JP2013035956A - Primer layer for plating process, laminate with primer layer for plating process, production method thereof, multilayer wiring board with primer layer for plating process, and production method thereof - Google Patents
Primer layer for plating process, laminate with primer layer for plating process, production method thereof, multilayer wiring board with primer layer for plating process, and production method thereof Download PDFInfo
- Publication number
- JP2013035956A JP2013035956A JP2011173855A JP2011173855A JP2013035956A JP 2013035956 A JP2013035956 A JP 2013035956A JP 2011173855 A JP2011173855 A JP 2011173855A JP 2011173855 A JP2011173855 A JP 2011173855A JP 2013035956 A JP2013035956 A JP 2013035956A
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- JP
- Japan
- Prior art keywords
- primer layer
- plating process
- epoxy resin
- plating
- 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.)
- Granted
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- 238000007747 plating Methods 0.000 title claims abstract description 81
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- 239000004744 fabric Substances 0.000 claims abstract description 38
- 239000011256 inorganic filler Substances 0.000 claims abstract description 32
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 32
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- 239000000463 material Substances 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 14
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- 239000011889 copper foil Substances 0.000 description 16
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
本発明は、配線板を製造する際にガラスクロス入り基材に用いられるめっきプロセス用プライマー層、それを用いた積層板及びその製造方法、多層配線板及びその製造方法に関する。 The present invention relates to a primer layer for a plating process used for a substrate with glass cloth when a wiring board is manufactured, a laminated board using the same, a manufacturing method thereof, a multilayer wiring board and a manufacturing method thereof.
近年、電子機器の小型化、軽量化、多機能化が一段と進み、これに伴い、ＬＳＩやチップ部品等の高集積化が進み、その形態も多ピン化、小型化へと急速に変化している。このため、多層配線板は、電子部品の実装密度を向上させるために微細配線化の開発が進められている。これらの要求に合致する多層配線板として、ガラスクロスを含まない絶縁樹脂をプリプレグの代わりに絶縁層として用い、ビアホールで接続しながら配線層を形成するビルドアップ方式の多層配線板が、軽量化や小型化、微細化に適した手法として多く用いられるようになった。 In recent years, electronic devices have become increasingly smaller, lighter, and more functional, and as a result, LSIs and chip components have become more highly integrated, and their forms have rapidly changed to multi-pin and miniaturized. Yes. For this reason, in order to improve the mounting density of electronic components, development of micro wiring has been advanced for multilayer wiring boards. As a multilayer wiring board that meets these requirements, a build-up multilayer wiring board that uses an insulating resin that does not contain glass cloth as an insulating layer instead of a prepreg and forms a wiring layer while being connected by via holes, It has been widely used as a method suitable for miniaturization and miniaturization.
このようなビルドアップ方式の多層配線板は、絶縁樹脂フィルムを内層回路板にラミネートし、加熱により硬化させた後、レーザ加工によってビアホールを形成する。そして、アルカリ過マンガン酸処理等によって粗化処理とスミア処理とを行って無電解銅めっきを行い、第二の回路と層間接続可能とするビアホールを形成する（例えば、特許文献１〜３参照）。 In such a build-up type multilayer wiring board, an insulating resin film is laminated on an inner circuit board, cured by heating, and then a via hole is formed by laser processing. And a roughening process and a smear process are performed by an alkali permanganate process etc., electroless copper plating is performed, and the via hole which enables interlayer connection with a 2nd circuit is formed (for example, refer patent documents 1-3) .
一方、多層配線板は、電子部品の薄型化に伴い、使用される配線板の厚みが薄くなりつつあるが、その結果ガラスクロスを含まない絶縁樹脂をプリプレグの代わりに絶縁層として用いた場合に、実装時のそりが大きくなり、接続信頼性が低下する傾向がある。そこで、ガラスクロスを含むプリプレグが再度見直されてきている。しかし、ガラスクロス入り基材においても、ビルドアップ方式で用いられるレーザ加工によるビアホール形成や、セミアディティブ工法による高密度配線が必要となっている。 On the other hand, multilayer wiring boards are becoming thinner as electronic components become thinner, and as a result, when insulating resin that does not contain glass cloth is used as an insulating layer instead of prepreg The warpage during mounting tends to increase and the connection reliability tends to decrease. Therefore, prepregs containing glass cloth have been reviewed again. However, a glass cloth-containing base material also requires via hole formation by laser processing used in a build-up method and high-density wiring by a semi-additive method.
このような状況において、従来のような表面を粗化して得られる大きな粗化形状（アンカー効果）を利用して無電解銅めっきとの接着力を確保する方法では、１０μｍ以下の微細な回路はショート不良やオープン不良が発生し、歩留り良く製造することができない。一方で、粗化形状を小さくすると、無電解銅めっきとの接着力が低下し、ラインが剥離する等の不良が発生する。
これらの理由から、微細な粗化形状でありながら無電解銅めっきと高接着力を示す、配線板材料が求められている。
In such a situation, a fine circuit having a size of 10 μm or less is obtained by a method of securing an adhesive force with electroless copper plating using a large roughened shape (anchor effect) obtained by roughening the surface as in the prior art. Short circuit defects and open defects occur, making it impossible to manufacture with good yield. On the other hand, when the roughened shape is reduced, the adhesive force with the electroless copper plating is reduced, and defects such as line peeling occur.
For these reasons, there is a need for a wiring board material that exhibits electroless copper plating and high adhesive strength while having a fine roughened shape.
ところで、ガラスクロス入り基材に用いられている樹脂は、そりの観点から低いＣＴＥ（Ｃｏｅｆｆｉｃｉｅｎｔ ｏｆ ｔｈｅｒｍａｌ ｅｘｐａｎｓｉｏｎ：熱膨張率）化が求められているが、このような樹脂系は剛直骨格を有しているため伸びが小さく、めっき銅との接着力は小さい。そこで、無電解めっき層の代わりに極薄銅箔を給電層として用い、セミアディティブ工法により回路形成するＭ−ＳＡＰ（Ｍｏｄｉｆｉｅｄ Ｓｅｍｉ−Ａｄｄｉｔｉｖｅ Ｐｒｏｃｅｓｓ）法が提案されてきた。しかしながら、この方法ではビルドアップ方式における無電解銅めっきと比較して給電層が厚すぎるため、１５μｍ以下の微細な回路形成は困難であった（例えば、特許文献４参照）。 By the way, the resin used for the glass cloth-containing substrate is required to have a low CTE (Coefficient of Thermal Expansion) from the viewpoint of warpage, but such a resin system has a rigid skeleton. Therefore, the elongation is small and the adhesive strength with the plated copper is small. Therefore, an M-SAP (Modified Semi-Additive Process) method has been proposed in which an ultrathin copper foil is used as a power feeding layer instead of the electroless plating layer, and a circuit is formed by a semi-additive method. However, in this method, since the power feeding layer is too thick as compared with the electroless copper plating in the build-up method, it is difficult to form a fine circuit of 15 μm or less (see, for example, Patent Document 4).
本発明者らは、ガラスクロスを含むプリプレグにめっき銅との高接着性を有するプライマー層を設けることにより、高剛性・低熱膨張等の基材の性質を維持したまま、めっき銅との良好な接着性を確保できるめっきプロセス対応の積層板及び多層板を作製可能であることをこれまでに見出した。 The present inventors have provided a primer layer having high adhesion to the plated copper on a prepreg containing a glass cloth, thereby maintaining good properties with the plated copper while maintaining the properties of the substrate such as high rigidity and low thermal expansion. It has been found so far that it is possible to produce a laminated board and a multilayer board compatible with a plating process capable of ensuring adhesion.
しかしながら、プライマー層とガラスクロス入り基材とは、異種材料の組合せであるため、レーザ加工によりプライマー層と界面付近でガラスクロス入り基材の一部がえぐれてしまう問題が生じた。
具体的には、図１に示すように、基板１０上に回路となる導電層１２が形成されたてなり、その上にガラスクロス入り基材１４であるプリプレグとプライマー層１６とが順次形成された積層板２０にレーザ加工を施すと、ガラスクロス入り基材１４の上部でプライマー層１６との界面付近がえぐれてしまい、プライマー層の一部がひさしのように突出してしまうアンダーカット部１８が発生してしまうといった問題が生じた。
このようなアンダーカットが生じると、無電解めっき時にアンダーカット部分にボイドができやすく、電気的な信頼性を低下させるという問題が生じる。
However, since the primer layer and the glass cloth-containing base material are a combination of different materials, there has been a problem in that a part of the glass cloth-containing base material is removed near the interface with the primer layer by laser processing.
Specifically, as shown in FIG. 1, a
When such an undercut occurs, voids are easily formed in the undercut portion during electroless plating, resulting in a problem that electrical reliability is lowered.
以上から、本発明は、粗化処理後の表面粗さが小さく、かつめっき銅との良好な接着性を確保しつつ、レーザ加工の際にアンダーカットが生じない、めっきプロセス用プライマー層付き多層配線板を製造することが可能な、プライマー層及び当該プライマー層を有するめっきプロセス用プライマー層付き積層板、並びにめっきプロセス用プライマー層付き多層配線板を提供することを目的とする。また、当該めっきプロセス用プライマー層付き積層板の製造方法、めっきプロセス用プライマー層付き多層配線板の製造方法を提供することを目的とする。 From the above, the present invention is a multilayer with a primer layer for a plating process, in which the surface roughness after the roughening treatment is small and undercut does not occur during laser processing while ensuring good adhesion with the plated copper. An object of the present invention is to provide a primer layer capable of producing a wiring board, a laminate with a primer layer for plating process having the primer layer, and a multilayer wiring board with a primer layer for plating process. Moreover, it aims at providing the manufacturing method of the said laminated board with a primer layer for plating processes, and the manufacturing method of the multilayer wiring board with a primer layer for plating processes.
本発明者らはこのような問題を解決するために研究を進めた結果、プライマー層とガラスクロス入り基材と間でのレーザ加工性の違いが生じる原因は、ガラスクロス入り基材は無機充填材を高充填していることにより、プライマー層と比較して熱伝導率が高く、レーザのエネルギーが効率良く伝播してしまうためであると推測した。プライマー層とガラスクロス入り基材とのレーザ加工性を同等にするためには、プライマー層にも無機充填材を含有することが有効であると考えられるが、プライマー層は厚さ１０μｍ以下の薄い層であることや、粗化後の表面粗さの観点から、ガラスクロス入り基材に用いられるような粒径の大きな無機充填材は好ましくないと考えた。そこで、比表面積が２０ｍ2／ｇ以上の無機充填材を所定量用いれば、粗化処理後の表面粗さが小さく、かつめっき銅との良好な接着性を確保しつつ、レーザ加工性が向上することが分かり、本発明に想到した。すなわち本発明は、下記の通りである。 As a result of the inventors conducting research to solve such problems, the cause of the difference in laser processability between the primer layer and the glass cloth-containing base material is that the glass cloth-containing base material is inorganicly filled. It was presumed that due to the high filling of the material, the thermal conductivity was higher than that of the primer layer, and the laser energy propagated efficiently. In order to equalize the laser processability of the primer layer and the glass cloth-containing base material, it is considered that the primer layer also contains an inorganic filler, but the primer layer is thin with a thickness of 10 μm or less. From the viewpoint of the layer and the surface roughness after roughening, it was considered that an inorganic filler having a large particle size used for a glass cloth-containing substrate was not preferable. Therefore, if a predetermined amount of an inorganic filler having a specific surface area of 20 m 2 / g or more is used, the surface roughness after the roughening treatment is small and the laser workability is improved while ensuring good adhesion to the plated copper. As a result, the present invention has been conceived. That is, the present invention is as follows.
［１］ （Ａ）エポキシ樹脂、（Ｂ）エポキシ樹脂硬化剤、（Ｃ）ポリアミド、ポリアミドイミド、ポリイミドからなる群から選ばれる耐熱樹脂、（Ｄ）比表面積が２０ｍ2／ｇ以上の無機充填材を含有し、（Ｄ）無機充填材の含有量が１〜１０質量％であり、ガラスクロス入り基材上に形成される、めっきプロセス用プライマー層。
［２］ 厚みが１〜１０μｍである［１］に記載のめっきプロセス用プライマー層。
［３］ （Ａ）エポキシ樹脂が、多官能エポキシ樹脂である［１］又は［２］に記載のめっきプロセス用プライマー層。
［４］ （Ａ）エポキシ樹脂が、ビフェニルアラルキル型エポキシ樹脂である［１］〜［３］のいずれかに記載のめっきプロセス用プライマー層。
［５］ （Ｂ）エポキシ樹脂硬化剤が、フェノール系硬化剤である［１］〜［４］のいずれかに記載のめっきプロセス用プライマー層。
［６］ （Ｃ）耐熱樹脂であるポリアミドが、ポリブタジエンとの共重合体である［１］〜［５］のいずれかに記載のめっきプロセス用プライマー層。
［７］ （Ａ）エポキシ樹脂、（Ｂ）エポキシ樹脂硬化剤、（Ｃ）耐熱樹脂、及び（Ｄ）無機充填材の合計配合量中の（Ｃ）耐熱樹脂の配合割合が、全質量中の３〜３０質量％である［１］〜［６］のいずれかに記載のめっきプロセス用プライマー層。
［８］ （Ｄ）無機充填材が、ヒュームドシリカ及び／又はコロイダルシリカである［１］〜［７］のいずれかに記載のめっきプロセス用プライマー層。
［９］ （Ｄ）無機充填材が、表面処理を施されているシリカフィラーである［１］〜［８］のいずれかに記載のめっきプロセス用プライマー層。
［１０］ 支持体を有する［１］〜［９］いずれかに記載のめっきプロセス用プライマー層。
[1] (A) Epoxy resin, (B) Epoxy resin curing agent, (C) Heat-resistant resin selected from the group consisting of polyamide, polyamideimide and polyimide, (D) Inorganic filler having a specific surface area of 20 m 2 / g or more (D) The primer layer for a plating process, wherein the content of the inorganic filler is 1 to 10% by mass, and is formed on a glass cloth-containing substrate.
[2] The primer layer for a plating process according to [1], which has a thickness of 1 to 10 μm.
[3] The primer layer for a plating process according to [1] or [2], wherein (A) the epoxy resin is a polyfunctional epoxy resin.
[4] The primer layer for a plating process according to any one of [1] to [3], wherein (A) the epoxy resin is a biphenyl aralkyl type epoxy resin.
[5] The primer layer for a plating process according to any one of [1] to [4], wherein the (B) epoxy resin curing agent is a phenol-based curing agent.
[6] The primer layer for a plating process according to any one of [1] to [5], wherein the polyamide (C) which is a heat resistant resin is a copolymer with polybutadiene.
[7] (A) The epoxy resin, (B) the epoxy resin curing agent, (C) the heat resistant resin, and (D) the blending ratio of the heat resistant resin in the total blending amount of the inorganic filler is in the total mass. The primer layer for a plating process according to any one of [1] to [6], which is 3 to 30% by mass.
[8] The primer layer for a plating process according to any one of [1] to [7], wherein (D) the inorganic filler is fumed silica and / or colloidal silica.
[9] (D) The primer layer for a plating process according to any one of [1] to [8], wherein the inorganic filler is a silica filler subjected to a surface treatment.
[10] The primer layer for a plating process according to any one of [1] to [9], which has a support.
［１１］ ガラスクロス入り基材の片面又は両面に、［１］〜［９］のいずれかに記載のめっきプロセス用プライマー層が設けられているめっきプロセス用プライマー層用付き積層板。
［１２］ ガラスクロス入り基材の両面又は片面に、［１０］に記載のめっきプロセス用プライマー層を重ね、さらに鏡板を重ねて加熱及び加圧する、めっきプロセス用プライマー層付き配線板用積層板の製造方法。
[11] A laminate with a primer layer for a plating process, wherein the primer layer for a plating process according to any one of [1] to [9] is provided on one side or both sides of a substrate with glass cloth.
[12] A laminate for a wiring board with a primer layer for a plating process, wherein the primer layer for a plating process according to [10] is overlaid on both sides or one side of a substrate with glass cloth, and further a mirror plate is overlaid and heated and pressed. Production method.
［１３］ 回路加工した配線板の両面又は片面に、ガラスクロス入り基材と、［１］〜［９］のいずれかに記載のめっきプロセス用プライマー層とがこの順に積層されてなるめっきプロセス用プライマー層付き多層配線板。
［１４］ 回路加工した配線板の両面に、ガラスクロス入り基材と、［１０］に記載のプロセス用プライマー層とをこの順に重ね、さらに鏡板を重ねて加熱及び加圧する、めっきプロセス用プライマー層付き多層配線板の製造方法。
[13] For a plating process in which a substrate with glass cloth and the primer layer for a plating process according to any one of [1] to [9] are laminated in this order on both sides or one side of a circuit-processed wiring board Multi-layer wiring board with primer layer.
[14] A primer layer for a plating process in which a substrate with glass cloth and the process primer layer described in [10] are stacked in this order on both surfaces of a circuit-processed wiring board, and a mirror plate is further stacked and heated and pressed. Of manufacturing a multilayer wiring board with a wiring.
ここで、本発明でいうめっきプロセスに用いられるプライマー層とは、例えば、多層配線板を製造する際に、回路層間に積層されるプリプレグや絶縁樹脂等の表面にめっきにより導体層を形成する際に用いられる薄い層で、この形成された薄い層の上にめっきを施すことにより、めっきにより形成された導体層のプリプレグや絶縁樹脂層に対する接着性を高め、形成された回路の電気的信頼性を確保するために設けられる層である。さらに、この層を設けることにより、層間の絶縁信頼性も向上する。なお、上記プライマー層は接着補助層といわれる場合がある。 Here, the primer layer used in the plating process referred to in the present invention is, for example, when a conductor layer is formed by plating on the surface of a prepreg or insulating resin layered between circuit layers when manufacturing a multilayer wiring board. This is a thin layer used for soldering. By plating on this formed thin layer, the adhesion of the conductor layer formed by plating to the prepreg and insulating resin layer is improved, and the electrical reliability of the formed circuit It is a layer provided in order to ensure. Furthermore, by providing this layer, the insulation reliability between layers is also improved. In addition, the said primer layer may be called an adhesion auxiliary layer.
本発明によれば、粗化処理後の表面粗さが小さく、かつめっき銅との良好な接着性を確保しつつ、レーザ加工の際にアンダーカットが生じない、めっきプロセス用プライマー層付き多層配線板を製造することが可能な、プライマー層及び当該プライマー層を有するめっきプロセス用プライマー層付き積層板、並びにめっきプロセス用プライマー層付き多層配線板を提供することができる。また、当該めっきプロセス用プライマー層付き積層板の製造方法、めっきプロセス用プライマー層付き多層配線板の製造方法を提供することができる。 According to the present invention, a multilayer wiring with a primer layer for a plating process in which the surface roughness after the roughening treatment is small and undercut does not occur during laser processing while ensuring good adhesion with plated copper. It is possible to provide a primer layer, a laminate with a primer layer for a plating process having the primer layer, and a multilayer wiring board with a primer layer for a plating process, which can produce a plate. Moreover, the manufacturing method of the said laminated board with a primer layer for plating processes, and the manufacturing method of the multilayer wiring board with a primer layer for plating processes can be provided.
本発明のめっきプロセスに用いられるプライマー層は、ガラスクロス入り基材と一括積層されるものであり、（Ａ）エポキシ樹脂、（Ｂ）エポキシ樹脂硬化剤、（Ｃ）ポリアミド、ポリアミドイミド、ポリイミドからなる群から選ばれる耐熱樹脂、（Ｄ）比表面積が２０ｍ2／ｇ以上の無機充填材を含有し、（Ｄ）無機充填材がプライマー層中に１〜１０質量％含有されてなる。
ここで、ガラスクロス入り基材とは、配線板の作製に使用される半硬化状態のプリプレグが挙げられる。
The primer layer used in the plating process of the present invention is laminated together with a glass cloth-containing base material, and is composed of (A) epoxy resin, (B) epoxy resin curing agent, (C) polyamide, polyamideimide, and polyimide. A heat resistant resin selected from the group consisting of: (D) an inorganic filler having a specific surface area of 20 m 2 / g or more, and (D) 1 to 10% by mass of the inorganic filler is contained in the primer layer.
Here, the glass cloth-containing substrate includes a semi-cured prepreg used for production of a wiring board.
本発明のプライマー層は、例えば半硬化状態のプリプレグと積層され、プライマー層とプリプレグの界面が一体化される。従って、プリプレグと積層する際には、プライマー層は未反応の（Ａ）エポキシ樹脂と（Ｂ）エポキシ樹脂硬化剤とが若干残った状態、いわゆる半硬化の状態（Ｂステージ）とすることが必要である。 The primer layer of the present invention is laminated with, for example, a semi-cured prepreg, and the interface between the primer layer and the prepreg is integrated. Therefore, when laminating with the prepreg, the primer layer needs to be in a state in which some unreacted (A) epoxy resin and (B) epoxy resin curing agent remain, so-called semi-cured state (B stage). It is.
本発明のプライマー層に用いることができる（Ｄ）無機充填材としては、シリカ、アルミナ、硫酸バリウム、タルク、クレー、雲母粉、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、窒化ホウ素、ホウ酸アルミニウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸ビスマス、酸化チタン、ジルコン酸バリウム、ジルコン酸カルシウム等が挙げられる。中でも、シリカが好ましい。 Examples of the inorganic filler (D) that can be used in the primer layer of the present invention include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, Examples thereof include boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferable.
無機充填材の粒径は、層間絶縁層上に微細配線を形成する観点から小さいことが必須で、比表面積が２０ｍ2／ｇ以上であることを必要とする。また、比表面積が２０ｍ2／ｇより小さいとレーザ加工の際にプライマー層の界面付近でのアンダーカットの発生が生じやすくなる。これに対し、比表面積が２０ｍ2／ｇ以上の場合、無機充填材とプライマー樹脂との界面の面積が大きくなり、レーザ加工の際に熱を効率よく伝播することができるため、アンダーカット抑制効果が良好に発現する。比表面積は、３０〜１５０ｍ2／ｇであることが好ましく、５０〜１３０ｍ2／ｇ以上であることがより好ましい。 The particle size of the inorganic filler is essential to be small from the viewpoint of forming fine wiring on the interlayer insulating layer, and the specific surface area is required to be 20 m 2 / g or more. On the other hand, if the specific surface area is less than 20 m 2 / g, undercut is likely to occur near the interface of the primer layer during laser processing. On the other hand, when the specific surface area is 20 m 2 / g or more, the area of the interface between the inorganic filler and the primer resin is increased, and heat can be efficiently propagated during laser processing, thereby suppressing the undercut effect. Expresses well. The specific surface area is preferably 30 to 150 m 2 / g, and more preferably 50~130m 2 / g or more.
本発明に係る（Ｄ）無機充填材は、特に球形である必要はない。そのため、比表面積の規定が必要となる。 The (D) inorganic filler according to the present invention is not particularly required to be spherical. Therefore, it is necessary to define the specific surface area.
比表面積は、この分野におけるメーカーが良く用いている方法で求めることが好ましく、ＢＥＴ法等がある。比表面積分析として、たとえば、粉体粒子表面に、吸着占有面積の分かった分子を液体窒素の温度で吸着させ、その量から試料の比表面積を求める方法がある。比表面積分析で、最も良く利用されているのが、不活性気体の低温低湿物理吸着によるＢＥＴ法である。 The specific surface area is preferably determined by a method often used by manufacturers in this field, such as a BET method. As a specific surface area analysis, for example, there is a method in which molecules having a known adsorption occupation area are adsorbed on the surface of powder particles at the temperature of liquid nitrogen, and the specific surface area of the sample is obtained from the amount. In the specific surface area analysis, the BET method based on low-temperature low-humidity physical adsorption of an inert gas is most often used.
また、耐湿性を向上させるために、シランカップリング剤等の表面処理剤で表面処理している無機充填材であることが好ましい。また、分散性を向上させるために、疎水性化処理をしているものが好ましい。 Moreover, in order to improve moisture resistance, it is preferable that it is an inorganic filler surface-treated with surface treatment agents, such as a silane coupling agent. Moreover, in order to improve dispersibility, what has been hydrophobized is preferable.
プライマー層中の（Ｄ）無機充填材の含有量は、１〜１０質量％であり、４〜７質量％であることが好ましく、５〜６質量％であることがより好ましい。
含有量が１質量％未満であると、ガラスクロス入り基材との熱伝導率差が大きく、レーザ加工の際にアンダーカットが生じてしまうため好ましくない。また、含有量が１０質量％を超えると、粗化処理後の表面形状が形成できなくなり、めっき特性が低下することに加え、層間の絶縁信頼性が低下するため好ましくない。また、接着強度が低下することもある。
The content of the inorganic filler (D) in the primer layer is 1 to 10% by mass, preferably 4 to 7% by mass, and more preferably 5 to 6% by mass.
If the content is less than 1% by mass, the difference in thermal conductivity from the glass cloth-containing base material is large, and an undercut occurs during laser processing, which is not preferable. On the other hand, when the content exceeds 10% by mass, the surface shape after the roughening treatment cannot be formed, and the plating characteristics are deteriorated. In addition, the insulation reliability between layers is not preferable. In addition, the adhesive strength may decrease.
例えば、日本アエロジル株式会社製のヒュームドシリカであるＡＥＲＯＳＩＬ Ｒ９７２（商品名）であると、比表面積は１１０±２０ｍ2／ｇ（カタログ値）であり、同社のＡＥＲＯＳＩＬ Ｒ２０２であると、比表面積は１００±２０ｍ2／ｇ（カタログ値）であり好ましい。また、上記日本アエロジル株式会社製以外の材料としては、ＰＬ−１（扶桑化学社製、商品名、１８１ｍ2／ｇ）、ＰＬ−７（扶桑化学社製、商品名、３６ｍ2／ｇ）等がある。
一方で、アドマテックス社製の球状シリカは例えば同社のＳＯ−Ｃ１（商品名）であると、１７ｍ2／ｇ（カタログ値）であり、酸化剤による粗化処理後の表面形状が大きくなるため、好ましくない。
For example, AEROSIL R972 (trade name), which is fumed silica manufactured by Nippon Aerosil Co., Ltd., has a specific surface area of 110 ± 20 m 2 / g (catalog value). It is preferably 100 ± 20 m 2 / g (catalog value). Examples of materials other than those manufactured by Nippon Aerosil Co., Ltd. include PL-1 (manufactured by Fuso Chemical Co., Ltd., trade name, 181 m 2 / g), PL-7 (manufactured by Fuso Chemical Co., Ltd., trade name, 36 m 2 / g), and the like. There is.
On the other hand, the spherical silica made by Admatechs, for example, is SO-C1 (trade name) of the company, and is 17 m 2 / g (catalog value), because the surface shape after the roughening treatment with an oxidizing agent becomes large. It is not preferable.
これらの無機充填材は、１種類のみでも構わなく、２種類以上の無機充填材を併用して使用しても構わない。 These inorganic fillers may be used alone, or two or more inorganic fillers may be used in combination.
さらに、樹脂の伸び性を向上させるために、架橋有機フィラー等を添加しても良い。架橋有機フィラー等は、どのようなものでもよいが、例えばアクリロニトリルブタジエンの共重合物として、アクリロニトリルとブタジエンとを共重合した架橋ＮＢＲ粒子や、アクリロニトリルとブタジエンとアクリル酸等のカルボン酸とを共重合したもの、ポリブタジエン、ＮＢＲ、シリコーンゴムをコアとしアクリル酸誘導体をシェルとした、いわゆるコア−シェルゴム粒子も使用可能である。 Furthermore, in order to improve the extensibility of the resin, a crosslinked organic filler or the like may be added. The cross-linked organic filler may be any type, for example, as a copolymer of acrylonitrile butadiene, a cross-linked NBR particle obtained by copolymerizing acrylonitrile and butadiene, or a copolymer of acrylonitrile, butadiene and carboxylic acid such as acrylic acid. In addition, so-called core-shell rubber particles in which polybutadiene, NBR, and silicone rubber are used as a core and an acrylic acid derivative as a shell can also be used.
例えば、架橋有機フィラーの市販品としては、ブタジエンゴム−アクリル樹脂のコアシェル粒子であるロームアンドハース株式会社製のパラロイドＥＸＬ２６５５や架橋シリコーンゴム−アクリル樹脂のコア−シェルゴム粒子である旭化成ワッカーシリコーン（株）製ＧＥＮＩＯＰＥＲＬ Ｐ５２等がある。
これらのポリマーは、樹脂組成物の全固形分中の配合量が０〜１０質量％であることが好ましい。１０質量％以下とすることで、耐薬品性を良好に維持し、耐熱性等のめっき特性の低下を抑制することができる。
For example, commercially available cross-linked organic fillers include butadiene rubber-acrylic resin core-shell particles, Rohm and Haas Co., Ltd. Paraloid EXL2655, and cross-linked silicone rubber-acrylic resin core-shell rubber particles, Asahi Kasei Wacker Silicone Co., Ltd. There are GENIOPERL P52 and the like.
It is preferable that the compounding quantity in the total solid of a resin composition is 0-10 mass% for these polymers. By setting it as 10 mass% or less, chemical-resistance can be maintained favorable and the fall of plating characteristics, such as heat resistance, can be suppressed.
さらに、本発明におけるプライマー層用樹脂組成物には、通常の樹脂組成物に使用されるチキソ性付与剤、界面活性剤、カップリング剤等の各種添加剤を適宜配合できる。 Furthermore, various additives such as a thixotropic agent, a surfactant, and a coupling agent that are used in ordinary resin compositions can be appropriately blended in the primer layer resin composition of the present invention.
本発明のプライマー層を形成するための樹脂組成物に用いることができる（Ａ）エポキシ樹脂としては、多官能エポキシ樹脂であることが好ましく、フェノールノボラック型エポキシ樹脂や、クレゾールノボラック型エポキシ樹脂、アラルキル型エポキシ樹脂等が挙げられる。特にエポキシ樹脂として、アラルキルノボラック型エポキシ樹脂を含むことが好ましい。本発明におけるアラルキルノボラック型エポキシ樹脂は、ビフェニルアラルキル型エポキシ樹脂（例えば、アラルキルノボラック型エポキシ樹脂）であることが好ましい。ビフェニルアラルキル型エポキシ樹脂であれば、樹脂の強靭化、高伸び率化により銅との接着性がさらに向上する。
ビフェニル構造を有するノボラック型エポキシ樹脂とは、分子中にビフェニル誘導体の芳香族環を含有したアラルキルノボラック型のエポキシ樹脂をいい、例えば、下記式（１）で示されるエポキシ樹脂が挙げられる。これらは単独でも、２種以上を組み合せて用いてもよい。
The epoxy resin (A) that can be used in the resin composition for forming the primer layer of the present invention is preferably a polyfunctional epoxy resin, such as a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, or an aralkyl. Type epoxy resin and the like. In particular, the epoxy resin preferably contains an aralkyl novolac type epoxy resin. The aralkyl novolac type epoxy resin in the present invention is preferably a biphenyl aralkyl type epoxy resin (for example, an aralkyl novolak type epoxy resin). If it is a biphenyl aralkyl type | mold epoxy resin, adhesiveness with copper will further improve by the toughening of resin and high elongation rate.
The novolac type epoxy resin having a biphenyl structure refers to an aralkyl novolac type epoxy resin containing an aromatic ring of a biphenyl derivative in the molecule, and examples thereof include an epoxy resin represented by the following formula (1). These may be used alone or in combination of two or more.
市販品としては、日本化薬株式会社製のＮＣ−３０００（ｐが１．７の式（１）のエポキシ樹脂）、ＮＣ−３０００−Ｈ（ｐが２．８の式（１）のエポキシ樹脂）が挙げられる。 Commercially available products include NC-3000 (epoxy resin of formula (1) where p is 1.7) and NC-3000-H (epoxy resin of formula (1) where p is 2.8) manufactured by Nippon Kayaku Co., Ltd. ).
（Ａ）エポキシ樹脂の配合量は、溶剤を除いた絶縁樹脂組成物の全固形分（（Ａ）エポキシ樹脂、（Ｂ）エポキシ樹脂硬化剤、（Ｃ）耐熱樹脂、及び（Ｄ）無機充填材の合計配合量）中の割合で２０〜８０質量％であることが好ましく、３０〜６０質量％であることがより好ましい。（Ａ）成分の配合量が、２０質量％以上であることで回路導体との接着強度を良好な状態とすることができ、８０質量％以下であることではんだ耐熱性良好な状態とすることができる。 The blending amount of (A) epoxy resin is the total solid content of the insulating resin composition excluding the solvent ((A) epoxy resin, (B) epoxy resin curing agent, (C) heat-resistant resin, and (D) inorganic filler. The total blending amount) is preferably 20 to 80% by mass, and more preferably 30 to 60% by mass. The blending amount of the component (A) is 20% by mass or more so that the adhesive strength with the circuit conductor can be in a good state, and if it is 80% by mass or less, the solder heat resistance is in a good state. Can do.
本発明のプライマー層用樹脂組成物に用いることができる（Ｂ）エポキシ樹脂硬化剤には、各種フェノール樹脂類、酸無水物類、アミン類、ヒドラジット類等が使用できる。フェノール樹脂類としては、ノボラック型フェノール樹脂、レゾール型フェノール樹脂等が使用でき、酸無水物類としては、無水フタル酸、ベンゾフェノンテトラカルボン酸二無水物、メチルハイミック酸等が使用でき、アミン類として、ジシアンジアミド、ジアミノジフェニルメタン、グアニル尿素等が使用できる。信頼性を向上させるためには、ノボラック型フェノール樹脂であることが好ましい。 As the (B) epoxy resin curing agent that can be used in the primer layer resin composition of the present invention, various phenol resins, acid anhydrides, amines, hydragits, and the like can be used. As phenolic resins, novolac-type phenolic resin, resol-type phenolic resin, etc. can be used, and as acid anhydrides, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, etc. can be used, and amines As dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used. In order to improve reliability, a novolac type phenol resin is preferable.
エポキシ樹脂硬化剤は、エポキシ基に対して０．５〜１．５当量であることが好ましい。エポキシ樹脂硬化剤がエポキシ基に対して０．５〜１．５当量であることで、外層銅との接着性の低下を防ぎ、かつＴｇ（ガラス転移温度）や絶縁性の低下をも防ぐことができる。 It is preferable that an epoxy resin hardening | curing agent is 0.5-1.5 equivalent with respect to an epoxy group. When the epoxy resin curing agent is 0.5 to 1.5 equivalents relative to the epoxy group, it prevents a decrease in adhesion with the outer layer copper, and also prevents a decrease in Tg (glass transition temperature) and insulation. Can do.
（Ｃ）耐熱樹脂としてのポリアミド、ポリアミドイミド、ポリイミドの製造に使用するジアミンとしては、芳香族ジアミンでも脂肪族ジアミンでも良く、芳香族ジアミンの具体例としては、ジアミノベンゼン、ジアミノトルエン、ジアミノフェノール、ジアミノジメチルベンゼン、ジアミノメシチレン、ジアミノニトロベンゼン、ジアミノジアゾベンゼン、ジアミノナフタレン、ジアミノビフェニル、ジアミノジメトキシビフェニル、ジアミノジフェニルエーテル、ジアミノジメチルジフェニルエーテル、メチレンジアミン、メチレンビス（ジメチルアニリン）、メチレンビス（メトキシアニリン）、メチレンビス（ジメトキシアニリン）、メチレンビス（エチルアニリン）、メチレンビス（ジエチルアニリン）、メチレンビス（エトキシアニリン）、メチレンビス（ジエトキシアニリン）、イソプロピリデンジアニリン、ジアミノベンゾフェノン、ジアミノジメチルベンゾフェノン、ジアミノアントラキノン、ジアミノジフェニルチオエーテル、ジアミノジメチルジフェニルチオエーテル、ジアミノジフェニルスルホン、ジアミノジフェニルスルホキシド、ジアミノフルオレン等が挙げられる。 (C) Polyamide, polyamideimide, and diamine used as a heat-resistant resin may be an aromatic diamine or an aliphatic diamine, and specific examples of the aromatic diamine include diaminobenzene, diaminotoluene, diaminophenol, Diaminodimethylbenzene, diaminomesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylenediamine, methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline) ), Methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxya) Phosphorus), methylenebis (diethoxy aniline) isopropylidene aniline, diaminobenzophenone, diamino dimethyl benzophenone, diaminoanthraquinone, diaminodiphenyl thioether, diaminodiphenyl dimethyl diphenyl thioether, diaminodiphenyl sulfone, diaminodiphenyl sulfoxide, diaminofluorene and the like.
脂肪族ジアミンの具体例としては、エチレンジアミン、プロパンジアミン、ヒドロキシプロパンジアミン、ブタンジアミン、ヘプタンジアミン、ヘキサンジアミン、ジアミノジエチルアミン、ジアミノプロピルアミン、シクロペンタンジアミン、シクロヘキサンジアミン、アザペンタンジアミン、トリアザウンデカジアミン等が挙げられる。これら芳香族及び脂肪族ジアミンは、１種のみを用いてもよく、２種以上を混合しても良い。 Specific examples of the aliphatic diamine include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, diaminodiethylamine, diaminopropylamine, cyclopentanediamine, cyclohexanediamine, azapentanediamine, and triazaundecadiamine. Etc. These aromatic and aliphatic diamines may be used alone or in combination of two or more.
本発明において、ポリアミドの製造に使用するジカルボン酸としては、芳香族ジカルボン酸でも脂肪族ジカルボン酸でも両末端にカルボキシル基を有するオリゴマーでも良い。 In the present invention, the dicarboxylic acid used for producing the polyamide may be an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or an oligomer having carboxyl groups at both ends.
芳香族ジカルボン酸のうち、フェノール性水酸基を含有しないジカルボン酸の具体例としては、フタル酸、イソフタル酸、テレフタル酸、ビフェニルジカルボン酸、メチレン二安息香酸、チオ二安息香酸、カルボニル二安息香酸、スルホニル二安息香酸、ナフタレンジカルボン酸等が、また、フェノール性水酸基含有のジカルボン酸としては、ヒドロキシイソフタル酸、ヒドロキシフタル酸、ヒドロキシテレフタル酸、ジヒドロキシイソフタル酸、ジヒドロキシテレフタル酸等が挙げられる。 Specific examples of dicarboxylic acids that do not contain a phenolic hydroxyl group among aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, methylene dibenzoic acid, thiodibenzoic acid, carbonyl dibenzoic acid, sulfonyl Examples of dicarboxylic acids include dibenzoic acid and naphthalenedicarboxylic acid, and examples of the phenolic hydroxyl group-containing dicarboxylic acid include hydroxyisophthalic acid, hydroxyphthalic acid, hydroxyterephthalic acid, dihydroxyisophthalic acid, and dihydroxyterephthalic acid.
脂肪族ジカルボン酸としては、シュウ酸、マロン酸、メチルマロン酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、りんご酸、酒石酸、（メタ）アクリロイルオキシコハク酸、ジ（メタ）アクリロイルオキシコハク酸、（メタ）アクリロイルオキシりんご酸、（メタ）アクリルアミドコハク酸や、（メタ）アクリルアミドりんご酸等が挙げられる。 Aliphatic dicarboxylic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, (meth) acryloyloxysuccinic acid, di (meth) acryloyl Examples thereof include oxysuccinic acid, (meth) acryloyloxymalic acid, (meth) acrylamide succinic acid, and (meth) acrylamide malic acid.
両末端にカルボキシル基を有するオリゴマーは、数平均分子量２００〜１００００、好ましくは数平均分子量５００〜５０００のオリゴマーであり、その具体例としては、両末端にカルボキシル基を持ったポリブタジエン、ブタジエン−アクリロニトリル共重合体、スチレン−ブタジエン共重合体、ポリイソプレン、エチレンプロピレン共重合体、ポリエーテル、ポリエステル、ポリカーボネート、ポリアクリレート、ポリメタクリレート、ポリウレタンやシリコーンゴム等が挙げられる。これら芳香族、脂肪族及び両末端にカルボキシル基を有するオリゴマーは、１種のみを用いてもよく、２種以上を混合しても良い。 The oligomer having a carboxyl group at both ends is an oligomer having a number average molecular weight of 200 to 10,000, preferably a number average molecular weight of 500 to 5000. Specific examples thereof include polybutadiene and butadiene-acrylonitrile copolymer having carboxyl groups at both ends. Examples include polymers, styrene-butadiene copolymers, polyisoprene, ethylene propylene copolymers, polyethers, polyesters, polycarbonates, polyacrylates, polymethacrylates, polyurethanes, and silicone rubbers. These aromatic, aliphatic and oligomers having carboxyl groups at both ends may be used alone or in combination of two or more.
耐熱樹脂であるポリアミドが、ポリブタジエンとの共重合体（ポリブタジエン変性ポリアミド樹脂）であればめっき銅との接着性がさらに向上する。このようなポリブタジエン変性ポリアミド樹脂は、ジアミンとフェノール性水酸基含有のジカルボン酸とフェノール性水酸基を含有しないジカルボン酸とをＮ−メチル−２−ピロリドン（ＮＭＰ）等の有機溶媒中で、触媒として亜リン酸エステルとピリジン誘導体の存在下でカルボン基とアミノ基とを重縮合させることにより合成されるフェノール性水酸基含有ポリアミドが挙げられる。但し、これらの割合が多い場合、樹脂全体のＴｇ及び耐薬品性が低下し、耐熱性に悪影響を及ぼしてしまうため、これらが影響しない程度の割合を維持する必要がある。
このようなポリアミド樹脂は、例えば、フェノール性水酸基含有ポリアミド樹脂の市販品としては日本化薬株式会社製のＢＰＡＭ−１５５が挙げられる。
If the polyamide, which is a heat resistant resin, is a copolymer with polybutadiene (polybutadiene-modified polyamide resin), the adhesion to the plated copper is further improved. Such a polybutadiene-modified polyamide resin is prepared by using diamine, dicarboxylic acid containing a phenolic hydroxyl group and dicarboxylic acid not containing a phenolic hydroxyl group as a catalyst in an organic solvent such as N-methyl-2-pyrrolidone (NMP). Examples thereof include a phenolic hydroxyl group-containing polyamide synthesized by polycondensation of a carboxylic group and an amino group in the presence of an acid ester and a pyridine derivative. However, when these ratios are large, the Tg and chemical resistance of the entire resin are lowered and adversely affect the heat resistance. Therefore, it is necessary to maintain a ratio that does not affect them.
As such a polyamide resin, for example, BPAM-155 manufactured by Nippon Kayaku Co., Ltd. can be mentioned as a commercial product of a phenolic hydroxyl group-containing polyamide resin.
本発明において、ポリアミドイミドは、例えば、無水トリメリット酸と芳香族ジイソシアネートとの反応による、いわゆるイソシアネート法で合成されるポリアミドイミドが挙げられる。ポリアミドイミドを合成するイソシアネート法の具体例としては、芳香族トリカルボン酸無水物と上記ジアミン化合物とをジアミン化合物過剰存在下で反応させ、次いでジイソシアネートを反応させる方法（例えば、特許２８９７１８６号公報に記載の方法）、芳香族ジアミン化合物と無水トリメリット酸とを反応させる方法（例えば、特開平０４−１８２４６６号公報に記載の方法）が挙げられる。 In the present invention, examples of the polyamideimide include polyamideimide synthesized by a so-called isocyanate method by reaction of trimellitic anhydride and aromatic diisocyanate. As a specific example of the isocyanate method for synthesizing polyamideimide, a method in which an aromatic tricarboxylic acid anhydride and the above diamine compound are reacted in the presence of excess diamine compound and then a diisocyanate is reacted (for example, as described in Japanese Patent No. 2897186). Method) and a method of reacting an aromatic diamine compound and trimellitic anhydride (for example, a method described in JP-A No. 04-182466).
ポリアミドイミド樹脂としては、東洋紡績株式会社製のバイロマックスＨＲ１１ＮＮ及びバイロマックスＨＲ１６ＮＮ等が挙げられる。 Examples of the polyamide-imide resin include Viromax HR11NN and Viromax HR16NN manufactured by Toyobo Co., Ltd.
本発明において、ポリイミドは、現在工業的に利用されているもっとも一般的な合成法で合成してもよい。例えばテトラカルボン酸２無水物と上記ジアミンを原料に等モルで 重合させ、ポリイミドの前駆体であるポリアミック酸を得た後、２００℃以上の加熱又は 触媒を用いて脱水・環化反応を進め、ポリイミドを得る。触媒を用いる場合はアミン系化合物が多く用いられ、イミド化によって発生した水を速やかに除去するための脱水剤としてカルボン酸無水物を併用する場合もある。 In the present invention, polyimide may be synthesized by the most general synthesis method currently used industrially. For example, tetracarboxylic acid dianhydride and the above diamine are polymerized in equimolar amounts to obtain a polyamic acid that is a polyimide precursor, and then the dehydration and cyclization reaction is advanced using heating at 200 ° C. or higher or using a catalyst. Obtain polyimide. When a catalyst is used, an amine compound is often used, and a carboxylic acid anhydride may be used in combination as a dehydrating agent for quickly removing water generated by imidization.
ポリイミド樹脂としては、日本理化株式会社製のリカコ−トＳＮ２０及びリカコートＰＮ２０等が挙げられる。 Examples of the polyimide resin include Rikacoat SN20 and Ricacoat PN20 manufactured by Nippon Rika Co., Ltd.
また、この（Ｃ）成分の配合割合は、（Ａ）エポキシ樹脂、（Ｂ）エポキシ樹脂硬化剤、（Ｃ）耐熱樹脂、及び（Ｄ）無機充填材の合計配合量中の３〜３０質量％であることが好ましく、１０〜２０質量％であることがより好ましい。３質量％以上であることで、樹脂の強靭性を良好な状態とし、さらに緻密な粗化形状が得られやすくなり、めっき銅との接着力を向上させることができる。また、３０質量％以下であることで、耐熱性が低下することを防ぐことができる。
なお、（Ｃ）成分は各々単独で用いても良く、２種類以上を組合せて用いても構わない。
Moreover, the compounding ratio of this (C) component is 3-30 mass% in the total compounding quantity of (A) epoxy resin, (B) epoxy resin hardening | curing agent, (C) heat-resistant resin, and (D) inorganic filler. It is preferable that it is 10-20 mass%. By being 3% by mass or more, the toughness of the resin is in a good state, and a finer roughened shape can be easily obtained, and the adhesive force with the plated copper can be improved. Moreover, it can prevent that heat resistance falls because it is 30 mass% or less.
In addition, (C) component may be used independently, respectively and may be used in combination of 2 or more types.
本発明のプライマー層を形成するためのプライマー層用樹脂組成物は、（Ａ）〜（Ｄ）の成分に、必要に応じ、他の成分を加え、これらを充分に撹拌、混合した後、泡がなくなるまで静置して得られる。
なお、プライマー層用樹脂組成物に含有する無機充填材を均一に分散させることを目的に、ニーダー、ボールミル、ビーズミル、３本ロール、ナノマイザー等既知の混練・分散方法を用いても良い。
In the primer layer resin composition for forming the primer layer of the present invention, other components are added to the components (A) to (D) as necessary, and these are sufficiently stirred and mixed. It is obtained by standing until it disappears.
For the purpose of uniformly dispersing the inorganic filler contained in the resin composition for the primer layer, a known kneading / dispersing method such as a kneader, ball mill, bead mill, three rolls, or nanomizer may be used.
本発明におけるプライマー層用の樹脂組成物は溶剤中で混合して希釈又は分散させてワニスの形態とするのが作業性の点で好ましい。この溶剤には、メチルエチルケトン、キシレン、トルエン、アセトン、エチレングリコールモノエチルエーテル、シクロヘキサノン、エチルエトキシプロピオネート、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等を使用できる。これらの溶剤は、単独あるいは混合系でも良い。この溶剤の前記樹脂組成物に対する割合は、従来使用している割合でよく、プライマー層用樹脂組成物の塗膜形成の設備にあわせてその使用量を調整する。一方、分散調製した後、上記の溶剤により、プライマー層用の樹脂組成物をさらに希釈又は分散し、ワニスを調製することもできる。 In terms of workability, the primer layer resin composition of the present invention is preferably mixed in a solvent and diluted or dispersed to form a varnish. As this solvent, methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used. These solvents may be used alone or in a mixed system. The ratio of the solvent to the resin composition may be a ratio used in the past, and the amount used is adjusted in accordance with the equipment for forming the coating film of the primer layer resin composition. On the other hand, after the dispersion preparation, the resin composition for the primer layer can be further diluted or dispersed with the above solvent to prepare a varnish.
次いで、得られたプライマー層用の樹脂組成物のワニスを用いて、支持体となる銅箔や樹脂フィルム上に塗工し、乾燥することにより、プライマー層付きの銅箔や樹脂フィルムが得られ、このプライマー層を、プリプレグ等のガラスクロス入り基材に積層することでプライマー層付き配線板用積層板やプライマー層付き多層配線板を得ることができる。そして、このプライマー層付き配線板用積層板やプライマー層付き多層配線板のプライマー層の上に無電解めっきや電解めっきによりめっき層を設け、回路を形成することで多層配線板を製造することができる。 Next, using the varnish of the obtained resin composition for the primer layer, the copper foil or resin film with the primer layer is obtained by coating on a copper foil or resin film to be a support and drying. By laminating this primer layer on a substrate with glass cloth such as a prepreg, a laminated board for a wiring board with a primer layer and a multilayer wiring board with a primer layer can be obtained. A multilayer wiring board can be manufactured by providing a plating layer on the primer layer of the multilayer wiring board with primer layer or the multilayer wiring board with primer layer by electroless plating or electrolytic plating, and forming a circuit. it can.
プライマー層を作製する方法はどのようなものでも良いが、例としてはコンマコータ、グラビアコータ、ダイコータ等を用いて支持体に塗布乾燥する方法がある。また、プライマー層の厚みは１〜１０μｍであることが好ましく、３〜５μｍであることがより好ましい。厚みが１〜１０μｍであることで低ＣＴＥ等のガラスクロス入り基材の特性を維持しつつ、良好なめっき特性を発現することができる。 Any method may be used for producing the primer layer, and examples thereof include a method of applying and drying on a support using a comma coater, a gravure coater, a die coater or the like. Moreover, it is preferable that the thickness of a primer layer is 1-10 micrometers, and it is more preferable that it is 3-5 micrometers. A favorable plating characteristic can be expressed, maintaining the characteristic of glass cloth containing base materials, such as low CTE, because thickness is 1-10 micrometers.
また、このようにして得られるプライマー層付きの銅箔や樹脂フィルムのプライマー層は、Ｂステージのプリプレグ等と接着させる必要があるため、半硬化の状態、いわゆるＢステージ状態にあることが好ましく、この硬化度を制御することも重要である。硬化度は樹脂組成物によっても異なるが、示差走査熱量計等でも測定できる。 Moreover, since the primer layer with the primer layer thus obtained and the primer layer of the resin film need to be adhered to a B-stage prepreg or the like, it is preferably in a semi-cured state, so-called B-stage state, It is also important to control the degree of cure. The degree of cure varies depending on the resin composition, but can also be measured with a differential scanning calorimeter or the like.
ガラスクロス入り基材であるプリプレグは、どのようなものでもよい。一般にはエポキシ樹脂、エポキシ樹脂硬化剤、硬化促進剤、溶剤と無機フィラーを混合し、積層板用ガラスクロスに含浸・乾燥させて得られる。市販品としては、日立化成工業（株）製ＧＥＡ−６７９ＦＧ、ＧＥＡ−６７９ＧＴ等があるが、どのようなものでも構わない。 The prepreg which is a glass cloth-containing base material may be anything. In general, it is obtained by mixing an epoxy resin, an epoxy resin curing agent, a curing accelerator, a solvent and an inorganic filler, and impregnating and drying the glass cloth for laminate. Commercially available products include GEA-679FG, GEA-679GT, etc. manufactured by Hitachi Chemical Co., Ltd., but any products may be used.
本発明のプライマー層付き配線板用積層板は、ガラスクロス入り基材の両面又は片面に、めっきプロセス用プライマー層を重ね、その後鏡板を重ねてプレス成型することにより加圧及び加熱して硬化させた後、樹脂フィルムや銅箔のような支持体を剥離あるいはエッチング等で除去して得ることができる。 The laminated board for a wiring board with a primer layer of the present invention is cured by pressing and heating by overlapping a primer layer for a plating process on both sides or one side of a glass cloth-containing base material, and then laminating a mirror plate and press molding. Then, a support such as a resin film or copper foil can be obtained by peeling or etching.
また、本発明のプライマー層付き多層配線板は、回路加工した配線板（内層回路板）の両面にガラスクロス入り基材と、本発明のプロセス用プライマー層とをこの順に重ね、その後鏡板を重ねてプレス成型することにより加圧・加熱して硬化させた後、樹脂フィルムや銅箔のような支持体を剥離あるいはエッチング等で除去して得ることができる。成形条件は用いるプリプレグの種類によって異なるが、加圧積層条件は、通常０．５〜２０ＭＰａが好ましく、加熱温度は１８０〜２３０℃程度である。 Moreover, the multilayer wiring board with a primer layer of the present invention is obtained by stacking a glass cloth base material and a process primer layer of the present invention in this order on both surfaces of a circuit-processed wiring board (inner circuit board), and then stacking a mirror plate. After press-molding and curing by pressurization and heating, a support such as a resin film or copper foil can be removed by peeling or etching. Although the molding conditions vary depending on the type of prepreg to be used, the pressure lamination conditions are usually preferably 0.5 to 20 MPa, and the heating temperature is about 180 to 230 ° C.
さらに、本発明のプライマー層付き多層配線板は、回路加工した内層板（内層回路板）の上下に真空ラミネーターに対応した配線板用プリプレグを配置し、その上にＰＥＴフィルムを支持体としためっきプロセス用プライマー層をＰＥＴフィルムが外側になるように重ね、真空ラミネーターを用いて積層し、その後、ＰＥＴフィルムを剥離して乾燥機で１８０℃程度に加熱して得ることもできる。 Furthermore, the multilayer wiring board with a primer layer of the present invention has a wiring board prepreg corresponding to a vacuum laminator arranged above and below a circuit-processed inner layer board (inner layer circuit board), on which a PET film is used as a support. It can also be obtained by stacking the process primer layer so that the PET film is on the outside, laminating using a vacuum laminator, then peeling the PET film and heating to about 180 ° C. with a dryer.
内層回路板は、例えば、第一の回路層（内層配線）が表面に形成された内層基板であり、内層基板として、通常の配線板において用いられている公知の積層板、例えば、ガラス布−エポキシ樹脂、紙−フェノール樹脂、紙−エポキシ樹脂、ガラス布・ガラス紙−エポキシ樹脂等が使用でき特に制限はない。また、ビスマレイミド−トリアジン樹脂を含浸させたＢＴ基板、さらにはポリイミドフィルムを基材として用いたポリイミドフィルム基板等も用いることができる。 The inner layer circuit board is, for example, an inner layer board having a first circuit layer (inner layer wiring) formed on the surface, and a known laminated board used in an ordinary wiring board as the inner layer board, for example, a glass cloth- Epoxy resin, paper-phenol resin, paper-epoxy resin, glass cloth / glass paper-epoxy resin, and the like can be used and are not particularly limited. Further, a BT substrate impregnated with a bismaleimide-triazine resin, a polyimide film substrate using a polyimide film as a base material, and the like can also be used.
また、回路を形成するための方法についても特に制限はなく、銅箔と前記絶縁基板を張り合わせた銅張り積層板を用い、銅箔の不要な部分をエッチング除去するサブトラクティブ法や、前記絶縁基板の必要な個所に無電解めっきによって回路を形成するアディティブ法等、公知の配線板の製造方法を用いることができる。 In addition, there is no particular limitation on the method for forming the circuit, and a subtractive method in which an unnecessary portion of the copper foil is removed by etching using a copper-clad laminate obtained by bonding a copper foil and the insulating substrate, or the insulating substrate. A known method for manufacturing a wiring board, such as an additive method for forming a circuit by electroless plating, can be used.
次に、必要に応じて回路層の表面を接着性に適した状態に表面処理する。この手法も、特に制限はなく、例えば、次亜塩素酸ナトリウムのアルカリ水溶液により回路層１の表面に酸化銅の針状結晶を形成し、形成した酸化銅の針状結晶をジメチルアミンボラン水溶液に浸漬して還元するなど公知の製造方法を用いることができる。 Next, if necessary, the surface of the circuit layer is surface-treated in a state suitable for adhesion. This technique is also not particularly limited. For example, a copper oxide needle crystal is formed on the surface of the circuit layer 1 with an alkaline aqueous solution of sodium hypochlorite, and the formed copper oxide needle crystal is converted into a dimethylamine borane aqueous solution. A known production method such as immersion and reduction can be used.
次いで、内層回路の上に設けられたプライマー層付き配線板用積層板又はプライマー層付き多層配線板のプライマー層を用い、これらのプライマー層の上に、めっき法により外層回路を形成する。外層回路の形成では、まず、プライマー層を粗化処理するのが好ましい。粗化液としては、クロム／硫酸粗化液、アルカリ過マンガン酸粗化液、フッ化ナトリウム／クロム／硫酸粗化液、ホウフッ酸粗化液などの酸化性粗化液を用いることができる。粗化処理としては、例えば、先ず膨潤液として、ジエチレングリコールモノブチルエーテルとＮａＯＨとの水溶液を８０℃に加温して積層板又は多層配線板を５分間浸漬処理する。次に、粗化液として、ＫＭｎＯ4とＮａＯＨとの水溶液を８０℃に加温して１０分間浸漬処理する。引き続き、中和液、例えば塩化第一錫（ＳｎＣｌ2）の塩酸水溶液に室温で５分間浸漬処理し、ＫＭｎＯ4を還元する。 Next, using the primer layer of the wiring board with primer layer or the multilayer wiring board with primer layer provided on the inner layer circuit, an outer layer circuit is formed on these primer layers by plating. In forming the outer layer circuit, it is preferable to first roughen the primer layer. As the roughening liquid, an oxidizing roughening liquid such as a chromium / sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, or a borofluoric acid roughening liquid can be used. As the roughening treatment, for example, an aqueous solution of diethylene glycol monobutyl ether and NaOH is first heated as a swelling solution to 80 ° C., and the laminate or multilayer wiring board is immersed for 5 minutes. Next, as a roughening liquid, an aqueous solution of KMnO 4 and NaOH is heated to 80 ° C. and immersed for 10 minutes. Subsequently, KMnO 4 is reduced by immersing in a neutralizing solution, for example, a stannous chloride (SnCl 2 ) aqueous hydrochloric acid solution at room temperature for 5 minutes.
粗化処理後、パラジウムを付着させるめっき触媒付与処理を行う。めっき触媒処理は、塩化パラジウム系のめっき触媒液に浸漬して行われる。次に、無電解めっき液に浸漬してプライマー層の表面全面に厚さが０．１〜１．５μｍの無電解めっき層（導体層）を析出させる。必要により、更に電気めっきを行って必要な厚さとする。無電解めっきに使用する無電解めっき液は、公知の無電解めっき液を使用することができ、特に制限はない。また、電気めっきについても公知の方法によることができ特に制限はない。これらのめっきは銅めっきであることが好ましい。さらに不要な箇所をエッチング除去して回路層を形成することができる。更に同様の工程を繰り返して層数の多い多層配線板を製造できる。 After the roughening treatment, a plating catalyst applying treatment for attaching palladium is performed. The plating catalyst treatment is performed by immersing in a palladium chloride plating catalyst solution. Next, it is immersed in an electroless plating solution to deposit an electroless plating layer (conductor layer) having a thickness of 0.1 to 1.5 μm on the entire surface of the primer layer. If necessary, further electroplating is performed to obtain a necessary thickness. As the electroless plating solution used for electroless plating, a known electroless plating solution can be used, and there is no particular limitation. Also, electroplating can be performed by a known method and is not particularly limited. These platings are preferably copper platings. Furthermore, unnecessary portions can be removed by etching to form a circuit layer. Furthermore, a multilayer wiring board with many layers can be manufactured by repeating the same process.
なお、粗化処理はレーザビアのスミアを除去するためにも行われるため、粗化条件に関しては使用したガラスクロス入り基材のスミア除去性を考慮して選んでよい。 Since the roughening process is also performed to remove the smear of the laser via, the roughening condition may be selected in consideration of the smear removability of the used glass cloth-containing substrate.
次に実施例により本発明を説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.
（合成例１）ポリアミドＡの合成
まず、ディーンスターク還流冷却器、温度計、撹拌器を備えた１Ｌのセパラブルフラスコに、イソフタル酸２２ｇ（１３２ｍｍｏｌ）、３，４’−オキシジアニリン２６．４ｇ（１３２ｍｍｏｌ）、塩化リチウム３．９ｇ、塩化カルシウム１２．１ｇ、Ｎ−メチル−２−ピロリドン２４０ｍｌ、ピリジン５４ｍｌを入れ、攪拌溶解させた後、亜リン酸トリフェニル７４ｇを加えて、９０℃で４時間反応させて、ポリアミド樹脂の生成溶液を得た。この反応溶液をメタノール２０Ｌに投入してポリアミド樹脂を析出させ、ポリアミドＡを得た。
Synthesis Example 1 Synthesis of Polyamide A First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, 22 g (132 mmol) of isophthalic acid and 26.4 g of 3,4′-oxydianiline were synthesized. (132 mmol), lithium chloride 3.9 g, calcium chloride 12.1 g, N-methyl-2-pyrrolidone 240 ml, pyridine 54 ml were added and dissolved by stirring. Then, 74 g of triphenyl phosphite was added, and the mixture was heated at 90 ° C. for 4 hours. By reacting for a period of time, a polyamide resin production solution was obtained. This reaction solution was added to 20 L of methanol to precipitate a polyamide resin, and polyamide A was obtained.
（合成例２）ポリアミドイミドＡの合成
まず、ディーンスターク還流冷却器、温度計、撹拌器を備えた１Ｌのセパラブルフラスコに、飽和脂環式炭化水素基を有するジアミン化合物Ａとして（４，４’−ジアミノ）ジシクロヘキシルメタン（ワンダミンＨＭ（ＷＨＭ）、新日本理化社製、商品名）４５ｍｍｏｌ、シロキサンジアミン化合物Ｂとして反応性シリコーンオイル（Ｘ−２２−１６１−Ｂ、信越化学工業社製、アミン当量：１５００、商品名）５ｍｍｏｌ、無水トリメリット酸（ＴＭＡ）１０５ｍｍｏｌ、非プロトン性極性溶媒としてＮ−メチル−２−ピロリドン（ＮＭＰ）１４５ｇを入れ、フラスコ内の温度を８０℃に設定して３０分間撹拌した後、水と共沸可能な芳香族炭化水素としてトルエン１００ｍＬを更に添加し、フラスコ内の温度を１６０℃に昇温して約２時間還流した。水分定量受器に理論量の水が貯留され、水の留出が見られなくなっていることを確認した後、水分定量受器中の水を除去しながら、フラスコ内の温度を１９０℃まで上昇させて反応溶液中のトルエンを除去した。
フラスコ内の溶液を室温まで戻した後、ジイソシアネートとして４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）６０ｍｍｏｌを添加し、フラスコ内の温度を１９０℃に上昇させて２時間反応させた後、ＮＭＰで希釈してポリアミドイミドのＮＭＰ溶液を得た。この反応溶液をメタノール２０Ｌに投入してポリアミドイミド樹脂を析出させ、ポリアミドイミドＡを得た。
Synthesis Example 2 Synthesis of Polyamideimide A First, a diamine compound A having a saturated alicyclic hydrocarbon group (4, 4) was added to a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer. '-Diamino) dicyclohexylmethane (Wandamine HM (WHM), manufactured by Shin Nippon Chemical Co., Ltd., trade name) 45 mmol, reactive silicone oil as siloxane diamine compound B (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent) : 1500, trade name) 5 mmol, trimellitic anhydride (TMA) 105 mmol, 145 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent, and set the temperature in the flask to 80 ° C. for 30 minutes After stirring, 100 mL of toluene is further added as an aromatic hydrocarbon that can be azeotroped with water. It was refluxed for about 2 hours the temperature was raised inner to 160 ° C.. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.
After returning the solution in the flask to room temperature, 60 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide was obtained. This reaction solution was added to 20 L of methanol to precipitate a polyamideimide resin, and polyamideimide A was obtained.
［プライマー層用樹脂ワニスの調製］
（調製例１）
（Ｃ）成分である合成例１で得られたポリアミドＡ１．８ｇに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）を１５．９ｇ配合した後、続いて（Ａ）成分であるビフェニルアラルキル型エポキシ樹脂（ＮＣ３０００Ｈ、日本化薬社製、商品名）５．０ｇ、（Ｂ）成分であるクレゾールノボラック型フェノール樹脂（ＫＡ１１６５、ＤＩＣ社製、商品名）２．１ｇを加え、更に硬化促進剤として２−フェニルイミダゾール（２ＰＺ、四国化成工業社製、商品名）０．０５０ｇを添加した後、ＤＭＡｃ及びメチルエチルケトンからなる混合溶剤で希釈し、（Ｄ）成分である無機充填材（ＡＥＲＯＳＩＬ Ｒ９７２、日本アエロジル社製、商品名）０．５０ｇを加え、分散機（ナノマイザー、商品名、吉田機械興業株式会社製）を用いて均一なプライマー層用樹脂ワニス（固形分濃度約２５質量％）を得た。
[Preparation of resin varnish for primer layer]
(Preparation Example 1)
After blending 15.9 g of N, N-dimethylacetamide (DMAc) with 1.8 g of the polyamide A obtained in Synthesis Example 1 as the component (C), the biphenyl aralkyl type epoxy resin (component (A)) ( NC3000H, Nippon Kayaku Co., Ltd., trade name) 5.0 g, (B) component cresol novolac type phenolic resin (KA1165, DIC, trade name) 2.1 g is added, and further 2-phenyl as a curing accelerator After adding 0.050 g of imidazole (2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name), it is diluted with a mixed solvent composed of DMAc and methyl ethyl ketone, and an inorganic filler (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) (Product name) 0.50g was added, and a uniform ply using a disperser (Nanomizer, product name, manufactured by Yoshida Kikai Co., Ltd.) A resin varnish for a polymer layer (solid content concentration of about 25% by mass) was obtained.
（調製例２）
（Ｃ）成分であるフェノール性水酸基含有ポリアミド（ＢＰＡＭ−１５５、日本化薬社製、商品名）１．８ｇに、Ｎ、Ｎ−ジメチルアセトアミド（ＤＭＡｃ）を１５．９ｇ配合した後、続いて（Ａ）成分であるビフェニルアラルキル型エポキシ樹脂（ＮＣ３０００Ｈ、日本化薬社製、商品名）５．０ｇ、（Ｂ）成分であるクレゾールノボラック型フェノール樹脂（ＫＡ１１６５、ＤＩＣ社製、商品名）２．１ｇを加え、更に硬化促進剤として２−フェニルイミダゾール（２ＰＺ、四国化成工業社製、商品名）０．０５０ｇを添加し、ＤＭＡｃ及びメチルエチルケトンからなる混合溶剤で希釈した後、（Ｄ）成分である無機充填材（ＡＥＲＯＳＩＬ Ｒ２０２、日本アエロジル社製、商品名）０．５０ｇを加え、分散機（ナノマイザー、商品名、吉田機械興業株式会社製）を用いて均一なプライマー層用樹脂ワニス（固形分濃度約２５質量％）を得た。
(Preparation Example 2)
After blending 15.9 g of N, N-dimethylacetamide (DMAc) with 1.8 g of the phenolic hydroxyl group-containing polyamide (BPAM-155, Nippon Kayaku Co., Ltd., trade name) as component (C), A) component biphenyl aralkyl type epoxy resin (NC3000H, Nippon Kayaku Co., Ltd., trade name) 5.0 g, (B) component cresol novolac type phenol resin (KA1165, DIC, trade name) 2.1 g In addition, 0.050 g of 2-phenylimidazole (2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) is added as a curing accelerator, diluted with a mixed solvent composed of DMAc and methyl ethyl ketone, and then inorganic (D) component Add 0.50 g of filler (AEROSIL R202, Nippon Aerosil Co., Ltd., trade name), and disperser (Nanomizer, trade name, A uniform resin varnish for the primer layer (solid content concentration of about 25% by mass) was obtained using Yoshida Kikai Kogyo Co., Ltd.
（調製例３）
（Ｃ）成分であるフェノール性水酸基含有ポリアミド（ＢＰＡＭ−１５５、日本化薬社製、商品名）１．８ｇに、Ｎ、Ｎ−ジメチルアセトアミド（ＤＭＡｃ）を１５．９ｇ配合した後、続いて架橋有機フィラー（ＥＸＬ−２６５５、ローム＆ハース社製、商品名）０．２７ｇ、（Ａ）成分であるビフェニルアラルキル型エポキシ樹脂（ＮＣ３０００Ｈ、日本化薬社製、商品名）５．０ｇ、（Ｂ）成分であるビスフェノールＡノボラック型フェノール樹脂（ＹＬＨ１２９、油化シェルエポキシ社製、商品名）２．０ｇを加え、更に硬化促進剤として２−フェニルイミダゾール（２ＰＺ、四国化成工業社製、商品名）０．０５０ｇを添加し、ＤＭＡｃ及びメチルエチルケトンからなる混合溶剤で希釈した後、（Ｄ）成分である無機充填材（ＡＥＲＯＳＩＬ Ｒ２０２、日本アエロジル社製、商品名）０．５２ｇを加え、分散機（ナノマイザー、商品名、吉田機械興業株式会社製）を用いて均一なプライマー層用樹脂ワニス（固形分濃度約２５質量％）を得た。
(Preparation Example 3)
After blending 15.9 g of N, N-dimethylacetamide (DMAc) with 1.8 g of the phenolic hydroxyl group-containing polyamide (BPAM-155, Nippon Kayaku Co., Ltd., trade name) which is component (C), then crosslinking Organic filler (EXL-2655, manufactured by Rohm & Haas, trade name) 0.27 g, (A) component biphenylaralkyl epoxy resin (NC3000H, Nippon Kayaku Co., trade name) 5.0 g, (B) The component bisphenol A novolak type phenolic resin (YLH129, manufactured by Yuka Shell Epoxy Co., Ltd., trade name) 2.0 g was added, and 2-phenylimidazole (2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0 as a curing accelerator. After adding .050 g and diluting with a mixed solvent consisting of DMAc and methyl ethyl ketone, inorganic filler (AER) as component (D) SIL R202, manufactured by Nippon Aerosil Co., Ltd. (trade name) 0.52 g was added, and a uniform primer layer resin varnish (solid content concentration of about 25% by mass) using a disperser (Nanomizer, trade name, produced by Yoshida Kikai Co., Ltd.) )
（調製例４）
（Ｃ）成分である合成例２で得られたポリアミドイミドＡ０．３２ｇに、Ｎ、Ｎ−ジメチルアセトアミド（ＤＭＡｃ）を１．３ｇ配合した後、続いて架橋有機フィラー（ＥＸＬ−２６５５、ローム＆ハース社製、商品名）０．９６ｇ、（Ａ）成分であるフェノールノボラック型エポキシ樹脂（Ｎ７７０、ＤＩＣ社製、商品名）５．０ｇ、（Ｂ）成分であるフェノールノボラック型フェノール樹脂（ＴＤ２０９０、ＤＩＣ社製、商品名）２．８ｇを加え、更に硬化促進剤として２−フェニルイミダゾール（２ＰＺ、四国化成工業社製、商品名）０．０５０ｇを添加した後、ＤＭＡｃ及びメチルエチルケトンからなる混合溶剤で希釈し、（Ｄ）成分である無機充填材（ＡＥＲＯＳＩＬ Ｒ９７２、日本アエロジル社製、商品名）０．５４ｇを加え、分散機（ナノマイザー、商品名、吉田機械興業株式会社製）を用いて均一なプライマー層用樹脂ワニス（固形分濃度約２５質量％）を得た。
(Preparation Example 4)
After blending 1.3 g of N, N-dimethylacetamide (DMAc) with 0.32 g of polyamideimide A obtained in Synthesis Example 2 as component (C), subsequently, a crosslinked organic filler (EXL-2655, Rohm & Haas) (Product name) 0.96 g, (A) component phenol novolac type epoxy resin (N770, manufactured by DIC, product name) 5.0 g, (B) component phenol novolac type phenol resin (TD2090, DIC) After adding 2.8 g of product (trade name), and further adding 0.050 g of 2-phenylimidazole (2PZ, product name of Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator, dilute with a mixed solvent consisting of DMAc and methyl ethyl ketone. And 0.54 g of inorganic filler (AEROSIL R972, Nippon Aerosil Co., Ltd., trade name) as component (D), Using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.), a uniform primer layer resin varnish (solid content concentration of about 25% by mass) was obtained.
（比較調製例１）
調製例１の（Ｄ）成分を除く以外は、調製例１と同様として樹脂ワニスを得た。
(Comparative Preparation Example 1)
A resin varnish was obtained in the same manner as in Preparation Example 1 except that the component (D) in Preparation Example 1 was excluded.
（比較調製例２）
調製例１の（Ｄ）成分の代わりに、比表面積が１７ｍ2／ｇ（カタログ値）である球状シリカ（ＳＯ−Ｃ１、アドマテックス社製、商品名）を０．５０ｇ配合した以外は、調製例１と同様として樹脂ワニスを得た。
(Comparative Preparation Example 2)
Instead of component (D) in Preparation Example 1, preparation was performed except that 0.50 g of spherical silica (SO-C1, manufactured by Admatechs, trade name) having a specific surface area of 17 m 2 / g (catalog value) was blended. A resin varnish was obtained in the same manner as in Example 1.
（比較調製例３）
調製例２の（Ｄ）成分を除く以外は、調製例２と同様として樹脂ワニスを得た。
(Comparative Preparation Example 3)
A resin varnish was obtained in the same manner as in Preparation Example 2 except that the component (D) in Preparation Example 2 was omitted.
（比較調製例４）
調製例３の（Ｄ）成分の配合量を１．９ｇにした以外は調製例３と同様として樹脂ワニスを得た。
(Comparative Preparation Example 4)
A resin varnish was obtained in the same manner as in Preparation Example 3, except that the amount of component (D) in Preparation Example 3 was changed to 1.9 g.
（実施例１）
調製例１で得られたプライマー層用樹脂ワニスを銅箔（ＹＧＰ−１２、日本電解社製、商品名）の光沢面に、乾燥後５μｍになるように塗布し、２００℃で５分間乾燥させ、プライマー層付銅箔を得た。
Example 1
The primer layer resin varnish obtained in Preparation Example 1 was applied to a glossy surface of a copper foil (YGP-12, manufactured by Nippon Electrolytic Co., Ltd.) to a thickness of 5 μm after drying, and dried at 200 ° C. for 5 minutes. A copper foil with a primer layer was obtained.
次いで、プライマー層付き配線板用積層板は次のようにして製造した。プリプレグ（ＧＥＡ−６７９ＦＧ（Ｒ）、日立化成工業社製、商品名）の０．１０ｍｍ厚４枚を重ね、その上下に上記プライマー層付銅箔を銅箔が外側になるように重ね、さらに鏡板と、クッション紙を重ねて、プレス機を用いて、４．０ＭＰａ、１８５℃で１時間加熱硬化させた。冷却後、銅箔をエッチングして、本発明のプライマー層付き配線板用積層板を得た。 Subsequently, the laminated board for wiring boards with a primer layer was manufactured as follows. 4 sheets of prepreg (GEA-679FG (R), manufactured by Hitachi Chemical Co., Ltd., trade name) are stacked in a thickness of 0.10 mm, and the above copper foil with primer layer is stacked on the top and bottom so that the copper foil is on the outside. And the cushion paper was piled up, and it heat-hardened at 4.0 MPa and 185 degreeC for 1 hour using the press machine. After cooling, the copper foil was etched to obtain a laminated board for a wiring board with a primer layer of the present invention.
また、多層配線板は次のようにして製造した。このプライマー層付き配線板用積層板を化学粗化するために、膨潤液として、ジエチレングリコールモノブチルエーテル：２００ｍｌ／Ｌ、ＮａＯＨ：５ｇ／Ｌの水溶液を作製し、８０℃に加温して１０分間浸漬処理した。次に、粗化液として、ＫＭｎＯ4：６０ｇ／Ｌ、ＮａＯＨ：４０ｇ／Ｌの水溶液を作製し、８０℃に加温して１５分間浸漬処理した。引き続き、中和液（ＳｎＣｌ2：３０ｇ／Ｌ、ＨＣｌ：３００ｍｌ／Ｌ）の水溶液を作製し、４０℃に加温して５分間浸漬処理し、ＫＭｎＯ4を還元した。 The multilayer wiring board was manufactured as follows. In order to chemically roughen this laminated board for wiring board with primer layer, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, NaOH: 5 g / L was prepared as a swelling liquid, heated to 80 ° C. and immersed for 10 minutes. Processed. Next, an aqueous solution of KMnO 4 : 60 g / L and NaOH: 40 g / L was prepared as a roughening solution, heated to 80 ° C. and immersed for 15 minutes. Subsequently, an aqueous solution of a neutralizing solution (SnCl 2 : 30 g / L, HCl: 300 ml / L) was prepared, heated to 40 ° C. and immersed for 5 minutes to reduce KMnO 4 .
プライマー層付き配線板用積層板に回路層を形成するために、まず、ＰｄＣｌ2を含む無電解めっき用触媒であるアクチベーターネオガント８３４（アトテック・ジャパン社製、商品名）を３５℃に加温して５分間浸漬処理し、無電解銅めっき用であるめっき液プリントガントＭＳＫ−ＤＫ（アトテック・ジャパン社製、商品名）に室温−１５分間浸漬し、さらに硫酸銅電解めっきを行った。その後、アニールを１８０℃−６０分間行い厚さ２０μｍの導体層を形成し、めっきプロセス用プライマー層付き多層配線板を作製した。 In order to form a circuit layer on a laminate for a wiring board with a primer layer, first, an activator Neogant 834 (trade name, manufactured by Atotech Japan), which is an electroless plating catalyst containing PdCl 2 , is added to 35 ° C. It was heated and immersed for 5 minutes, immersed in a plating solution print Gantt MSK-DK (trade name, manufactured by Atotech Japan) for electroless copper plating, and further subjected to copper sulfate electrolytic plating. Thereafter, annealing was performed at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 20 μm, and a multilayer wiring board with a primer layer for a plating process was produced.
（実施例２）
実施例１の調製例１のワニスの代わりに調製例２を用いた以外は、実施例１と同様として、めっきプロセス用プライマー層付き多層配線板を作製した。
(Example 2)
A multilayer wiring board with a primer layer for a plating process was produced in the same manner as in Example 1 except that Preparation Example 2 was used instead of the varnish of Preparation Example 1 of Example 1.
（実施例３）
実施例１の調製例１のワニスの代わりに調製例３を用いた以外は、実施例１と同様として、めっきプロセス用プライマー層付き多層配線板を作製した。
(Example 3)
A multilayer wiring board with a primer layer for a plating process was produced in the same manner as in Example 1 except that Preparation Example 3 was used instead of the varnish of Preparation Example 1 of Example 1.
（実施例４）
実施例１の調製例１のワニスの代わりに調製例４を用いた。さらにプライマー層付き配線板用積層板は次のようにして製造した。プリプレグ（ＧＥＡ−７００Ｇ、日立化成工業社製、商品名）の０．１０ｍｍ厚４枚を重ね、その上下に上記プライマー層付銅箔を銅箔が外側になるように重ね、さらに鏡板と、クッション紙を重ねて、プレス機を用いて、３．０ＭＰａ、２３０℃で１時間加熱硬化させた。冷却後、銅箔をエッチングして、本発明のプライマー層付き配線板用積層板を得た。それ以外は、実施例１と同様とした
Example 4
Preparation Example 4 was used in place of the varnish of Preparation Example 1 of Example 1. Furthermore, the laminated board for wiring boards with a primer layer was manufactured as follows. 4 sheets of prepreg (GEA-700G, manufactured by Hitachi Chemical Co., Ltd., product name) 4 layers of 0.10mm thickness are stacked, and the copper foil with primer layer is stacked on the top and bottom so that the copper foil is on the outside. The paper was piled up and cured by heating at 3.0 MPa and 230 ° C. for 1 hour using a press machine. After cooling, the copper foil was etched to obtain a laminated board for a wiring board with a primer layer of the present invention. Other than that, it was the same as Example 1.
（実施例５）
プライマー層として調製例２で作製したワニスを離型処理したＰＥＮフィルム（帝人社製）に乾燥後５μｍになるように塗布し、２００℃で５分間乾燥させた以外、実施例１と同様として、めっきプロセス用プライマー層付き多層配線板を作製した。
(Example 5)
As a primer layer, the varnish produced in Preparation Example 2 was applied to a PEN film (manufactured by Teijin Limited) so as to have a thickness of 5 μm after drying, and was dried at 200 ° C. for 5 minutes. A multilayer wiring board with a primer layer for a plating process was produced.
（比較例１）
実施例１において、プライマー層を形成していない単独の銅箔粗化面を用いた以外、実施例１と同様として、多層配線板を作製した。
(Comparative Example 1)
In Example 1, a multilayer wiring board was produced in the same manner as in Example 1 except that a single roughened copper foil surface on which no primer layer was formed was used.
（比較例２）
プライマー層として比較調製例１で作製した樹脂ワニスを用いた以外、実施例１と同様として、多層配線板を作製した。
(Comparative Example 2)
A multilayer wiring board was produced in the same manner as in Example 1 except that the resin varnish produced in Comparative Preparation Example 1 was used as the primer layer.
（比較例３）
プライマー層として比較調製例２で作製した樹脂ワニスを用いた以外、実施例１と同様として、多層配線板を作製した。
(Comparative Example 3)
A multilayer wiring board was produced in the same manner as in Example 1 except that the resin varnish produced in Comparative Preparation Example 2 was used as the primer layer.
（比較例４）
プライマー層として比較調製例３で作製した樹脂ワニスを用いた以外、実施例１と同様として、多層配線板を作製した。
(Comparative Example 4)
A multilayer wiring board was produced in the same manner as in Example 1 except that the resin varnish produced in Comparative Preparation Example 3 was used as the primer layer.
（比較例５）
プライマー層として比較調製例４で作製した樹脂ワニスを用いた以外、実施例１と同様として、多層配線板を作製した。
(Comparative Example 5)
A multilayer wiring board was produced in the same manner as in Example 1 except that the resin varnish produced in Comparative Preparation Example 4 was used as the primer layer.
以上のようにして作製した樹脂組成物及び多層配線板について、外層回路との接着強度、絶縁樹脂の表面粗さ、レーザ加工後の断面観察を行った。その結果を下記表１、２に示す。なお、測定方法は次のとおりである。 The resin composition and the multilayer wiring board produced as described above were observed for adhesion strength with the outer layer circuit, surface roughness of the insulating resin, and cross-section after laser processing. The results are shown in Tables 1 and 2 below. The measurement method is as follows.
［外層回路との接着強度］
各実施例及び比較例で得た積層板の導体層にエッチング処理によって、幅１０ｍｍ、長さ１００ｍｍの部分を形成し、この一端を回路層／樹脂界面で剥がしてつかみ具でつかみ、垂直方向に引張り速度約５０ｍｍ／分、室温中で引き剥がした時の荷重を測定した。
[Adhesion strength with outer layer circuit]
The conductor layer of the laminated board obtained in each example and comparative example was etched to form a portion having a width of 10 mm and a length of 100 mm. One end of the conductor layer was peeled off at the circuit layer / resin interface and held with a holding tool. The load when it was peeled off at room temperature at a pulling rate of about 50 mm / min was measured.
［絶縁樹脂の表面粗さ］
各実施例及び比較例で得た積層板の導体層の一部のエッチング処理によって得た絶縁樹脂表面を菱化システム社製マイクロマップＭＮ５０００型を用い、表面粗さＲａを測定した。Ｒａは本発明の趣旨から、微細配線を形成するために、小さいほうが好ましく、０．３μｍ未満をＯＫとした。
[Insulation resin surface roughness]
The surface roughness Ra was measured for the surface of the insulating resin obtained by etching a part of the conductor layer of the laminate obtained in each Example and Comparative Example, using a Ryoka System Micromap MN5000 type. For the purpose of the present invention, Ra is preferably smaller in order to form fine wiring, and less than 0.3 μm is OK.
［レーザ加工及び断面観察］
各実施例及び比較例で得た積層板の必要な箇所に層間接続用のビアホールを形成した。ビアホールは、三菱製レーザ加工機（ＭＬ−６０５ＧＴＸ、外注先：レーザジョブ（株））を用い、ビア径６０μｍ、周波数５００Ｈｚ、パルス幅５μｓ、ショット数３ショット、パルスエネルギー０．８ｍＪの条件で加工し形成した。その後、実施例に記載の方法で粗化処理を行い、次いで断面加工を行い、走査型電子顕微鏡（Ｓ−４７００、日立ハイテクノロジーズ社製、商品名）を用いてビア断面を観察し、アンダーカットの有無を確認した。ビア断面において、アンダーカットが生じない場合を合格（表中の○）とし、図１に示すようにアンダーカットが生じた場合を不合格（表中の×）とした。
[Laser processing and cross-sectional observation]
Via holes for interlayer connection were formed at necessary portions of the laminates obtained in the examples and comparative examples. The via hole is processed using a Mitsubishi laser processing machine (ML-605GTX, subcontractor: Laser Job Co., Ltd.) with a via diameter of 60 μm, frequency of 500 Hz, pulse width of 5 μs, number of shots of 3 shots, and pulse energy of 0.8 mJ. Formed. Thereafter, a roughening treatment is performed by the method described in the examples, then a cross-section is processed, and a via cross-section is observed using a scanning electron microscope (S-4700, manufactured by Hitachi High-Technologies Corporation), and an undercut is performed. The presence or absence was confirmed. In the cross section of the via, the case where no undercut occurred was determined to pass (◯ in the table), and the case where the undercut occurred as shown in FIG.
表１から、本発明のめっきプロセス用のプライマー層付き積層板並びに多層配線板の特性は、実施例１〜５に示したように、Ｒａが０．３μｍ未満の平滑な樹脂表面上においても、無電解銅めっきとの高接着力を示し、さらに、良好なレーザ加工性を発現することが分かった。一方、表２に示すとおり、本発明の絶縁樹脂組成物を必須に含んでいない比較例１〜５に示す多層配線板は、表面粗さが大きいか、無電解銅めっきとの接着力が低い、もしくはレーザ加工性が悪化することが確認できた。 From Table 1, the characteristics of the laminate with a primer layer for the plating process of the present invention and the multilayer wiring board, as shown in Examples 1 to 5, even on a smooth resin surface with Ra less than 0.3 μm, It has been shown that it exhibits high adhesive strength with electroless copper plating, and also exhibits good laser processability. On the other hand, as shown in Table 2, the multilayer wiring boards shown in Comparative Examples 1 to 5 that do not necessarily contain the insulating resin composition of the present invention have large surface roughness or low adhesion with electroless copper plating. It was also confirmed that the laser processability deteriorated.
１０・・・基板
１２・・・導電層
１４・・・ガラスクロス入り基材
１６・・・プライマー層
１８・・・アンダーカット部
２０・・・積層板
DESCRIPTION OF
Claims (14)
（Ｄ）無機充填材の含有量が１〜１０質量％であり、ガラスクロス入り基材上に形成される、めっきプロセス用プライマー層。 (A) an epoxy resin, (B) an epoxy resin curing agent, (C) a heat resistant resin selected from the group consisting of polyamide, polyamideimide, and polyimide, and (D) an inorganic filler having a specific surface area of 20 m 2 / g or more. ,
(D) A primer layer for a plating process, wherein the inorganic filler content is 1 to 10% by mass and is formed on a glass cloth-containing substrate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016016532A (en) * | 2014-07-04 | 2016-02-01 | 日立化成株式会社 | Prepreg with primer layer for plating process, multilayer printed wiring board and manufacturing method therefor each using the same |
| CN111560171A (en) * | 2019-02-13 | 2020-08-21 | 味之素株式会社 | Resin composition |
Citations (5)
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|---|---|---|---|---|
| JP2002076621A (en) * | 2000-08-31 | 2002-03-15 | Elna Co Ltd | Multilayer circuit board and its manufacturing method |
| JP2006137943A (en) * | 2004-10-15 | 2006-06-01 | Ajinomoto Co Inc | Resin composition |
| WO2008153208A1 (en) * | 2007-06-14 | 2008-12-18 | Ajinomoto Co., Inc. | Resin composition for interlayer insulation of multilayer printed wiring board |
| WO2010061980A1 (en) * | 2008-11-28 | 2010-06-03 | 味の素株式会社 | Resin composition |
| JP2012233101A (en) * | 2011-05-02 | 2012-11-29 | Hitachi Chemical Co Ltd | Resin composition for adhesion adjuvant layer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002076621A (en) * | 2000-08-31 | 2002-03-15 | Elna Co Ltd | Multilayer circuit board and its manufacturing method |
| JP2006137943A (en) * | 2004-10-15 | 2006-06-01 | Ajinomoto Co Inc | Resin composition |
| WO2008153208A1 (en) * | 2007-06-14 | 2008-12-18 | Ajinomoto Co., Inc. | Resin composition for interlayer insulation of multilayer printed wiring board |
| WO2010061980A1 (en) * | 2008-11-28 | 2010-06-03 | 味の素株式会社 | Resin composition |
| JP2012233101A (en) * | 2011-05-02 | 2012-11-29 | Hitachi Chemical Co Ltd | Resin composition for adhesion adjuvant layer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016016532A (en) * | 2014-07-04 | 2016-02-01 | 日立化成株式会社 | Prepreg with primer layer for plating process, multilayer printed wiring board and manufacturing method therefor each using the same |
| CN111560171A (en) * | 2019-02-13 | 2020-08-21 | 味之素株式会社 | Resin composition |
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