a,
Drying and curing the varnish to form an insulating resin layer;
Forming a via hole in the insulating resin layer to expose the first wiring pattern;
Forming a copper wiring layer covering the via hole above the insulating resin layer;
Etching the copper wiring layer with a desired pattern to obtain a second wiring pattern that is electrically connected to the first wiring pattern. 4. The build according to claim 3 , wherein the step of forming the copper wiring layer includes a step of electroless plating copper and then electrolytically plating copper after roughening the insulating resin layer. Manufacturing method of up-wiring board.

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