JP2010028036A - Production method of multilayer printed wiring board - Google Patents
Production method of multilayer printed wiring board Download PDFInfo
- Publication number
- JP2010028036A JP2010028036A JP2008191093A JP2008191093A JP2010028036A JP 2010028036 A JP2010028036 A JP 2010028036A JP 2008191093 A JP2008191093 A JP 2008191093A JP 2008191093 A JP2008191093 A JP 2008191093A JP 2010028036 A JP2010028036 A JP 2010028036A
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- layer
- resin sheet
- insulating resin
- insulating
- thermosetting
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Landscapes
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
Description
本発明は、多層プリント配線板の製造方法及び該製造方法に使用される絶縁樹脂シートに関する。 The present invention relates to a method for producing a multilayer printed wiring board and an insulating resin sheet used in the production method.
従来、多層プリント配線板の製造技術として、コア基板上に絶縁層と導体層とを交互に積み重ねるビルトアップ方式による製造方法が知られている。絶縁層形成には、専ら支持体上に熱硬化性樹脂層が形成された絶縁樹脂シートが使用され、接着フィルムを内層回路基板に積層し、熱硬化性樹脂を熱硬化することにより、絶縁層が形成される。 Conventionally, as a manufacturing technique of a multilayer printed wiring board, a manufacturing method by a built-up method in which insulating layers and conductor layers are alternately stacked on a core substrate is known. An insulating resin sheet in which a thermosetting resin layer is formed on a support is used exclusively for forming an insulating layer, and an insulating film is laminated by laminating an adhesive film on an inner circuit board and thermosetting the thermosetting resin. Is formed.
近年の、電子機器や電子部品の小型化のニーズにより、多層プリント配線板においては、絶縁層厚の薄型化が要求されている。また、高度情報化社会では情報処理能力あるいは情報伝達能力の向上が求められ、電子機器はその処理能力を上げるために動作周波数が高くなっている。動作周波数の高いプリント配線板は、インピーダンスコントロールのために絶縁層厚みを均一化が求められる。特に、絶縁層厚みが薄い場合には、より高度な絶縁層厚のコントロールが必要となる。 Due to recent needs for miniaturization of electronic devices and electronic components, multilayer printed wiring boards are required to have a thin insulating layer. Further, in an advanced information society, improvement in information processing capability or information transmission capability is required, and electronic devices have higher operating frequencies in order to increase their processing capabilities. A printed wiring board having a high operating frequency is required to have a uniform insulating layer thickness for impedance control. In particular, when the insulating layer thickness is thin, it is necessary to control the insulating layer thickness to a higher degree.
特許文献１には、絶縁樹脂シートを真空ラミネーターで内層回路基板に積層する際に、耐熱ゴムで積層した後、金属板等で絶縁樹脂層表面を平滑化する方法が開示されている。
特許文献１記載の方法によれば、積層された絶縁樹脂シート表面が平滑化されるため、絶縁層厚も均一化されることになるが、薄型化された絶縁層厚を高度に均一化するには不十分である。 According to the method described in Patent Document 1, since the surface of the laminated insulating resin sheet is smoothed, the insulating layer thickness is also made uniform, but the thickness of the thinned insulating layer is made highly uniform. Is not enough.
従って、本願発明の課題は、絶縁層厚をより高度に均一化することができる、多層プリント配線板の製造方法及び該方法に用いる絶縁樹脂シートを提供することにある。 Therefore, the subject of this invention is providing the manufacturing method of a multilayer printed wiring board which can make the insulating layer thickness uniform more highly, and the insulating resin sheet used for this method.
本発明者らは、上記課題を解決すべく鋭意検討した結果、支持体層、該支持体層上に熱硬化性樹脂組成物の硬化物で形成された硬化物層、及び該硬化物層上に熱硬化性樹脂組成物で形成された接着層を有する絶縁樹脂シートを使用し、該絶縁樹脂シートを内層回路基板に積層した後、絶縁樹脂シートを金属板等で平滑化することにより、厚みが高度に均一化された絶縁層が形成できることを見出し、本発明を完成させた。すなわち、本発明は以下の内容を含むものである。 As a result of intensive studies to solve the above problems, the present inventors have found that a support layer, a cured product layer formed of a cured product of a thermosetting resin composition on the support layer, and on the cured product layer Using an insulating resin sheet having an adhesive layer formed of a thermosetting resin composition, laminating the insulating resin sheet on the inner circuit board, and then smoothing the insulating resin sheet with a metal plate or the like, the thickness The inventors have found that a highly uniform insulating layer can be formed and completed the present invention. That is, the present invention includes the following contents.
［１］ 支持体層、該支持体層上に熱硬化性樹脂組成物の硬化物で形成された硬化物層、及び該硬化物層上に熱硬化性樹脂組成物で形成された接着層を有する絶縁樹脂シートを、接着層を内層回路基板側とし、加熱及び加圧することにより内層回路基板に積層する積層工程、積層された絶縁樹脂シートを金属板又は金属ロールにより加熱及び加圧することにより平滑化する平滑化工程、及び平滑化された絶縁樹脂シートを熱硬化する熱硬化工程、を含む多層プリント配線板の製造方法。
［２］ 積層工程が減圧下に行われる、上記［１］に記載の方法。
［３］ 積層工程が支持体側より弾性材を介して加熱及び加圧することにより行われる、上記［１］又は［２］に記載の方法。
［４］ 平滑化工程が金属板により行われる、上記［１］〜［３］いずれかに記載の方法。
［５］ 加熱及び加圧により、平滑化工程と熱硬化工程が同時に行われる、上記［１］〜［４］いずれかに記載の方法。
［６］ 硬化物層のガラス転移温度が８０℃以上である、上記［１］〜［５］いずれかに記載の方法。
［７］ 硬化物層の厚みが１〜５０μｍである、上記［１］〜［６］いずれかに記載の方法。
［８］ 接着層の厚みが５〜５０μｍである、上記［１］〜［７］いずれかに記載の方法。
［９］ 支持体層、該支持体層上に熱硬化性樹脂組成物の硬化物層、及び該硬化物層上に接着層を有する絶縁樹脂シート。
［１０］ 硬化物層のガラス転移温度が８０℃以上である、上記［９］に記載の絶縁樹脂シート。
［１１］ 硬化物層の厚みが１〜５０μｍである、上記［９］又は［１０］に記載の絶縁樹脂シート。
［１２］ 接着層の厚みが５〜５０μｍである、上記［９］〜［１１］いずれかに記載の絶縁樹脂シート。
[1] A support layer, a cured layer formed of a cured product of a thermosetting resin composition on the support layer, and an adhesive layer formed of a thermosetting resin composition on the cured product layer. Laminating step of laminating the insulating resin sheet having the adhesive layer on the inner layer circuit board side and laminating on the inner layer circuit board by heating and pressing, smoothing by heating and pressing the laminated insulating resin sheet with a metal plate or metal roll A method for producing a multilayer printed wiring board, comprising: a smoothing step for forming a heat treatment; and a thermosetting step for thermosetting the smoothed insulating resin sheet.
[2] The method according to [1] above, wherein the laminating step is performed under reduced pressure.
[3] The method according to [1] or [2] above, wherein the laminating step is performed by heating and pressurizing from the support side through an elastic material.
[4] The method according to any one of [1] to [3], wherein the smoothing step is performed with a metal plate.
[5] The method according to any one of [1] to [4] above, wherein the smoothing step and the thermosetting step are simultaneously performed by heating and pressurization.
[6] The method according to any one of [1] to [5] above, wherein the glass transition temperature of the cured product layer is 80 ° C. or higher.
[7] The method according to any one of [1] to [6] above, wherein the thickness of the cured product layer is 1 to 50 μm.
[8] The method according to any one of [1] to [7], wherein the adhesive layer has a thickness of 5 to 50 μm.
[9] An insulating resin sheet having a support layer, a cured product layer of a thermosetting resin composition on the support layer, and an adhesive layer on the cured product layer.
[10] The insulating resin sheet according to [9], wherein the cured product layer has a glass transition temperature of 80 ° C. or higher.
[11] The insulating resin sheet according to the above [9] or [10], wherein the cured product layer has a thickness of 1 to 50 μm.
[12] The insulating resin sheet according to any one of [9] to [11], wherein the adhesive layer has a thickness of 5 to 50 μm.
本発明の絶縁樹脂シートは、絶縁層厚の均一性に優れた多層プリント配線板を製造することができ、特に薄型化された絶縁層を有する多層プリント配線場の製造に好適に用いることができる。 INDUSTRIAL APPLICABILITY The insulating resin sheet of the present invention can produce a multilayer printed wiring board excellent in uniformity of the insulating layer thickness, and can be suitably used particularly for the production of a multilayer printed wiring field having a thinned insulating layer. .
本発明の多層プリント配線板用の絶縁樹脂シートは、支持体層、該支持体層上に熱硬化性樹脂組成物の硬化物で形成された硬化物層、該硬化物層上に熱硬化性樹脂組成物で形成された接着層から構成される。 The insulating resin sheet for multilayer printed wiring boards of the present invention comprises a support layer, a cured product layer formed from a cured product of a thermosetting resin composition on the support layer, and a thermosetting product on the cured product layer. It is comprised from the contact bonding layer formed with the resin composition.
支持体層としては、プラスチックフィルムが好適に用いられる。プラスチックフィルムの他には、離型紙や銅箔、アルミニウム箔等の金属箔なども支持体層として用いることができるプラスチックフィルムとしては、ポリエチレンテレフタレート（以下「PET 」と略称することがある。）、ポリエチレンナフタレート等のポリエステル、ポリカーボネート、アクリル、環状ポリオレフィン、トリアセチルセルロース、ポリエーテルサルファイド、ポリエーテルケトン、ポリイミドなどが挙げられる。中でも、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルムが好ましく、特に安価なポリエチレンテレフタレートフィルムが好ましい。支持体において、特にプラスチックフィルムを使用する場合、熱硬化性樹脂組成物の硬化物層から剥離可能とするために、その熱硬化性樹脂組成物層の被形成面が離型処理された、離型層を有する支持体を使用するのが好ましい。金属箔はエッチング溶液により除去することもできるが、プラスチックフィルムを支持体として熱硬化性樹脂組成物を熱硬化した場合、離型層がないと、硬化物からプラスチックフィルムを剥離することが困難となる。離型処理に使用する離型剤としては、硬化物が支持体から剥離可能であれば特に限定されず、例えば、シリコン系離型剤、アルキッド樹脂系離型剤等が挙げられる。なお、市販されている離型層付きプラスチックフィルムを用いてもよく、好ましいものとしては、例えば、アルキッド樹脂系離型剤を主成分とする離型層を有するPET フィルムである、リンテック（株）製のＳＫ−１、ＡＬ−５、ＡＬ−７などが挙げられる。また、プラスチックフィルムはマット処理、コロナ処理を施してあってもよく、当該処理面上に離型層を形成してもよい。また銅箔を支持体として使用した場合は、剥離せずに該銅箔を導体層として利用してもよい。支持体の厚さは特に限定されないが、通常１０〜１５０μｍであり、好ましくは２５〜５０μｍの範囲で用いられる。 A plastic film is preferably used as the support layer. In addition to the plastic film, a release film, a copper foil, a metal foil such as an aluminum foil, or the like can be used as the support layer. As the plastic film, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), Examples thereof include polyester such as polyethylene naphthalate, polycarbonate, acrylic, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone, and polyimide. Among these, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and an inexpensive polyethylene terephthalate film is particularly preferable. In the case of using a plastic film in the support, in particular, in order to make it peelable from the cured product layer of the thermosetting resin composition, the formation surface of the thermosetting resin composition layer is subjected to a release treatment. It is preferred to use a support having a mold layer. The metal foil can be removed with an etching solution, but when the thermosetting resin composition is thermoset using the plastic film as a support, it is difficult to peel the plastic film from the cured product without a release layer. Become. The release agent used for the release treatment is not particularly limited as long as the cured product can be peeled from the support, and examples thereof include silicon release agents and alkyd resin release agents. A commercially available plastic film with a release layer may be used, and preferable examples include, for example, a PET film having a release layer mainly composed of an alkyd resin release agent, Lintec Corporation. Examples include SK-1, AL-5, and AL-7. Further, the plastic film may be subjected to mat treatment or corona treatment, and a release layer may be formed on the treated surface. Moreover, when using copper foil as a support body, you may utilize this copper foil as a conductor layer, without peeling. Although the thickness of a support body is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers.
本発明における「熱硬化性樹脂組成物の硬化物で形成された硬化物層」は、熱硬化性樹脂組成物を熱硬化して得られるものであり、熱硬化性樹脂組成物としては、多層プリント配線板の絶縁層に適するものであれば、特に制限なく使用できる。かかる熱硬化性樹脂組成物の具体例としては、エポキシ樹脂、シアネートエステル樹脂、フェノール樹脂、ビスマレイミドートリアジン樹脂、ポリイミド樹脂、アクリル樹脂、ビニルベンジル樹脂等の熱硬化性樹脂とその硬化剤とを、少なくとも含有する組成物が挙げられる。それらの中でも、熱硬化性樹脂としてエポキシ樹脂を含有する組成物が好ましく、例えば、エポキシ樹脂、熱可塑性樹脂及び硬化剤を含有する組成物が好ましい。 The “cured product layer formed of a cured product of a thermosetting resin composition” in the present invention is obtained by thermosetting a thermosetting resin composition. If it is suitable for the insulating layer of a printed wiring board, it can be used without a restriction | limiting in particular. Specific examples of such a thermosetting resin composition include an epoxy resin, a cyanate ester resin, a phenol resin, a bismaleimide-triazine resin, a polyimide resin, an acrylic resin, a vinylbenzyl resin, and a thermosetting resin. And a composition containing at least. Among them, a composition containing an epoxy resin as the thermosetting resin is preferable, and for example, a composition containing an epoxy resin, a thermoplastic resin, and a curing agent is preferable.
エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、リン含有エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、ビスフェノールのジグリシジルエーテル化物、ナフタレンジオールのジグリシジルエーテル化物、フェノール類のグリシジルエーテル化物、及びアルコール類のジグリシジルエーテル化物、並びにこれらのエポキシ樹脂のアルキル置換体、ハロゲン化物及び水素添加物等が挙げられる。これらのエポキシ樹脂は、いずれか１種のみを単独で使用してもよく、２種以上を混合して使用してもよい。 Examples of the epoxy resin include bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, and alicyclic epoxy resin. , Aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, epoxy resin having butadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, phenol Glycidyl etherified products of alcohols, diglycidyl etherified products of alcohols, and alkyl-substituted products, halides and hydrogenated products of these epoxy resins. It is. These epoxy resins may be used alone or in combination of two or more.
エポキシ樹脂は、これらの中でも、耐熱性、絶縁信頼性、金属膜との密着性の観点からビスフェノールＡ型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂が好ましい。かかるエポキシ樹脂の具体例としては、液状ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「エピコート８２８ＥＬ」）、ナフタレン型２官能エポキシ樹脂（大日本インキ化学工業（株）製「ＨＰ４０３２」、「ＨＰ４０３２Ｄ」 ）、ナフタレン型４官能エポキシ樹脂（大日本インキ化学工業（株）製「ＨＰ４７００」）、ナフトール型エポキシ樹脂（東都化成（株）製「ＥＳＮ−４７５Ｖ」）、ブタジエン構造を有するエポキシ樹脂（ダイセル化学工業（株）製「ＰＢ−３６００」）、ビフェニル構造を有するエポキシ樹脂（日本化薬（株）製「ＮＣ３０００Ｈ」、「ＮＣ３０００Ｌ」、ジャパンエポキシレジン（株）製「ＹＸ４０００」）などが挙げられる。 Among these, epoxy resins are bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, epoxy having a butadiene structure, from the viewpoint of heat resistance, insulation reliability, and adhesion to a metal film. Resins are preferred. Specific examples of such an epoxy resin include a liquid bisphenol A type epoxy resin (“Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.), a naphthalene type bifunctional epoxy resin (“HP4032” manufactured by Dainippon Ink and Chemicals, Inc.), “ HP4032D "), naphthalene type tetrafunctional epoxy resin (" HP4700 "manufactured by Dainippon Ink & Chemicals, Inc.), naphthol type epoxy resin (" ESN-475V "manufactured by Tohto Kasei Co., Ltd.), epoxy resin having a butadiene structure ( "PB-3600" manufactured by Daicel Chemical Industries, Ltd.), epoxy resins having a biphenyl structure ("NC3000H", "NC3000L" manufactured by Nippon Kayaku Co., Ltd., "YX4000" manufactured by Japan Epoxy Resins Co., Ltd.), etc.) It is done.
熱硬化性樹脂組成物には、硬化後の樹脂組成物に適度な可携性を付与すること等を目的として、熱可塑性樹脂を配合することができる。かかる熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリイミド、ポリアミドイミド、ポリエーテルスルホン、ポリスルホン等が挙げられる。これらの熱可塑性樹脂は、いずれか1 種のみを単独で使用してもよく、２種以上を併用してもよい。当該熱可塑性樹脂は、熱硬化性樹脂組成物の不揮発成分を１００質量％としたとき、０．５〜６０質量％の割合で配合するのが好ましく、３〜５０質量％の割合で配合するのがより好ましい。 A thermoplastic resin can be blended with the thermosetting resin composition for the purpose of imparting moderate portability to the cured resin composition. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone, polysulfone, and the like. Any one of these thermoplastic resins may be used alone, or two or more thereof may be used in combination. The thermoplastic resin is preferably blended at a rate of 0.5 to 60% by weight, preferably 3 to 50% by weight, when the nonvolatile component of the thermosetting resin composition is 100% by weight. Is more preferable.
フェノキシ樹脂の市販品としては、例えば、東都化成（株）製ＦＸ２８０、ＦＸ２９３、ジャパンエポキシレジン（株）製ＹＸ８１００、ＹＬ６９５４、ＹＬ６９７４等が挙げられる。 Examples of commercially available phenoxy resins include FX280 and FX293 manufactured by Toto Kasei Co., Ltd., YX8100, YL6954, and YL6974 manufactured by Japan Epoxy Resin Co., Ltd.
ポリビニルアセタール樹脂としては、ポリビニルブチラール樹脂が好ましく、かかるポリビニルアセタール樹脂の市販品としては、例えば、電気化学工業（株）製、電化ブチラール４０００−２、５０００−Ａ、６０００−Ｃ、６０００−ＥＰ、積水化学工業（株）製エスレックＢＨシリーズ、ＢＸシリーズ、ＫＳシリーズ、ＢＬシリーズ、ＢＭシリーズ等が挙げられる。 As the polyvinyl acetal resin, a polyvinyl butyral resin is preferable. Examples of commercially available polyvinyl acetal resin include, for example, Denka Butyral 4000-2, 5000-A, 6000-C, 6000-EP, manufactured by Denki Kagaku Kogyo Co., Ltd. Sekisui Chemical Co., Ltd. S REC BH series, BX series, KS series, BL series, BM series, etc. are mentioned.
ポリイミドの市販品としては、例えば、新日本理化（株）製のポリイミド「リカコートＳＮ２０」及び「リカコートＰＮ２０」が挙げられる。また、２官能性ヒドロキシル基末端ポリブタジエン、ジイソシアネート化合物及び四塩基酸無水物を反応させて得られる線状ポリイミド（特開２００６−３７０８３号公報に記載のもの）、ポリシロキサン骨格含有ポリイミド（特開２００２−１２６６７号公報、特開２０００−３１９３８６号公報等に記載のもの）等の変性ポリイミドが挙げられる。 As a commercial item of polyimide, for example, polyimide “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. may be mentioned. Also, linear polyimides (described in JP-A-2006-37083) obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, and polysiloxane skeleton-containing polyimides (JP-A-2002). Modified polyimides such as those described in JP-A No. 12667 and JP-A No. 2000-319386.
ポリアミドイミドの市販品としては、例えば、東洋紡績（株）製のポリアミドイミド「バイロマックスＨＲ１１ＮＮ」及び「バイロマックスＨＲ１６ＮＮ」が挙げられる。また日立化成工業（株）製のポリシロキサン骨格含有ポリアミドイミド「ＫＳ９１００」、「ＫＳ９３００」等の変性ポリアミドイミドが挙げられる。 Examples of commercially available polyamideimides include polyamideimides “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd. Further, modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd. may be mentioned.
ポリエーテルスルホンの市販品としては、例えば、住友化学（株）社製のポリエーテルスルホン「ＰＥＳ５００３Ｐ」等が挙げられる。 Examples of commercially available products of polyethersulfone include polyethersulfone “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
ポリスルホンの市販品としては、例えば、ソルベンアドバンストポリマーズ（株）社製のポリスルホン「Ｐ１７００」、「Ｐ３５００」等が挙げられる。 Examples of commercially available products of polysulfone include polysulfone “P1700” and “P3500” manufactured by Solven Advanced Polymers Co., Ltd.
硬化剤としては、例えば、アミン系硬化剤、グアニジン系硬化剤、イミダゾール系硬化剤、フェノール系硬化剤、ナフトール系硬化剤、酸無水物系硬化剤又はこれらのエポキシアダクトやマイクロカプセル化したもの、シアネートエステル樹脂等が挙げられる。それらの中でも、フェノール系硬化剤、ナフトール系硬化剤、シアネートエステル樹脂が好ましい。これらの硬化剤は、いずれか１種のみを単独で使用してもよく、２種以上を併用してもよい。 Examples of the curing agent include amine-based curing agents, guanidine-based curing agents, imidazole-based curing agents, phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, or epoxy adducts and microcapsules thereof. Examples include cyanate ester resins. Among these, a phenol type curing agent, a naphthol type curing agent, and a cyanate ester resin are preferable. These curing agents may be used alone or in combination of two or more.
フェノール系硬化剤、ナフトール系硬化剤の市販品としては、例えば、ＭＥＨ−７７００、ＭＥＨ−７８１０、ＭＥＨ−７８５１（明和化成（株）製）、ＮＨＮ、ＣＢＮ、ＧＰＨ（日本化薬（株）製）、ＳＮ１７０、ＳＮ１８０、ＳＮ１９０、ＳＮ４７５、ＳＮ４８５、ＳＮ４９５、ＳＮ３７５、ＳＮ３９５（東都化成（株）製）、ＬＡ７０５２、ＬＡ７０５４、ＬＡ３０１８、ＬＡ１３５６ （大日本インキ化学工業（株）製）等が挙げられる。 As a commercial item of a phenol type hardening | curing agent and a naphthol type hardening | curing agent, for example, MEH-7700, MEH-7810, MEH-7851 (made by Meiwa Kasei Co., Ltd.), NHN, CBN, GPH (made by Nippon Kayaku Co., Ltd.) ), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.), LA7052, LA7054, LA3018, LA1356 (manufactured by Dainippon Ink & Chemicals, Inc.), and the like.
シアネートエステル樹脂としては、例えば、ビスフェノールＡジシアネート、ポリフエノールシアネート（オリゴ（３−メチレン−１，５ −フェニレンシアネート）、４，４’−メチレンビス（２，６−ジメチルフェニルシアネート）、４，４’−エチリデンジフェニルジシアネート、へキサフルオロビスフエノールＡジシアネート、２，２−ビス（４−シアネート）フェニルプロパン、１，１−ビス（４−シアネートフェニルメタン）、ビス（４−シアネート−３，５−ジメチルフェニル）メタン、１，３−ビス（４−シアネートフェニル−１−(メチルエチリデン））べンゼン、ビス（４−シアネートフェニル）チオエーテル、ビス（４−シアネートフェニル）エーテル等の２官能シアネート樹脂、フェノールノボラック、クレゾールノボラック等から誘導される多官能シアネート樹脂、これらシアネート樹脂が一部トリアジン化したプレポリマー等が挙げられる。かかるシアネートエステル樹脂の具体例としては、フェノールノボラック型多官能シアネートエステル樹脂（ロンザジャパン（株）製「ＰＴ３０」、シアネート当量１２４）やビスフェノールＡジシアネートの一部又は全部がトリアジン化され三量体となったプレポリマー（ロンザジャパン（株）製「ＢＡ２３０」、シアネート当量２３２）等が挙げられる。 Examples of the cyanate ester resin include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4 ′. Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, Phenol novolac, cresolno Examples thereof include polyfunctional cyanate resins derived from racks, prepolymers in which these cyanate resins are partially triazines, etc. Specific examples of such cyanate ester resins include phenol novolac type polyfunctional cyanate ester resins (Lonza Japan Ltd.). ) “PT30”, cyanate equivalent 124), or a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer (“BA230” manufactured by Lonza Japan Co., Ltd., cyanate equivalent 232), and the like. .
エポキシ樹脂と硬化剤の配合比率は、フェノール系硬化剤又はナフトール系硬化剤を用いる場合は、エポキシ樹脂のエポキシ当量１に対してこれら硬化剤のフェノール性水酸基当量が０．４〜２．０の範囲となる比率が好ましく、より好ましくは０．５〜１．０の範囲となる比率である。シアネートエステル樹脂を用いる場合は、エポキシ当量１に対してシアネート当量が０．３〜３．３の範囲となる比率が好ましく、０．５〜２．０の範囲となる比率がより好ましい。 The mixing ratio of the epoxy resin and the curing agent is such that when a phenolic curing agent or a naphthol curing agent is used, the phenolic hydroxyl group equivalent of these curing agents is 0.4 to 2.0 with respect to the epoxy equivalent 1 of the epoxy resin. The ratio that is in the range is preferable, and the ratio that is in the range of 0.5 to 1.0 is more preferable. When a cyanate ester resin is used, a ratio in which the cyanate equivalent is in the range of 0.3 to 3.3 with respect to the epoxy equivalent 1 is preferable, and a ratio in the range of 0.5 to 2.0 is more preferable.
熱硬化性樹脂組成物には、硬化剤に加え、硬化促進剤をさらに含有させることができる。かかる硬化促進剤としては、例えば、イミダゾール系化合物、有機ホスフイン系化合物等が挙げられ、具体例としては、２−メチルイミダゾール、トリフェニルホスフイン等が挙げられる。硬化促進剤を用いる場合、硬化促進剤はエポキシ樹脂に対して０．１〜３．０質量％の範囲で用いるのが好ましい。なお、エポキシ樹脂硬化剤としてシアネートエステル樹脂を使用する場合には、硬化時間を短縮する目的で、従来からエポキシ樹脂組成物とシアネート化合物とを併用した系において硬化触媒として用いられている有機金属化合物を、添加してもよい。このような有機金属化合物としては、例えば、銅（ＩＩ）アセチルアセトナート等の有機銅化合物、亜鉛（ＩＩ）アセチルアセトナート等の有機亜鉛化合物、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナート等の有機コバルト化合物などが挙げられる。これらの有機金属化合物は、いずれか１種のみを単独で使用してもよく、２種以上を併用してもよい。有機金属化合物の添加量は、シアネートエステル樹脂に対し、金属換算で通常１０〜５００ｐｐｍの範囲であることが好ましく、２５〜２００ｐｐｍの範囲であることがより好ましい。 The thermosetting resin composition may further contain a curing accelerator in addition to the curing agent. Examples of such curing accelerators include imidazole compounds and organic phosphine compounds, and specific examples include 2-methylimidazole and triphenylphosphine. When using a hardening accelerator, it is preferable to use a hardening accelerator in 0.1-3.0 mass% with respect to an epoxy resin. In addition, when using a cyanate ester resin as an epoxy resin curing agent, an organometallic compound that has been used as a curing catalyst in a conventional system in which an epoxy resin composition and a cyanate compound are used together for the purpose of shortening the curing time. May be added. Examples of such organometallic compounds include organic copper compounds such as copper (II) acetylacetonate, organic zinc compounds such as zinc (II) acetylacetonate, cobalt (II) acetylacetonate, and cobalt (III) acetyl. Examples include organic cobalt compounds such as acetonate. These organometallic compounds may be used alone or in combination of two or more. The amount of the organometallic compound added is usually in the range of 10 to 500 ppm, more preferably in the range of 25 to 200 ppm in terms of metal relative to the cyanate ester resin.
また、熱硬化性樹脂組成物には、硬化後の樹脂組成物の低熱膨張化のために、無機充填剤を含有させることができる。かかる無機充填剤としては、例えば、シリカ、アルミナ、雲母、マイカ、珪酸塩、硫酸バリウム、水酸化マグネシウム、酸化チタン等が挙げられ、これらの中でも、シリカ、アルミナが好ましく、シリカが特に好ましい。なお、無機充填剤の平均粒径は、絶縁信頼性の観点から、３μｍ以下が好ましく、１．５μｍ以下が特に好ましい。無機充填剤の含有量は、熱硬化性樹脂組成物の不揮発成分を１００質量％とした時、好ましくは２０〜７０質量％であり、より好ましくは３０〜７０質量％である。 Further, the thermosetting resin composition can contain an inorganic filler in order to reduce the thermal expansion of the cured resin composition. Examples of the inorganic filler include silica, alumina, mica, mica, silicate, barium sulfate, magnesium hydroxide, titanium oxide, and the like. Among these, silica and alumina are preferable, and silica is particularly preferable. The average particle size of the inorganic filler is preferably 3 μm or less, and particularly preferably 1.5 μm or less, from the viewpoint of insulation reliability. The content of the inorganic filler is preferably 20 to 70% by mass and more preferably 30 to 70% by mass when the nonvolatile component of the thermosetting resin composition is 100% by mass.
さらに、熱硬化性樹脂組成物には、必要に応じて他の成分を含有させることができる。他の成分としては、例えば、有機リン系難燃剤、有機系窒素含有リン化合物、窒素化合物、シリコン系難燃剤、金属水酸化物等の難燃剤；シリコンパウダー、ナイロンパウダー、フッ素パウダー等の有機充填剤；オルべン、ベントン等の増粘剤；シリコン系、フッ素系等の高分子系消泡剤又はレベリング剤；イミダゾール系、チアゾール系、トリアゾール系、シラン系カップリング剤等の密着性付与剤；フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、カーボンブラック等の着色剤等が挙げられる。 Furthermore, the thermosetting resin composition can contain other components as necessary. Other components include, for example, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon flame retardants, flame retardants such as metal hydroxides; organic filling such as silicon powder, nylon powder, fluorine powder, etc. Agents: Thickeners such as Orben and Benton; Silicone and fluorine polymer defoamers or leveling agents; Adhesive agents such as imidazole, thiazole, triazole and silane coupling agents Colorants such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and the like.
ワニスを調製する場合の有機溶剤としては、例えば、アセトン、メチルエチルケトン、シクロへキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類、セロソルブ、ブチルカルビトール等のカルビトール類、トルエン、キシレン等の芳香族炭化水素類、ジメチルホルムアミド、ジメチルアセトアミド、N ーメチルピロリドン等を挙げることができる。有機溶剤は２種以上を組み合わせて用いてもよい。 Examples of the organic solvent for preparing the varnish include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and cellosolve. Carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Two or more organic solvents may be used in combination.
本発明の絶縁樹脂シートにおける硬化物層の形成は、例えば、支持体上に熱硬化性樹脂組成物層が形成された樹脂シートの熱硬化性樹脂組成物を熱硬化する方法が挙げられる。樹脂シートは、当業者に公知の方法、例えば、有機溶剤に熱硬化性樹脂組成物を溶解した樹脂ワニスを調製し、支持体上に該樹脂ワニスを塗布し、熱風吹きつけ等により加熱し、有機溶剤を乾燥させて熱硬化性樹脂組成物層を形成させることにより製造することができる。また、支持体上に塗布された該樹脂ワニスを加熱し、乾燥及び硬化を同時又は逐次的に行なうことで、熱硬化性樹脂組成物の硬化物層を形成することもできる。 The formation of the cured product layer in the insulating resin sheet of the present invention includes, for example, a method of thermosetting a thermosetting resin composition of a resin sheet in which a thermosetting resin composition layer is formed on a support. The resin sheet is a method known to those skilled in the art, for example, preparing a resin varnish in which a thermosetting resin composition is dissolved in an organic solvent, applying the resin varnish on a support, and heating by blowing hot air or the like. It can manufacture by drying an organic solvent and forming a thermosetting resin composition layer. Moreover, the hardened | cured material layer of a thermosetting resin composition can also be formed by heating this resin varnish apply | coated on the support body, and performing drying and hardening simultaneously or sequentially.
熱硬化性樹脂組成物の硬化物層の厚みは、通常１〜５０μｍの範囲であり、１〜４０μｍとするのが好ましく、１〜３０μｍとするのがより好ましい。薄すぎると硬化物層の製造が困難となる。また厚すぎると多層プリント配線板の薄型化に不利となる。なお厚みは熱硬化性樹脂組成物の支持体への塗布量を調整することにより、容易にコントロールする事が出来る。 The thickness of the cured product layer of the thermosetting resin composition is usually in the range of 1 to 50 μm, preferably 1 to 40 μm, and more preferably 1 to 30 μm. If it is too thin, it becomes difficult to produce a cured product layer. Moreover, when too thick, it will become disadvantageous for thickness reduction of a multilayer printed wiring board. The thickness can be easily controlled by adjusting the amount of the thermosetting resin composition applied to the support.
本発明における「接着層」は、内層回路基板に絶縁樹脂シートを接着させ、また熱硬化することにより、硬化物層と共に絶縁層を形成する層である。接着層は熱硬化性樹脂組成物から形成される。熱硬化性樹脂組成物としては、多層プリント配線板の絶縁層に適するものであれば、特に制限なく使用でき、前記「熱硬化性樹脂組成物の硬化物層」に使用する熱硬化性樹脂組成物と同様のものを使用することができる。硬化物層に使用する熱硬化性樹脂組成物と接着層に使用する熱硬化性樹脂組成物は同じものを使用してもよく、異なるものを使用してもよい。 The “adhesive layer” in the present invention is a layer that forms an insulating layer together with a cured product layer by adhering an insulating resin sheet to an inner layer circuit board and thermally curing the same. The adhesive layer is formed from a thermosetting resin composition. The thermosetting resin composition can be used without particular limitation as long as it is suitable for the insulating layer of the multilayer printed wiring board, and the thermosetting resin composition used for the “cured material layer of the thermosetting resin composition”. The thing similar to a thing can be used. The thermosetting resin composition used for the cured product layer and the thermosetting resin composition used for the adhesive layer may be the same or different.
接着層の厚みは通常５〜２００μｍの範囲であるが、薄型化に適した絶縁樹脂シートとするには、５〜５０μｍの範囲が好ましく、５〜４０μｍの範囲がより好ましく、５〜３０μｍの範囲がより好ましい。接着層の厚みが薄すぎると絶縁層を形成する上で回路の埋め込みが不十分となる傾向があり、また製造も困難である。また接着層の厚みが厚すぎると、多層プリント配線板の薄型化に不利になる。 The thickness of the adhesive layer is usually in the range of 5 to 200 μm, but in order to obtain an insulating resin sheet suitable for thinning, the range of 5 to 50 μm is preferable, the range of 5 to 40 μm is more preferable, and the range of 5 to 30 μm. Is more preferable. If the thickness of the adhesive layer is too thin, circuit embedding tends to be insufficient in forming the insulating layer, and manufacturing is difficult. Moreover, when the thickness of the adhesive layer is too thick, it is disadvantageous for making the multilayer printed wiring board thinner.
本発明の絶縁樹脂シートは、先ず、硬化物層を構成する熱硬化性樹脂組成物を有機溶剤に溶解して樹脂ワニスとした後、これを支持体層上に塗布し、熱風吹き付け等により溶剤を乾燥させて、既述の所定の厚みで硬化物層を形成する事が出来る。また、支持体上に塗布された該樹脂ワニスを加熱し、乾燥及び硬化を同時又は逐次的に行なうことで、熱硬化性樹脂組成物の硬化物層を形成することもできる。次に、硬化物層の上に接着層を構成する熱硬化性樹脂組成物を有機溶剤に溶解した樹脂ワニスを塗布し、熱風吹き付け等により溶剤を乾燥させて、既述の所定の厚みで接着層を形成することで絶縁樹脂シートが製造される。 The insulating resin sheet of the present invention is prepared by first dissolving the thermosetting resin composition constituting the cured product layer in an organic solvent to form a resin varnish, and then applying the solution onto the support layer and spraying with hot air or the like. Can be dried to form a cured product layer with the predetermined thickness described above. Moreover, the hardened | cured material layer of a thermosetting resin composition can also be formed by heating this resin varnish apply | coated on the support body, and performing drying and hardening simultaneously or sequentially. Next, a resin varnish in which the thermosetting resin composition constituting the adhesive layer is dissolved in an organic solvent is applied on the cured product layer, and the solvent is dried by hot air blowing or the like, and bonded to the predetermined thickness described above. An insulating resin sheet is manufactured by forming a layer.
また硬化物層を塗布形成し、続いて接着層を塗布形成し、更に接着層の硬化物層と密着していない面に支持体層に準じた保護フィルムを更に積層することで、支持体層／硬化物層／接着層／保護フィルムという構成の絶縁樹脂シートとして製造される。かかる積層構成の絶縁樹脂シートはロール状に巻き取って貯蔵することも出来る。また、保護フィルムで接着層を保護することで、接着層表面へのゴミ等の付着や傷を防止する事ができ、かかる絶縁樹脂シート用いて製造されるプリント配線板の信頼性向上にも有効である。ここで、保護フィルムとしては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン、ポリエチレンテレフタレート等のポリエステル、ポリカーボネート、ポリイミド、更には離型紙、アルミニウム箔等を挙げる事が出来る。なお、保護フィルムはマッド処理、コロナ処理、シリコン系離型フィルム層を設けるなどの離型処理を施してあってもよい。また保護フィルムの厚みは１〜４０μｍとするのが好ましい。 Also, a support layer is formed by coating and forming a cured product layer, subsequently applying and forming an adhesive layer, and further laminating a protective film according to the support layer on the surface of the adhesive layer that is not in close contact with the cured product layer. It is manufactured as an insulating resin sheet having a structure of / hardened product layer / adhesive layer / protective film. The insulating resin sheet having such a laminated structure can be wound and stored in a roll shape. In addition, by protecting the adhesive layer with a protective film, it is possible to prevent adhesion and scratches of dust etc. on the surface of the adhesive layer, which is also effective for improving the reliability of printed wiring boards manufactured using such insulating resin sheets. It is. Here, examples of the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonate, polyimide, release paper, and aluminum foil. The protective film may be subjected to a release treatment such as a mud treatment, a corona treatment, or a silicon release film layer. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.
また他の絶縁樹脂シートの態様としては、支持体層上に硬化物層を塗布形成した積層フィルムと、支持体層上に接着層を塗布形成した積層フィルムを各々形成しておき、その後、硬化物層と接着層を張り合わせることで、支持体層／硬化物層／接着層／支持体層という構成の絶縁樹脂シートを得る事が出来る。この場合、接着層と隣接する支持体層が保護フィルムとなる。この場合、接着層と隣接する支持体層の接着層側には、剥離を容易にするために、離型処理が施されている事が好ましい。 Further, as other embodiments of the insulating resin sheet, a laminated film in which a cured product layer is applied and formed on a support layer and a laminated film in which an adhesive layer is applied and formed on a support layer are formed, and then cured. By laminating the physical layer and the adhesive layer, an insulating resin sheet having a structure of support layer / cured product layer / adhesive layer / support layer can be obtained. In this case, the support layer adjacent to the adhesive layer is a protective film. In this case, it is preferable that a release treatment is performed on the adhesive layer side of the support layer adjacent to the adhesive layer in order to facilitate peeling.
硬化物層において、熱硬化性樹脂組成物は必ずしも完全に熱硬化されている必要はなく、本発明の効果が発揮される程度に硬化されていればよい。一般に、層間絶縁層形成に用いられる、支持体と熱硬化性樹脂組成物からなる接着シートは、内層回路基板への積層により回路の埋め込みを行う必要があるため、十分な流動性を有する必要がある。一方、本発明における熱硬化性樹脂組成物の硬化物層は、絶縁層厚みを確保するために、積層工程及び平滑化工程又は熱プレス工程で流動性をほとんど有しないことが重要であり、実施的に流動性を有しないのがより好ましい。 In the cured product layer, the thermosetting resin composition does not necessarily need to be completely thermoset, and may be cured to such an extent that the effect of the present invention is exhibited. In general, an adhesive sheet made of a support and a thermosetting resin composition used for forming an interlayer insulating layer needs to have sufficient fluidity because it is necessary to embed a circuit by lamination on an inner circuit board. is there. On the other hand, it is important that the cured product layer of the thermosetting resin composition in the present invention has almost no fluidity in the laminating step and the smoothing step or the hot pressing step in order to ensure the insulating layer thickness. It is more preferable that it does not have fluidity.
熱硬化性樹脂組成物の硬化の程度は、ガラス転移温度によって評価することができる。本願発明においては、少なくとも硬化物のガラス転移温度が観測される程度まで硬化するのが好ましい。一般に、層間絶縁層形成に用いられる、支持体と熱硬化性樹脂組成物からなる接着シートは、上述したように流動性を有し、例えば熱硬化性樹脂組成物層がＢステージであっても、反応度は著しく低く、通常ガラス転移温度を測定することは不可能であり、少なくとも室温以下のガラス転移温度となる。一般に、ガラス転移温度が観測される程度まで硬化された場合、一般の積層工程の温度及び平滑化工程の温度（７０〜１４０℃）範囲では、熱硬化性樹脂組成物が実質的に流動性を有しないか、又はほとんど流動性を有しない。これらの点で、一般の接着シートと本発明における硬化物シートとは明確に区別される。硬化物のガラス転移温度は８０℃以上であるのが好ましく、さらには１００℃以上であるのがより好ましい。なお、ガラス転移温度の上限は特に限定されず、一般には硬化した熱硬化性樹脂組成物のガラス転移温度は、３００℃以下の範囲に収まることが多い。 The degree of curing of the thermosetting resin composition can be evaluated by the glass transition temperature. In this invention, it is preferable to harden at least to such an extent that the glass transition temperature of hardened | cured material is observed. In general, an adhesive sheet made of a support and a thermosetting resin composition used for forming an interlayer insulating layer has fluidity as described above, for example, even if the thermosetting resin composition layer is a B stage. The reactivity is extremely low, and it is usually impossible to measure the glass transition temperature, and the glass transition temperature is at least room temperature or lower. Generally, when cured to such an extent that the glass transition temperature is observed, the thermosetting resin composition substantially exhibits fluidity in the temperature range of the general lamination process and the temperature of the smoothing process (70 to 140 ° C.). Has little or no fluidity. From these points, the general adhesive sheet and the cured product sheet in the present invention are clearly distinguished. The glass transition temperature of the cured product is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher. The upper limit of the glass transition temperature is not particularly limited, and generally the glass transition temperature of the cured thermosetting resin composition often falls within the range of 300 ° C. or less.
ここでいう「ガラス転移温度」とは、耐熱性を示す値であり、JISK7179 に記載の方法にしたがって決定され、具体的には、熱機械分析（ＴＭＡ）、動的機械分析（ＤＭＡ）などを用いて測定される。熱機械分析（ＴＭＡ）としては、例えば、TMA-SS6100 （セイコーインスツルメンツ社製）、TMA-8310 （リガク株式会社製）などが挙げられ、動的機械分析（ＤＭＡ）としては、例えば、DMS-6100（セイコーインスツルメンツ社製）などが挙げられる。本発明では動的機械分析（ＤＭＡ）で測定した値を採用する。また、ガラス転移温度が分解温度よりも高く、実際にはガラス転移温度が観測されない場合には、分解温度を本発明におけるガラス転移温度とみなすことができる。ここでいう分解温度とは、JISK7120 に記載の方法にしたがって測定したときの質量減少率が５％となる温度で定義される。 The “glass transition temperature” here is a value indicating heat resistance, and is determined according to the method described in JISK7179. Specifically, thermomechanical analysis (TMA), dynamic mechanical analysis (DMA), etc. Measured. Examples of thermomechanical analysis (TMA) include TMA-SS6100 (manufactured by Seiko Instruments Inc.) and TMA-8310 (manufactured by Rigaku Corporation). Examples of dynamic mechanical analysis (DMA) include DMS-6100. (Manufactured by Seiko Instruments Inc.). In the present invention, values measured by dynamic mechanical analysis (DMA) are adopted. Further, when the glass transition temperature is higher than the decomposition temperature and the glass transition temperature is not actually observed, the decomposition temperature can be regarded as the glass transition temperature in the present invention. The decomposition temperature here is defined as the temperature at which the mass reduction rate is 5% when measured according to the method described in JISK7120.
以下、本発明の絶縁樹脂シートを使用した多層プリント配線板の製造方法について詳しく説明する。 Hereinafter, the manufacturing method of the multilayer printed wiring board using the insulating resin sheet of this invention is demonstrated in detail.
本発明においては、支持体層、該支持体層上に熱硬化性樹脂組成物を硬化して形成された硬化物層、及び該硬化物層上に熱硬化性樹脂組成物で形成された接着層を有する絶縁樹脂シートを、接着層を回路基板側にして、回路基板の片面又は両面に積層する工程、積層された絶縁樹脂シートを金属板により加熱及び加圧して平滑化する工程、平滑化された絶縁樹脂シートを熱硬化することにより、絶縁層を熱硬化する工程を少なくとも経て多層プリント配線板を製造する。 In the present invention, a support layer, a cured product layer formed by curing a thermosetting resin composition on the support layer, and an adhesion formed with the thermosetting resin composition on the cured product layer A step of laminating an insulating resin sheet having a layer on one or both sides of the circuit board with the adhesive layer facing the circuit board, a step of smoothing the laminated insulating resin sheet by heating and pressing with a metal plate, smoothing By thermally curing the insulating resin sheet thus obtained, a multilayer printed wiring board is manufactured through at least a process of thermosetting the insulating layer.
積層工程においては、絶縁樹脂シートを加熱及び加圧し、内層回路基板に積層する。積層工程における当該加熱及び加圧は、加熱されたSUS鏡板等の金属板を支持体層側からプレスすることにより行うことが出来る。その際、金属板を直接プレスするのではなく、内層回路基板の回路凸凹に絶縁樹脂シートが十分に追随するよう、耐熱ゴム等の弾性材を介してプレスするのが好ましい。金属板と弾性材は必ずしも接している必要は無く、金属板と弾性材間に空気を存在させ、圧縮空気により弾性材に圧力を掛けてプレスすることで積層を行っても良い。なお、かかるプレスの温度は、好ましくは７０〜１４０℃であり、より好ましくは８０〜１３０℃である。また掛かるプレス圧力については１〜１１ｋｇｆ／ｃｍ２（９．８×１０４〜１０７．９×１０４N／ｍ２）の範囲内にあることが望ましい。一般に積層工程は、ボイドが発生することを防ぐために減圧下で行われ、その空気圧は２０ｍｍＨｇ（２６．７ｈＰａ）以下の減圧下であることが好ましい。 In the laminating step, the insulating resin sheet is heated and pressurized to be laminated on the inner layer circuit board. The heating and pressurization in the laminating step can be performed by pressing a heated metal plate such as a SUS mirror plate from the support layer side. In that case, it is preferable not to press the metal plate directly, but to press it through an elastic material such as heat-resistant rubber so that the insulating resin sheet sufficiently follows the circuit unevenness of the inner layer circuit board. The metal plate and the elastic material are not necessarily in contact with each other, and lamination may be performed by causing air to exist between the metal plate and the elastic material and applying pressure to the elastic material with compressed air and pressing. In addition, the temperature of this press becomes like this. Preferably it is 70-140 degreeC, More preferably, it is 80-130 degreeC. The pressing pressure applied is preferably in the range of 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 10 4 N / m 2 ). In general, the lamination step is performed under reduced pressure in order to prevent the generation of voids, and the air pressure is preferably 20 mmHg (26.7 hPa) or less.
積層工程の後、好ましくは金属板又は金属ロールによる熱プレスにより、積層された絶縁樹脂シートの平滑化を行う。該平滑化工程は、加熱されたＳＵＳ鏡板等の金属板又は金属ロールを用いて、絶縁樹脂シートを加熱及び加圧することにより行われる。該平滑化工程は、常圧下（大気圧下）で行うのが好ましい。また平滑化工程は金属板により行うのが好ましい。加熱及び加圧条件としては上記積層工程と同様の条件を用いることが出来る。 After the lamination step, the laminated insulating resin sheets are preferably smoothed by hot pressing with a metal plate or a metal roll. The smoothing step is performed by heating and pressurizing the insulating resin sheet using a heated metal plate such as a SUS mirror plate or a metal roll. The smoothing step is preferably performed under normal pressure (atmospheric pressure). The smoothing step is preferably performed with a metal plate. As heating and pressurizing conditions, the same conditions as in the laminating step can be used.
本発明における積層工程及び平滑化工程は、市販されている真空ラミネーターによって連続的に行うことが出来る。市販されている真空ラミネーターとしては、たとえば（株）名機製作所製真空加圧式ラミネーター、ニチゴー・モートン（株）製バキューム・アプリケータなどが上げられる。 The laminating step and the smoothing step in the present invention can be continuously performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.
積層工程及び平滑化工程は別々の装置を用いて行っても良い。この場合、積層工程は前述の真空ラミネーターのほか、ロールラミネータなどを使用して行うことも出来る。平滑化工程は真空プレスを用いることが出来る。真空プレスは市販されている通常の電気絶縁材料用積層板及び多層板製造用の装置が適用でき、例えば多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等が使用でき、成形条件としては通常、温度１００〜２５０℃、圧力２〜１００ｋｇ／ｃｍ２、加熱時間０．１〜３時間の範囲で成形することが出来る。 You may perform a lamination process and a smoothing process using a separate apparatus. In this case, the laminating process can be performed using a roll laminator or the like in addition to the vacuum laminator described above. The smoothing process can use a vacuum press. Vacuum presses can be applied to commercially available ordinary laminates for electrical insulation materials and multilayer boards. For example, multi-stage presses, multi-stage vacuum presses, continuous molding, autoclave molding machines, etc. can be used. , Temperature 100 to 250 ° C., pressure 2 to 100 kg / cm 2 , heating time 0.1 to 3 hours.
回路基板に積層された絶縁樹脂シートを熱硬化処理する。熱硬化の条件は硬化性樹脂の種類によっても異なるが、一般的に１５０〜２００℃、硬化時間が１５〜６０分である。なお、比較的低い温度から高い温度へ上昇させながら硬化した方が形成される絶縁層表面のシワ防止の観点から好ましい。また支持体層を硬化物層の熱硬化後に剥離する場合は、樹脂と支持体層の熱膨張係数が異なる事を考慮して２段階硬化、すなわち、まず８０〜１３０℃で１５〜６０分、次いで１７０〜２００℃で１５〜６０分の２段階の硬化処理をした後に支持体層を剥離するのが好ましい。なお、離型処理の施された支持体層を使用した場合には、加熱処理させた後に支持体層を剥離しても良い。 The insulating resin sheet laminated on the circuit board is heat-cured. The conditions for thermosetting vary depending on the type of curable resin, but are generally 150 to 200 ° C. and the curing time is 15 to 60 minutes. In addition, it is preferable from the viewpoint of preventing wrinkles on the surface of the insulating layer that is formed while being cured while being raised from a relatively low temperature to a high temperature. Moreover, when peeling a support body layer after thermosetting of a hardened | cured material layer, considering that the thermal expansion coefficient of resin and a support body layer differs, two-stage hardening, ie, first, 15 to 60 minutes at 80-130 degreeC, Next, it is preferable to peel the support layer after performing a two-stage curing process at 170 to 200 ° C. for 15 to 60 minutes. In addition, when the support body layer in which the mold release process was performed is used, you may peel a support body layer, after making it heat-process.
本発明の多層プリント配線板の製造方法においては、絶縁層に穴あけする穴あけ工程、該絶縁層を粗化処理する粗化工程をさらに含んでもよい。これらの工程は、当業者に公知である、多層プリント配線板の製造に用いられている各種方法に従って行うことができる。本発明の多層プリント配線板の製造方法においては、熱硬化された絶縁樹脂シートから支持体を剥離する工程をさらに含んでもよい。支持体の剥離は熱硬化工程後又は穴あけ工程後に行うのが好ましい。支持体の剥離は、手動で剥離してもよく、自動剥離装置により機械的に剥離してもよい。支持体として金属箔を用いた場合はエッチング溶液によりエッチングすることで除去してもよい。 The method for producing a multilayer printed wiring board of the present invention may further include a drilling step for drilling an insulating layer and a roughening step for roughening the insulating layer. These steps can be performed according to various methods known to those skilled in the art and used in the production of multilayer printed wiring boards. In the manufacturing method of the multilayer printed wiring board of this invention, you may further include the process of peeling a support body from the thermosetting insulating resin sheet. Peeling of the support is preferably performed after the thermosetting process or the drilling process. The support may be peeled off manually or mechanically by an automatic peeling device. When a metal foil is used as the support, it may be removed by etching with an etching solution.
穴あけ工程は、例えば、絶縁層に、ドリル、炭酸ガスレーザー、ＹＡＧレーザー等によりビアホール、スルーホール等のホールを形成することにより行うことができる。多層プリント配線板においては、スルーホールの形成は一般にコア基板において行われ、ビルドアップされた絶縁層は一般にはビアホールにより導通が行われる。またスルーホール形成は、一般に機械ドリルが用いられる。 The drilling step can be performed, for example, by forming a hole such as a via hole or a through hole in the insulating layer with a drill, a carbon dioxide laser, a YAG laser, or the like. In a multilayer printed wiring board, formation of a through hole is generally performed in a core substrate, and a built-up insulating layer is generally conducted by a via hole. In addition, a mechanical drill is generally used for forming the through hole.
粗化工程は、例えば、絶縁層表面をアルカリ性過マンガン酸水溶液等の酸化剤で処理することにより行うことができる。該粗化工程は、ビアホール、スルーホール等のホールのデスミア工程を兼ねる場合がある。アルカリ性過マンガン酸水溶液に先立って膨潤液による膨潤処理を行うのが好ましい。膨潤液には、例えば、アトテックジャパン株式会社製のスウェリング・ディップ・セキュリガンスＰ(Swelling Dip Securiganth P）、スウェリング・ディップ・セキュリガンスＳＢＵ(Swelling Dip Securiganth SBU）等を挙げることができる。膨潤処理は、通常６０〜８０℃程度に加熱した膨潤液に絶縁層を５〜１０分程度付すことで行われる。アルカリ性過マンガン酸水溶液としては、例えば、水酸化ナトリウムの水溶液に過マンガン酸カリウムや過マンガン酸ナトリウムを溶解した溶液を挙げることができる。アルカリ性過マンガン酸水溶液による粗化処理は、通常６０〜８０℃、１０〜３０分程度付すことで行われる。アルカリ性過マンガン酸水溶液は、市販品としては、アトテックジャパン株式会社製のコンセントレートコンパクトCP 、ドージングソリューションセキュリガンスP 、等が挙げられる。 A roughening process can be performed by processing the insulating layer surface with oxidizing agents, such as alkaline permanganic acid aqueous solution, for example. The roughening process may also serve as a desmear process for holes such as via holes and through holes. Prior to the alkaline permanganate aqueous solution, the swelling treatment with a swelling liquid is preferably performed. Examples of the swelling liquid include Swelling Dip Securiganth P (Swelling Dip Securiganth S) and Swelling Dip Securiganth SBU (ABUTEC Japan). The swelling treatment is usually performed by attaching an insulating layer to the swelling liquid heated to about 60 to 80 ° C. for about 5 to 10 minutes. Examples of the alkaline permanganate aqueous solution include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with the alkaline permanganic acid aqueous solution is usually performed at 60 to 80 ° C. for about 10 to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include Concentrate Compact CP manufactured by Atotech Japan KK, Dosing Solution Securigans P, and the like.
本発明の多層プリント配線板の製造方法においては、さらに粗化された絶縁層表面にめっきにより導体層を形成するめっき工程、導体層形成後、加熱により回路基板をアニール処理する工程、及び導体層に回路を形成する回路形成工程をさらに含んでもよい。これらの工程は、当業者に公知である、多層プリント配線板の製造に用いられている各種方法に従って行うことができる。 In the method for producing a multilayer printed wiring board of the present invention, a plating step of forming a conductor layer by plating on the surface of the further roughened insulating layer, a step of annealing the circuit board by heating after forming the conductor layer, and a conductor layer A circuit forming step for forming a circuit may be further included. These steps can be performed according to various methods known to those skilled in the art and used in the production of multilayer printed wiring boards.
めっき工程は、例えば、粗化処理により凸凹のアンカーが形成された絶縁層表面に無電解めっきと電解めっきを組み合わせた方法で導体層を形成することにより行われる。この際、ビアホール内にもめっきが形成される。導体層としては銅めっき層が好ましい。銅めっき層は、無電解銅めっきと電解銅めっきを組み合わせた方法か、導体層とは逆パターンのめっきレジストを形成し、無電解銅めっきのみで導体層を形成する。無電解めっき層の厚さは、好ましくは０．１〜３μｍ 、より好ましくは０．３〜２μｍである。一方、電解めっき層の厚さとしては、無電解めっき層の厚さとの合計が３〜３５μｍとなる厚さが好ましく、５〜２０μｍとなる厚さがより好ましい。またビアホールはめっきによりフィルドビアを形成することもできる。 A plating process is performed by forming a conductor layer by the method which combined the electroless plating and the electrolytic plating on the insulating layer surface in which the uneven anchor was formed by the roughening process, for example. At this time, plating is also formed in the via hole. A copper plating layer is preferable as the conductor layer. The copper plating layer is a method in which electroless copper plating and electrolytic copper plating are combined, or a plating resist having a pattern opposite to that of the conductor layer is formed, and the conductor layer is formed only by electroless copper plating. The thickness of the electroless plating layer is preferably 0.1 to 3 μm, more preferably 0.3 to 2 μm. On the other hand, the thickness of the electroplating layer is preferably a thickness of 3 to 35 μm, more preferably 5 to 20 μm, with the total thickness of the electroless plating layer. The via hole can be filled via by plating.
アニール処理工程は、例えば、導体層形成後、回路基板を１５０〜２００℃で２０〜９０分間加熱することにより行うことができる。アニール処理することにより、導体層のピール強度をさらに向上、安定化させることができる。 The annealing treatment step can be performed, for example, by heating the circuit board at 150 to 200 ° C. for 20 to 90 minutes after forming the conductor layer. By performing the annealing treatment, the peel strength of the conductor layer can be further improved and stabilized.
回路形成工程としては、例えば、サブトラクティブ法、セミアディディブ法等を用いることができる。ファインライン形成にはセミアディティブ法が好ましく、無電解めっき層上にパターンレジストを施し、所望の厚さの電解めっき層を形成後、パターンレジストを剥離し、無電解めっき層をフラッシュエッチで除去することにより、回路形成することができる。 As the circuit formation process, for example, a subtractive method, a semi-additive method, or the like can be used. The semi-additive method is preferable for fine line formation. A pattern resist is applied on the electroless plating layer, an electroplating layer having a desired thickness is formed, the pattern resist is peeled off, and the electroless plating layer is removed by flash etching. Thus, a circuit can be formed.
なお、本発明でいう「内層回路基板」とは、ガラスエポキシ基板、金属基板、ポリエステル基板、ポリイミド基板、ＢＴレジン基板、熱硬化型ポリフェニレンエーテル基板の片面又は両面にパターン加工された（回路形成された）導体層を有し、多層プリント配線板を製造する際に、さらに絶縁層及び導体層が形成されるべき中間製造物を言う。なお導体層表面は黒化処理等により予め粗化処理が施されていた方が絶縁層の内層回路基板一の密着性の観点から好ましい。 The “inner layer circuit board” in the present invention is a pattern processed on one or both sides of a glass epoxy board, metal board, polyester board, polyimide board, BT resin board, thermosetting polyphenylene ether board (circuit formation). I) An intermediate product having a conductor layer and having an insulating layer and a conductor layer to be further formed when a multilayer printed wiring board is produced. In addition, it is preferable from the viewpoint of the adhesiveness of the inner layer circuit board of the insulating layer that the surface of the conductor layer has been previously roughened by blackening or the like.
以下、実施例及び比較例を示して本発明をより具体的に説明する。
なお、以下の記載において「部」は「質量部」を意味する。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
In the following description, “part” means “part by mass”.
（樹脂ワニスの作成）
液状ビスフェノールＡ型エポキシ樹脂（エポキシ当量１８０、ジャパンエポキシレジン（株）製「エピコート８２８ＥＬ」）２８部と、ナフタレン型４官能エポキシ樹脂（エポキシ当量１６３、大日本インキ化学工業（株）製「ＨＰ４７００」）２８部とをＭＥＫ１５部とシクロヘキサノン１５部との混合液に撹拌しながら加熱溶解させた。そこへ、ノボラック構造を有するフェノール系硬化剤（大日本インキ化学工業（株）製「ＬＡ７０５２」、固形分が６０質量％のＭＥＫ溶液、フェノール性水酸基当量１２０）５０部、フェノキシ樹脂（分子量５００００、ジャパンエポキシレジン（株）製「Ｅ１２５６」の不揮発分４０質量％のＭＥＫ溶液）２０部、硬化触媒（四国化成工業（株）製、「２Ｅ４ＭＺ」）０．１部、球形シリカ（ＳＯＣ２）５５部、ポリビニルアセタール樹脂溶液（不揮発分１５重量％、積水化学工業（株）製「ＫＳ−１」）３０部、ブタジエン構造を有するエポキシ樹脂（分子量２７０００、ダイセル化学工業（株）製「ＰＢ−３６００」）３部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した。
(Create resin varnish)
28 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "Epicoat 828EL" manufactured by Japan Epoxy Resin Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, "HP4700" manufactured by Dainippon Ink & Chemicals, Inc.) ) 28 parts was dissolved by heating in a mixed solution of 15 parts of MEK and 15 parts of cyclohexanone with stirring. There, a phenolic curing agent having a novolak structure ("LA7052" manufactured by Dainippon Ink & Chemicals, Inc., MEK solution having a solid content of 60% by mass, phenolic hydroxyl group equivalent 120), 50 parts of phenoxy resin (molecular weight 50000, 20 parts of MEK solution of non-volatile content of 40% by mass “E1256” manufactured by Japan Epoxy Resin Co., Ltd., 0.1 part of curing catalyst (“2E4MZ” manufactured by Shikoku Chemicals Co., Ltd.), 55 parts of spherical silica (SOC2) , 30 parts of a polyvinyl acetal resin solution (non-volatile content: 15% by weight, “KS-1” manufactured by Sekisui Chemical Co., Ltd.), epoxy resin having a butadiene structure (molecular weight: 27000, “PB-3600” manufactured by Daicel Chemical Industries, Ltd.) 3 parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.
（硬化物シートの製造）
前記樹脂ワニスを古河サーキットフォイル製電解銅箔Ｆ２−ＷＳ（１２μｍ）の粗面上に、乾燥後の熱硬化性樹脂組成物層の厚さが２０μｍになるよう、ダイコータにて均一に塗布し、８０〜１２０℃（平均１００℃）で６〜８分間乾燥することにより樹脂シートを得た。該樹脂シートを、ひとつは１７０℃で１０分、もうひとつは１６５℃で１５分間熱硬化させ、形成された硬化物層のガラス転移温度がそれぞれ１００℃、１２０℃である２種類の硬化物シートを得た。
(Manufacture of cured product sheet)
The resin varnish was uniformly applied on a rough surface of electrolytic copper foil F2-WS (12 μm) manufactured by Furukawa Circuit Foil with a die coater so that the thickness of the thermosetting resin composition layer after drying was 20 μm, A resin sheet was obtained by drying at 80 to 120 ° C. (average 100 ° C.) for 6 to 8 minutes. The resin sheet is thermally cured at 170 ° C. for 10 minutes and the other at 165 ° C. for 15 minutes, and the cured sheet formed has two kinds of cured sheet, the glass transition temperatures of which are 100 ° C. and 120 ° C., respectively. Got.
（接着シートの製造）
前記樹脂ワニスをアルキッド系離型剤で処理されたＰＥＴフィルム（３８μｍ）の離型処理面上に、乾燥後の熱硬化性樹脂組成物層の厚さが１０μｍになるよう、ダイコータにて均一に塗布し、８０〜１２０℃（平均１００℃）で６〜８分間乾燥することにより接着シートを得た。
(Manufacture of adhesive sheets)
Uniformly with a die coater so that the thickness of the thermosetting resin composition layer after drying is 10 μm on the release-treated surface of the PET film (38 μm) treated with the alkyd mold release agent. The adhesive sheet was obtained by applying and drying at 80 to 120 ° C. (average 100 ° C.) for 6 to 8 minutes.
（絶縁樹脂シートの製造）
ガラス転移温度が１００℃の硬化物シートの硬化物面に、接着シートの接着層が接するように配置し、モートン・インターナショナル・インコーポレイティド製の真空ラミネーター７２４を使用して温度１００℃にて２０秒間真空吸引後、圧力１．０ｋｇｆ／ｃｍ２の条件で、ＰＥＴフィルム上から、耐熱ゴムを介して２０秒間積層して、硬化物層と接着層を有する絶縁樹脂シートを得た。
(Manufacture of insulating resin sheets)
The cured sheet having a glass transition temperature of 100 ° C. is disposed so that the adhesive layer of the adhesive sheet is in contact with the cured surface of the cured sheet, and a vacuum laminator 724 manufactured by Morton International Inc. is used. After vacuum suction for 2 seconds, an insulating resin sheet having a cured product layer and an adhesive layer was obtained by laminating for 20 seconds via a heat-resistant rubber from a PET film under the condition of a pressure of 1.0 kgf / cm 2 .
（絶縁樹脂シートの積層及び平滑化）
得られた絶縁樹脂シートの接着層面からPETフィルムを剥離し、内層回路基板（ＩＰＣ ＭＵＬＴＩ−ＰＵＲＰＯＳＥ ＴＥＳＴＢＯＡＲＤ Ｎｏ．ＩＰＣ−Ｂ−２５、導体厚１８μｍ、０．８ｍｍ厚）の両面に、接着層が接するように積層した。積層は、モートン・インターナショナル・インコーポレイティド製バキューム・アプリケータ７２４を使用し、温度８０℃、２０秒真空引き、耐熱ゴムを介してＳＵＳ鏡板により２０秒プレスことで行った。次いで北川精機（株）製の真空熱プレスＶＨ１−１６０３を用い、減圧下で３０℃から９０℃まで１５分掛けて昇温させた後、９０℃に維持しながら１０分間、２０ｋｇｆ／ｃｍ２の圧力でＳＵＳ鏡板による真空プレスを行い、絶縁樹脂シートの平滑化を行った。
(Lamination and smoothing of insulating resin sheets)
The PET film is peeled from the adhesive layer surface of the obtained insulating resin sheet, and the adhesive layer is in contact with both surfaces of the inner layer circuit board (IPC MULTI-PURPOSE TESTBOARD No. IPC-B-25, conductor thickness 18 μm, 0.8 mm thickness). The layers were laminated as follows. Lamination was performed by using a vacuum applicator 724 manufactured by Morton International, Inc., evacuated at a temperature of 80 ° C. for 20 seconds, and pressed with a SUS end plate for 20 seconds through heat-resistant rubber. Next, using a vacuum heat press VH1-1603 manufactured by Kitagawa Seiki Co., Ltd., the temperature was raised from 30 ° C. to 90 ° C. over 15 minutes under reduced pressure, and then maintained at 90 ° C. for 10 minutes, 20 kgf / cm 2 The insulating resin sheet was smoothed by vacuum pressing with a SUS end plate under pressure.
（樹脂組成物の硬化）
絶縁樹脂シートを積層した基板を、熱風循環炉を用いて１８０℃、３０分の硬化条件で、熱硬化性樹脂組成物を硬化させて、絶縁層を形成した。これにより、内層回路基板の両面に絶縁層が形成された積層板を得た。
(Curing resin composition)
The board | substrate which laminated | stacked the insulating resin sheet was hardened | cured on 180 degreeC and the hardening conditions for 30 minutes using the hot air circulation furnace, and the thermosetting resin composition was hardened, and the insulating layer was formed. Thereby, the laminated board in which the insulating layer was formed on both surfaces of the inner circuit board was obtained.
絶縁樹脂シートの積層工程の温度を３０℃から１１０℃まで１５分掛けて昇温させた後、平滑化工程の温度を１１０℃に維持したこと以外は、実施例１と同様にして多層プリント配線板を得た。 Multilayer printed wiring as in Example 1, except that the temperature of the insulating resin sheet laminating step was raised from 30 ° C. to 110 ° C. over 15 minutes, and then the temperature of the smoothing step was maintained at 110 ° C. I got a plate.
絶縁樹脂シートの積層工程の温度を３０℃から１１０℃まで１５分掛けて昇温させた後、平滑化工程のプレス条件を、１１０℃に維持しながら１０分間、１０ｋｇｆ／ｃｍ２の圧力で行ったこと以外は、実施例１と同様にして多層プリント配線板を得た。 After raising the temperature of the insulating resin sheet lamination process from 30 ° C. to 110 ° C. over 15 minutes, the pressing condition of the smoothing process is maintained at 110 ° C. for 10 minutes at a pressure of 10 kgf / cm 2. A multilayer printed wiring board was obtained in the same manner as in Example 1 except that.
絶縁樹脂シートの積層工程の温度を３０℃から１３０℃まで１５分掛けて昇温させた後、平滑化工程の温度を１３０℃に維持したこと以外は、実施例１と同様にして多層プリント配線板を得た。 Multilayer printed wiring as in Example 1 except that the temperature of the insulating resin sheet laminating step was increased from 30 ° C. to 130 ° C. over 15 minutes, and then the temperature of the smoothing step was maintained at 130 ° C. I got a plate.
絶縁樹脂シートの積層工程の温度を３０℃から１３０℃まで１５分掛けて昇温させた後、平滑化工程のプレス条件を、１３０℃に維持しながら１０分間、１０ｋｇｆ／ｃｍ２の圧力で行ったこと以外は、実施例１と同様にして多層プリント配線板を得た。 After raising the temperature of the insulating resin sheet lamination process from 30 ° C. to 130 ° C. over 15 minutes, the pressing condition of the smoothing process is maintained at 130 ° C. for 10 minutes at a pressure of 10 kgf / cm 2. A multilayer printed wiring board was obtained in the same manner as in Example 1 except that.
硬化物層のガラス転移温度が１００℃である以外は、実施例と同様にして多層プリント配線板を得た。 A multilayer printed wiring board was obtained in the same manner as in Example except that the glass transition temperature of the cured product layer was 100 ° C.
硬化物層のガラス転移温度が１００℃であり、絶縁樹脂シートの積層工程の温度を３０℃から１３０℃まで１５分掛けて昇温させた後、平滑化工程の温度を１３０℃に維持したこと以外は、実施例１と同様にして多層プリント配線板を得た。 The glass transition temperature of the cured product layer is 100 ° C., the temperature of the laminating step of the insulating resin sheet is increased from 30 ° C. to 130 ° C. over 15 minutes, and then the temperature of the smoothing step is maintained at 130 ° C. A multilayer printed wiring board was obtained in the same manner as Example 1 except for the above.
硬化物層のガラス転移温度が１００℃であり、絶縁樹脂シートの積層工程の温度を３０℃から１３０℃まで１５分掛けて昇温させた後、平滑化工程のプレス条件を、１３０℃に維持しながら１０分間、１０ｋｇｆ／ｃｍ２の圧力で行ったこと以外は、実施例１と同様にして多層プリント配線板を得た。 The glass transition temperature of the cured product layer is 100 ° C., and the temperature of the insulating resin sheet laminating step is increased from 30 ° C. to 130 ° C. over 15 minutes, and then the pressing condition of the smoothing step is maintained at 130 ° C. A multilayer printed wiring board was obtained in the same manner as in Example 1 except that the test was performed at a pressure of 10 kgf / cm 2 for 10 minutes.
絶縁樹脂シートの積層工程を、（株）名機製作所製の真空加圧式ラミネーターＭＶＬＰ−５００を用い、温度１００℃にて３０秒間真空吸引後、温度１００℃、圧力７．０ｋｇ／ｃｍ２の条件でＰＥＴフィルム上から、耐熱ゴムを介して３０秒間プレスすることにより積層し、次いで、大気圧下で、ＳＵＳ鏡板を用いて、温度１２０℃、圧力１０．０ｋｇ／ｃｍ２の条件で９０秒間プレスを行ったこと以外は、実施例１と同様にして、多層プリント配線板を得た。 The insulating resin sheet was laminated using a vacuum pressurizing laminator MVLP-500 manufactured by Meiki Seisakusho Co., Ltd., after vacuum suction at a temperature of 100 ° C. for 30 seconds, and then at a temperature of 100 ° C. and a pressure of 7.0 kg / cm 2 . And then laminated by pressing for 30 seconds through heat-resistant rubber on a PET film, and then for 90 seconds under atmospheric pressure using a SUS end plate at a temperature of 120 ° C. and a pressure of 10.0 kg / cm 2. A multilayer printed wiring board was obtained in the same manner as in Example 1 except that.
硬化物シートのガラス転移温度が１００℃であり、絶縁樹脂シートの積層工程を、（株）名機製作所製の真空加圧式ラミネーターＭＶＬＰ−５００を用い、温度１００℃にて３０秒間真空吸引後、温度１００℃、圧力７．０ｋｇ／ｃｍ２の条件でＰＥＴフィルム上から、耐熱ゴムを介してＳＵＳ鏡板により３０秒間プレスすることにより積層し、次いで、大気圧下で、ＳＵＳ鏡板を用いて、温度１２０℃、圧力１０．０ｋｇ／ｃｍ２の条件で９０秒間プレスを行ったこと以外は、実施例１と同様にして、多層プリント配線板を得た。 The glass transition temperature of the cured sheet is 100 ° C., and the lamination process of the insulating resin sheet is performed by vacuum suction at a temperature of 100 ° C. for 30 seconds using a vacuum pressurizing laminator MVLP-500 manufactured by Meiki Seisakusho Co., Ltd. Lamination was performed by pressing for 30 seconds with a SUS end plate through heat-resistant rubber on a PET film under conditions of a temperature of 100 ° C. and a pressure of 7.0 kg / cm 2 , and then using an SUS end plate under atmospheric pressure, A multilayer printed wiring board was obtained in the same manner as in Example 1 except that pressing was performed for 90 seconds under the conditions of 120 ° C. and pressure 10.0 kg / cm 2 .
＜比較例１＞
実施例１と同じ樹脂ワニスを古河サーキットフォイル製電解銅箔Ｆ２−ＷＳ（１２μｍ）の粗面上に、乾燥後の熱硬化性樹脂組成物層の厚さが２０μｍになるよう、ダイコータにて均一に塗布し、８０〜１２０℃（平均１００℃）で６〜８分間乾燥することにより未硬化の樹脂シートを得た。硬化物シートの代わりに該未硬化の樹脂シートを用いる以外は、実施例１と同様にして、多層プリント配線板を得た。
<Comparative Example 1>
Uniform with a die coater so that the thickness of the thermosetting resin composition layer after drying the same resin varnish as in Example 1 on a rough surface of electrolytic copper foil F2-WS (12 μm) manufactured by Furukawa Circuit Foil is 20 μm. And dried at 80 to 120 ° C. (average 100 ° C.) for 6 to 8 minutes to obtain an uncured resin sheet. A multilayer printed wiring board was obtained in the same manner as in Example 1 except that the uncured resin sheet was used instead of the cured sheet.
＜比較例２＞
硬化物シートの代わりに前記未硬化の樹脂シートを用いる以外は実施例１と同様にして、絶縁樹脂シートを得た。また絶縁樹脂シートの積層工程を、（株）名機製作所製の真空加圧式ラミネーターＭＶＬＰ−５００を用い、温度１００℃にて３０秒間真空吸引後、温度１００℃、圧力７．０ｋｇ／ｃｍ２の条件でＰＥＴフィルム上から、耐熱ゴムを介して３０秒間プレスすることにより積層し、次いで、大気圧下で、ＳＵＳ鏡板を用いて、温度１２０℃、圧力１０．０ｋｇ／ｃｍ２の条件で９０秒間プレスを行ったこと以外は、実施例１と同様にして、多層プリント配線板を得た。
<Comparative example 2>
An insulating resin sheet was obtained in the same manner as in Example 1 except that the uncured resin sheet was used instead of the cured sheet. In addition, the lamination process of the insulating resin sheet was performed using a vacuum pressurization type laminator MVLP-500 manufactured by Meiki Seisakusho Co., Ltd., after vacuum suction at a temperature of 100 ° C. for 30 seconds, and at a temperature of 100 ° C. and a pressure of 7.0 kg / cm 2 . Laminate by pressing for 30 seconds through heat-resistant rubber from a PET film under conditions, and then for 90 seconds under atmospheric pressure using a SUS end plate at a temperature of 120 ° C. and a pressure of 10.0 kg / cm 2. A multilayer printed wiring board was obtained in the same manner as in Example 1 except that the pressing was performed.
以上の実施例及び比較例で得られた硬化物シート、絶縁樹脂シート又は多層プリント板についての評価を、下記のとおりに行った。その結果を下記表１に示す。 Evaluation about the hardened | cured material sheet | seat, insulating resin sheet, or multilayer printed board obtained by the above Example and the comparative example was performed as follows. The results are shown in Table 1 below.
（ガラス転移温度の測定）
実施例及び比較例で得られた硬化物シート及び樹脂シートの小片を塩化第二鉄溶液に浸漬して銅箔を溶解除去してサンプルとし、セイコーインスツルメンツ（株）製の熱機械分析装置（ＤＭＡ）（型式ＤＭＡ−６１００）を用い、「引っ張りモード」にてガラス転移温度を測定した。かかる測定は、２℃／分の昇温にて、２５℃から２４０℃の範囲で行った。測定で得られた貯蔵弾性率（Ｅ’）と損失弾性率（Ｅ’’）との比で求められる損失正接（ｔａｎδ）の最大値の小数点第一位を四捨五入した値をガラス転移温度とした。なお未硬化であって、測定できない場合は、測定不能とした。
(Measurement of glass transition temperature)
Small pieces of cured product sheets and resin sheets obtained in the examples and comparative examples were immersed in a ferric chloride solution to dissolve and remove the copper foil to obtain a sample. A thermomechanical analyzer (DMA) manufactured by Seiko Instruments Inc. ) (Model DMA-6100), and the glass transition temperature was measured in “tensile mode”. This measurement was performed in the range of 25 ° C. to 240 ° C. at a temperature increase of 2 ° C./min. The value obtained by rounding off the first decimal place of the maximum value of the loss tangent (tan δ) obtained by the ratio between the storage elastic modulus (E ′) and the loss elastic modulus (E ″) obtained by the measurement was taken as the glass transition temperature. . If it was uncured and could not be measured, the measurement was impossible.
（絶縁樹脂シート、硬化物シート、接着シートの硬化物層、樹脂層又は接着層の厚さ測定）
実施例及び比較例で得られた硬化物シート及び樹脂シートの層厚と各々の支持体となる銅箔層、PETフィルム層の層厚を、接触式層厚計（（株）ミツトヨ製、ＭＣＤ−２５ＭＪ）を用いて測定し、それらの差を硬化物層、樹脂層又は接着層の厚さとした。
(Insulating resin sheet, cured sheet, cured sheet layer of adhesive sheet, thickness measurement of resin layer or adhesive layer)
The layer thickness of the cured product sheet and resin sheet obtained in Examples and Comparative Examples and the thickness of the copper foil layer and the PET film layer as the respective supports were measured using a contact-type thickness gauge (manufactured by Mitutoyo Corporation, MCD). -25 MJ), and the difference between them was the thickness of the cured product layer, the resin layer or the adhesive layer.
（積層後の硬化物層の厚みの測定）
前記内層回路基板（ＩＰＣ ＭＵＬＴＩ−ＰＵＲＰＯＳＥ ＴＥＳＴＢＯＡＲＤ Ｎｏ．ＩＰＣ−Ｂ−２５：、基板厚０．８ｍｍ、導体厚１８μｍ）において、導体密度の異なるＡクーポン部分とＰクーポン部分（図１参照）を切断し、断面部分を研磨し、各導体層上の絶縁層厚を走査型電子顕微鏡(ＳＥＭ）で測定した。
［評価］
○ ：硬化物層又は樹脂層の厚みと絶縁層の厚みの差が２μｍ未満。
× ：硬化物層又は樹脂層の厚みと絶縁層の厚みの差が２μｍ以上。
In the inner layer circuit board (IPC MULTI-PURPOSE TESTBOARD No. IPC-B-25: substrate thickness 0.8 mm, conductor thickness 18 μm), the A coupon portion and the P coupon portion (see FIG. 1) having different conductor densities are cut. The cross section was polished, and the insulating layer thickness on each conductor layer was measured with a scanning electron microscope (SEM).
[Evaluation]
○: The difference between the thickness of the cured product layer or the resin layer and the thickness of the insulating layer is less than 2 μm.
X: The difference of the thickness of a hardened | cured material layer or a resin layer and the thickness of an insulating layer is 2 micrometers or more.
表１の結果から明らかなように、実施例１〜１０の硬化物層と接着層から成る絶縁樹脂シートは、内層回路基板上に絶縁層を形成後における、Ａクーポン部及びＰクーポン部の導体層上の絶縁層厚の変化が、２０μｍの硬化物層で０．１〜０．５μｍ、４０μｍの硬化物層で１．１〜１．３μｍと小さかった。またＡクーポン部とＰクーポン部間の導体層上の絶縁層厚の差も０．１〜０．２μｍと小さく、導体密度の異なる内層回路基板面において、均一な厚みの絶縁層が形成された。
一方、硬化物層を含まない絶縁樹脂シートを使用した比較例１及び２では、導体層上の絶縁層厚が、２０μｍの樹脂層厚で３．５〜７μｍ、４０μｍの樹脂層厚で５〜８μｍと大きく減少した。さらにはＡクーポン部とＰクーポン部の導体層上の絶縁層厚の差も３〜３．５μと大きく、均一性に劣る結果となった。
As is apparent from the results in Table 1, the insulating resin sheets composed of the cured product layers and adhesive layers of Examples 1 to 10 are conductors of the A coupon part and the P coupon part after the insulating layer is formed on the inner circuit board. The change in the insulating layer thickness on the layer was as small as 0.1 to 0.5 μm for the 20 μm cured product layer and 1.1 to 1.3 μm for the 40 μm cured product layer. Also, the difference in insulation layer thickness on the conductor layer between the A coupon part and the P coupon part is as small as 0.1 to 0.2 μm, and an insulation layer having a uniform thickness was formed on the inner circuit board surface having different conductor densities. .
On the other hand, in Comparative Examples 1 and 2 using an insulating resin sheet that does not include a cured product layer, the insulating layer thickness on the conductor layer is 3.5 to 7 μm with a resin layer thickness of 20 μm, and 5 to 5 with a resin layer thickness of 40 μm. It greatly decreased to 8 μm. Furthermore, the difference of the insulation layer thickness on the conductor layer of A coupon part and P coupon part was as large as 3-3.5 micrometers, and became a result inferior to uniformity.
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| JP5896092B1 (en) * | 2014-10-16 | 2016-03-30 | 味の素株式会社 | Support, adhesive sheet, laminated structure, semiconductor device, and printed wiring board manufacturing method |
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| KR20140005783A (en) | 2012-07-06 | 2014-01-15 | 아지노모토 가부시키가이샤 | Insulating resin sheet |
| JP5896092B1 (en) * | 2014-10-16 | 2016-03-30 | 味の素株式会社 | Support, adhesive sheet, laminated structure, semiconductor device, and printed wiring board manufacturing method |
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