JPWO2008105563A1 - Flame retardant adhesive resin composition and flexible printed circuit board material using the same - Google Patents

Flame retardant adhesive resin composition and flexible printed circuit board material using the same Download PDF

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JPWO2008105563A1
JPWO2008105563A1 JP2009501333A JP2009501333A JPWO2008105563A1 JP WO2008105563 A1 JPWO2008105563 A1 JP WO2008105563A1 JP 2009501333 A JP2009501333 A JP 2009501333A JP 2009501333 A JP2009501333 A JP 2009501333A JP WO2008105563 A1 JPWO2008105563 A1 JP WO2008105563A1
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general formula
resin composition
retardant adhesive
hydrogen atom
flame
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JP5334127B2 (en
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茂顕 田内
茂顕 田内
横山　直樹
直樹 横山
哲則 佐藤
哲則 佐藤
会田　勝之
勝之 会田
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Tohto Kasei Co Ltd
Nippon Steel Chemical and Materials Co Ltd
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Tohto Kasei Co Ltd
Nippon Steel Chemical Co Ltd
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

フレキシブル配線基板に用いる難燃性接着剤樹脂組成物であって、（イ）特定のエポキシ樹脂、（ロ）特定のリン含有フェノキシ樹脂、（ハ）硬化剤、（二）硬化促進剤を必須成分として含有し、実質的にハロゲン元素を含まないで、ピール接着力、はんだ耐熱性、低流れ性等の接着剤特性に優れた難燃性接着剤樹脂組成物を提供する。A flame retardant adhesive resin composition used for a flexible wiring board, comprising (a) a specific epoxy resin, (b) a specific phosphorus-containing phenoxy resin, (c) a curing agent, and (ii) a curing accelerator. And a flame retardant adhesive resin composition that is excellent in adhesive properties such as peel adhesive strength, solder heat resistance, and low flowability.

Description

本発明は、耐熱性接着剤樹脂組成物に関し、詳しくは実質的にハロゲン元素を含まない高耐熱、難燃性の接着剤組成物並びにそれを用いた接着剤フィルム、カバーレイフィルム及びフレキシブル銅張積層板に関するものであり、特にフレキシブルプリント基板（以下、ＦＰＣともいう）に適した難燃性接着剤樹脂組成物に関する。   The present invention relates to a heat-resistant adhesive resin composition, and more specifically, a high heat-resistant and flame-retardant adhesive composition substantially free of halogen elements, and an adhesive film, a coverlay film, and flexible copper-clad using the same. More particularly, the present invention relates to a flame retardant adhesive resin composition suitable for a flexible printed circuit board (hereinafter also referred to as FPC).

プリント配線基板としては、従来、紙−フェノール樹脂、ガラス繊維−エポキシ樹脂からなる基材あるいはポリイミドフィルム、ポリエチレンテレフタレートフィルム等の基材と金属を貼り合わせたものが用いられている。
本明細書において、プリント配線基板は回路加工前の積層体をいい、この金属箔を回路加工したものをプリント配線板といい、両者をプリント基板という。
また、近年、電機・電子機器、精密機器の分野において用いるプリント配線板においては、配線占有面積が小さくなり、このため多層プリント基板の需要はますます高くなっている。プリント配線板を積層して多層プリント配線板を作製したり、異種の回路材料を複合化する工程においては、種々の接着剤あるいは接着剤フィルムが用いられている。
このような接着剤は、多層プリント基板用接着剤、カバーレイフィルム用接着剤として広く使われているが、接着強度、耐薬品性、はんだ耐熱性、耐折性等に優れた材料が求められるようになってきた。また、火災安全性確保の点から難燃性に優れた材料が求められてきた。
従来の接着剤フィルムは、難燃性を付与するために、臭素等のハロゲンを含有する樹脂又は添加物等が使用されていた。ハロゲンは難燃性の付与の他、コストパフォーマンスが高く、プラスチックを劣化させにくいなどの理由から広く用いられてきた。しかしここに含まれるハロゲンは、燃焼時にダイオキシン等の有害物質を発生させる原因となる可能性が懸念されており、材料からのハロゲンの排除が強く望まれている。
プリント基板用途に使用される接着剤は、例えば、特許文献１〜５等で提案されている。
特開平１０−１０２０２５号公報 特開２００１−１６４２２６号公報 特開２００１−３２３２４２号公報 特開２００１−３５４９３６号公報 特開２００３−１８１９９３号公報 As the printed wiring board, conventionally, a base material made of paper-phenolic resin, glass fiber-epoxy resin, or a base material such as a polyimide film or a polyethylene terephthalate film and a metal are used.
In the present specification, a printed wiring board refers to a laminate before circuit processing, a circuit processed from this metal foil is referred to as a printed wiring board, and both are referred to as printed boards.
Further, in recent years, printed wiring boards used in the fields of electrical / electronic equipment and precision equipment have a reduced wiring occupation area, and thus the demand for multilayer printed circuit boards has been increasing. Various adhesives or adhesive films are used in the process of producing a multilayer printed wiring board by laminating printed wiring boards or compounding different kinds of circuit materials.
Such adhesives are widely used as adhesives for multilayer printed circuit boards and coverlay films, but materials with excellent adhesive strength, chemical resistance, solder heat resistance, folding resistance, etc. are required. It has become like this. Moreover, the material excellent in the flame retardance from the point of ensuring fire safety has been calculated | required.
In the conventional adhesive film, a resin or additive containing halogen such as bromine has been used to impart flame retardancy. Halogen has been widely used for the purpose of imparting flame retardancy, cost performance, and resistance to plastic deterioration. However, there is a concern that the halogen contained therein may cause harmful substances such as dioxin during combustion, and it is strongly desired to eliminate the halogen from the material.
Adhesives used for printed circuit board applications are proposed in, for example, Patent Documents 1 to 5.
Japanese Patent Laid-Open No. 10-102025 JP 2001-164226 A JP 2001-323242 A JP 2001-354936 A JP 2003-181993 A

前記特許文献は、いずれもエポキシ樹脂、硬化剤、アクリロニトリルブタジエンゴムもしくはフェノキシ樹脂を主要成分とするものであり、難燃化の手段はいずれも臭素化エポキシ樹脂、臭素化フェノキシ樹脂を配合することによっている。
一方、ハロゲンに替わる難燃性付与材料として、非ハロゲン系の様々な材料が開発されている。その中でも最も一般的な手法はリンを含む樹脂の使用又は有機リン系化合物の添加である。このような難燃性接着剤としては、例えば、特許文献６〜１０等が挙げられる。
特開２００１−３３９１３１号公報 特開２００２−６０７２０号公報 特開２００３−１７６４７０号公報 特開２００４−３３１７８３号公報 特開２００５−２９０２２９号公報 The above-mentioned patent documents all have an epoxy resin, a curing agent, acrylonitrile butadiene rubber or phenoxy resin as main components, and all the means for flame retardancy include blending a brominated epoxy resin and a brominated phenoxy resin. Yes.
On the other hand, various non-halogen-based materials have been developed as flame retardant materials that replace halogen. Among them, the most common method is the use of a resin containing phosphorus or the addition of an organic phosphorus compound. Examples of such a flame retardant adhesive include Patent Documents 6 to 10 and the like.
JP 2001-339131 A JP 2002-60720 A JP 2003-176470 A JP 2004-331783 A JP-A-2005-290229

特許文献６、７、９は、有機リン化合物を、特許文献８および１０は、公知のリン含有エポキシ樹脂、リン含有フェノキシ樹脂を非ハロゲン系での難燃化の手段として各々配合することとしている。   Patent Documents 6, 7, and 9 contain organic phosphorus compounds, and Patent Documents 8 and 10 use known phosphorus-containing epoxy resins and phosphorus-containing phenoxy resins as non-halogen flame retardant means. .

本発明の目的は、ピール接着力、ハンダ耐熱性、フロー性等の接着剤特性に優れ、しかも環境に対応するために非ハロゲン化を実現した難燃性の接着剤樹脂組成物を提供することであり、更に、このような接着剤樹脂組成物を用いた難燃性の接着剤フィルム、カバーレイフィルム及びフレキシブル銅張積層板を提供することである。
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、接着剤樹脂組成物に特定の樹脂を使用し、特定の成分を見出したことで、本発明を完成させた。
すなわち、本発明は、下記（イ）〜（ニ）成分、
（イ）下記一般式（１）で表され、リン含有率が１重量％〜６重量％であり、且つゲルパーミエーミッションクロマトグラフィーを用いて測定した標準ポリエチレンオキサイド換算重量平均分子量が６０，０００〜２００，０００であるリン含有フェノキシ樹脂、
（ロ）下記一般式（１０）で表されるエポキシ樹脂、
（ハ）硬化剤、及び
（二）硬化促進剤、
を必須成分として含有し、実質的にハロゲン元素を含まないことを特徴とする難燃性接着剤樹脂組成物である。

Figure 2008105563
一般式（１）において、Ｘは下記一般式（２）又は（３）で表される２価の基を必須とする一般式（２）、（３）、（４）又は（５）から選ばれる少なくとも１種の２価の基を示し、Ｚは水素原子又は一般式（６）を示し、ｎは平均値で２１以上である。
Figure 2008105563
Figure 2008105563
ここで、式（２）〜（５）中、Ｙは一般式（７）又は（８）で表されるリン含有基を示し、Ｒ１〜Ｒ３、Ｒ１〜Ｒ４、Ｒ１〜Ｒ４、Ｒ１〜Ｒ８は独立に、水素原子、炭素数１〜４のアルキル基又はフェニル基を示す。Ａは単結合又は−ＣＨ２−、−Ｃ（ＣＨ３）２−、−ＣＨ（ＣＨ３）−、−Ｓ−、−ＳＯ２−、−Ｏ−、−ＣＯ−若しくは一般式（９）から選ばれる２価の基を示す。
Figure 2008105563
ここで、式（７）〜（９）中、Ｒ１〜Ｒ８、Ｒ１〜Ｒ１０、Ｒ１〜Ｒ８は独立に、水素原子、炭素数１〜４のアルキル基又はフェニル基を示す。
Figure 2008105563
ここで、式中、Ｗは一般式（５）で表される２価の基を示し、ｍは０以上の整数であり、ｍの平均は０．１〜１５である。
また、本発明は、（ロ）成分において、一般式（１０）における重合度ｍ＝０体の含有率が、ゲルパーミエーションクロマトグラフィーを用いて測定したクロマトグラムの面積パーセントで７０％以上であることを特徴とする難燃性接着剤樹脂組成物である。
更に、本発明は、（イ）成分が、一般式（１）において、Ｘが一般式（２）及び（５）で示される２価の基であり、一般式（２）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが−Ｃ（ＣＨ３）２−を示すことを特徴としてもよく、あるいは（イ）成分が、一般式（１）において、Ｘが一般式（３）及び（５）で示される２価の基であり、一般式（３）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが−Ｃ（ＣＨ３）２−を示すことを特徴としてもよく、あるいは（イ）成分が、一般式（１）において、Ｘが一般式（２）及び（５）で示される２価の基であり、一般式（２）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが一般式（９）を示すことを特徴としてもよく、あるいは（イ）成分が、一般式（１）において、Ｘが一般式（３）及び（５）で示される２価の基であり、一般式（３）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが一般式（９）を示すことを特徴としてもよい。
更にまた、本発明の難燃性接着剤樹脂組成物は、該組成物１００重量部に対し、（イ）成分を２０〜８０重量部配合してもよい。
また、本発明の難燃性接着剤フィルムは、本発明の難燃性接着剤樹脂組成物を、フィルム状に形成してなることを特徴とするものである。
また、本発明のカバーレイフィルムは、ポリイミドフィルムと、該ポリイミドフィルムに設けられた本発明の難燃性接着剤樹脂組成物からなる層とを有することを特徴とするものである。
また、本発明のフレキシブル銅張積層板は、ポリイミドフィルムと、該フィルムに設けられた本発明の難燃性接着剤樹脂組成物からなる層と、銅箔とを有することを特徴とするものである。
以下、難燃性接着剤樹脂組成物に関する本発明を説明し、次に難燃性接着剤フィルム、カバーレイフィルム及びフレキシブル銅張積層板に関する本発明の説明をするが、共通する部分は同時に説明する。まず、本発明の難燃性接着剤樹脂組成物の各構成要素について説明する。
本発明の難燃性接着剤樹脂組成物（接着剤樹脂組成物又は樹脂組成物と略称することがある。）は、上記（イ）〜（ニ）成分を必須成分として含有する。（イ）成分はリン含有フェノキシ樹脂であり、（ロ）成分はエポキシ樹脂であり、（ハ）成分は硬化剤であり、（ニ）成分は硬化促進剤であり、実質的にハロゲン元素を含まない。ここで、実質的にハロゲン元素を含まないとは、ハロゲン元素として９００ｗｔｐｐｍ以上のハロゲン及びハロゲン化合物を含まないことをいう。
（イ）成分のリン含有フェノキシ樹脂は、上記一般式（１）で表され、リン含有率が１重量％〜６重量％であり、且つゲルパーミエーションクロマトグラフィーを用いて測定した標準ポリエチレンオキサイド換算重量平均分子量が６０，０００〜２００，０００、好ましくは７０，０００〜１３０，０００、更に好ましくは８０，０００〜１２５，０００であるものを使用する。上記範囲内の重量平均分子量のものを使用することで、例えば、後述するカバーレイフィルムの接着剤層として適用した場合の耐折性を向上させることができる。一般式（１）において、Ｘは上記一般式（２）、（３）、（４）又は（５）から選ばれる少なくとも１種の２価の基を示すが、一般式（２）又は（３）で表される２価の基を必須とする。有利には、一般式（２）又は（３）で表される２価の基の一方又は両者をＸ中に２０モル％以上、好ましくは５０モル％以上含むことがよい。Ｚは水素原子又は上記式（６）で表されるグリシジル基を示す。ｎは平均値で２１以上であるが、好ましくは３０〜５０００の範囲である。かかるリン含有フェノキシ樹脂は、例えば、特開２００１−３１０９３９号公報に開示されている方法により製造することができる。
また、上記一般式（２）、（３）、（４）及び（５）において、Ｙは上記一般式（７）又は（８）で表されるリン含有基を示す。式（５）中のＡは単結合又は−ＣＨ２−、−Ｃ（ＣＨ３）２−、−ＣＨ（ＣＨ３）−、−Ｓ−、−ＳＯ２−、−Ｏ−、−ＣＯ−若しくは上記一般式（９）から選ばれる２価の基を示す。式（２）〜（５）及び（７）〜（９）中、Ｒ１〜Ｒ１０は独立に、水素原子、炭素数１〜４のアルキル基又はフェニル基を示す。好ましくは、水素原子又はメチル基であり、メチル基の数は４以下であることがよい。
また、（イ）成分が、上記一般式（１）において、Ｘが上記一般式（２）及び（５）で示される２価の基であり、一般式（２）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが−Ｃ（ＣＨ３）２−を示すものでもよい。
また、（イ）成分が、一般式（１）において、Ｘが一般式（３）及び（５）で示される２価の基であり、一般式（３）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが−Ｃ（ＣＨ３）２−を示すものでもよい。
また、（イ）成分が、一般式（１）において、Ｘが一般式（２）及び（５）で示される２価の基であり、一般式（２）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが一般式（９）を示すものでもよい。
また、（イ）成分が、一般式（１）において、Ｘが一般式（３）及び（５）で示される２価の基であり、一般式（３）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが一般式（９）を示すものでもよい。
（ロ）成分のエポキシ樹脂は、上記一般式（１０）で表されるエポキシ樹脂である。式（１０）において、Ｗは上記一般式（５）で表される２価の基を示し、ｍは０以上の整数であり、ｍの平均は０．１〜１５である。一般式（１０）で表される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、ビスフェノールＦ型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂等が挙げられ、これらは単独又は２種以上混合して使用することができる。エポキシ樹脂は、実質的にハロゲン元素を含まないものであることがよい。
樹脂組成物を乾燥して得られる乾燥物又はフィルム（以下、Ｂステージ状態組成物ともいう）の耐割れ性向上を考慮すると、上記一般式（１０）における重合度ｍ＝０体の含有率が、ゲルパーミエーションクロマトグラフィーの面積パーセントを用いて測定したクロマトグラムの面積パーセントで７０％以上であることが好ましく、より好ましくは８０％以上である。そして、常温で液状であることが好ましい。
本発明の難燃性接着剤樹脂組成物１００重量部中には、（イ）成分を２０〜８０重量部、好ましくは３０〜７０重量部、更に好ましくは４０〜６０重量部配合することがよい。２０重量部を下回ると柔軟性の低下、内部応力の増加により、接着力が発現せず、８０重量部を上回ると架橋成分の比率の減少により、ハンダ耐熱性が低下し、接着剤としての性能を損なう。また、（ロ）成分は２０〜７０重量部の範囲で配合することが好ましい。（ロ）成分がこの範囲より少ない場合には、架橋密度が低下して接着剤の耐熱性が低下し、反対に多すぎる場合には、接着剤の可とう性が低下して接着剤のはく離接着力が低下する、という問題が生ずる。
（ハ）成分の硬化剤は、（ロ）成分のエポキシ樹脂の硬化剤として知られているものが使用でき、例えば、ノボラック型フェノール樹脂、ジシアンジアミド、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、アジン類、イミダゾール類、酸無水物等が使用できる。また、（ハ）成分として、イミダゾール類を使用する場合、これは（ニ）成分でもあるので、（ニ）成分としても計算される。（ハ）成分の使用量は、（ロ）成分のエポキシ樹脂に対し当量比（（ハ）／（ロ））が０．５〜１．５となるように配合することが好ましい。一般に、フェノール樹脂系硬化剤を用いる場合は、０．８〜１．２、アミン系硬化剤を用いる場合は、０．５〜１．０とすることがよい。
（二）成分の硬化促進剤は、トリフェニルホスフィン等の有機リン系化合物や２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類、３級アミン、ルイス酸を用いることができる。その配合率は、求められる硬化時間に応じて適宜選定されるが、一般的には、難燃性接着剤樹脂組成物に対して、０．０１〜３．０重量％の範囲で用いられることがよい。
また、本発明の難燃性接着剤樹脂組成物を熱硬化して得られる硬化物のガラス転移温度（Ｔｇ）は、好ましくは１００℃以上、より好ましくは１００〜１７０℃の範囲にあることがよい。熱硬化後の硬化物のガラス転移温度が１００℃未満では、耐マイグレーション性が低下する。樹脂組成物の硬化後のガラス転移温度は、主に（ロ）成分のエポキシ樹脂及び（ハ）成分の硬化剤の種類及び配合量によって調整可能である。
ここで、硬化物のガラス転移温度の測定は、後述する特性評価方法の条件：＜硬化物特性＞［ガラス転移温度（Ｔｇ）］による。
本発明の難燃性接着剤樹脂組成物は、上記必須成分以外の成分として、無機系難燃剤としての水酸化アルミニウムおよび水酸化マグネシウム、補強剤もしくは増量剤としてのシリカ、炭酸カルシウム等の体質顔料、柔軟性付与剤として高分子エストラマーを配合することができ、あるいは粘度調整剤、カップリング剤等の添加剤も配合することができる。その添加率は、求められる特性に応じて適宜選定される。
また、本発明の難燃性接着剤樹脂組成物は、メチルエチルケトン、ジメチルホルムアミド、２−エトキシエタノール等の有機溶剤に溶解又は分散した接着剤樹脂溶液として使用に供される。その場合の固形分濃度は、使用条件によって適宜選定されるが、２０〜６０重量％とするのが一般的である。なお、溶剤は本発明の難燃性接着剤樹脂組成物を構成する成分ではなく、難燃性接着剤樹脂組成物を溶液とするために使用される成分と理解される。したがって、難燃性接着剤樹脂組成物中への各成分の配合量の計算にあたっては、溶剤は計算から除外される。
本発明の難燃性接着剤樹脂組成物は、フィルム状に成形して用いることができる。この場合、従来から公知の方法を用いてフィルム化することが可能であるが、好適な成形方法の例としては、難燃性接着剤樹脂組成物をメチルエチルケトン等の有機溶剤で希釈して溶液状にした後、得られた接着剤樹脂溶液を、表面が剥離処理された金属箔、ポリエステルフィルム、ポリイミドフィルム等の基材上に従来公知の方法により塗布し、溶剤を蒸発させてタックフリー化し、且つ接着剤樹脂層を構成する組成物が硬化反応しない温度、時間条件で乾燥して、接着剤フィルム層を形成し、これを基材より剥離して、難燃性接着剤フィルムとする。この乾燥条件は、使用する溶剤や樹脂組成物によって変化するが、一般的には１３０〜１６０℃、３〜１０分の温度、時間範囲が選定される。また、ポリエステル等の離型フィルム及び接着剤フィルム層よりなるボンディングシートとして使用する場合には、離型フィルムと接着剤フィルム層の厚みの比は、特に限定されないが、離型フィルム厚１２．５μｍに接着剤層１５〜３０μｍを設けたものが好適に利用できる。
本発明の難燃性接着剤フィルムの使用方法としては、例えば、フレキシブルプリント配線基板、ガラス繊維−エポキシ配線基板、紙−フェノール配線基板又はこれらを回路加工して得られる各種プリント配線板、金属、樹脂基材等の被接着物の接着に適する。金属箔と樹脂基材を接着することによりプリント配線基板を得ることができ、プリント配線基板又はプリント配線板同士を接着させることにより多層のプリント配線基板又はプリント配線板を得ることができ、プリント配線板とカバーレイを接着させることにより、カバーレイ付き、プリント配線板を得ることができる。その他、プリント配線基板又はプリント配線板の接続用接着剤フィルムとしても使用できる。いずれにしても、プリント基板の製造又は加工の工程に有利に使用される。
本発明の難燃性接着剤樹脂組成物は、カバーレイフィルムの接着剤層に適用することもできる。その場合、カバーレイフィルムはポリイミドフィルム及び前記の接着剤樹脂組成物より形成されるが、本発明のカバーレイフィルムを形成する方法としては、従来の方法を用いてフィルム化することが可能である。好適な成形方法の例としては、上記接着剤樹脂組成物をメチルエチルケトン等の有機溶剤で希釈して溶液状にした後、得られた接着剤樹脂溶液を、ポリイミドフィルム上に塗布し、溶剤を蒸発させてタックフリー化し、かつ接着剤層を構成する接着剤樹脂組成物は硬化反応しない温度、時間条件で乾燥して、カバーレイフィルムとする方法がある。ポリイミドフィルムに２〜２００μｍの厚さ、好ましくは５〜１００μｍ、更に好ましくは１０〜５０μｍの厚さでコーティングした後、乾燥する。この乾燥条件は、使用する溶剤や樹脂組成物によって変化するが、一般的には１３０〜１６０℃、３〜１０分の温度、時間範囲が選定される。また、ポリイミドフィルムは耐熱性及び難燃性を増すために必要であり、このポリイミドフィルムの厚さは、必要に応じて適切な厚さのものを使用すればよいが、好ましくは３〜５０μｍ、より好ましくは５〜３０μｍがよい。ポリイミドフィルムと接着剤層の厚みの比は、限定されないが、フィルム厚１２．５μｍに接着剤層１５〜２０μｍ、フィルム厚２５μｍに接着剤層２５〜３５μｍ、各々設けたカバーレイフィルムが一般的である。
本発明の難燃性接着剤樹脂組成物は、フレキシブル銅張積層板（以下、３層銅張積層板ともいう）の接着剤層に適用することもできる。その場合、フレキシブル銅張積層板はポリイミドフィルム、前記の接着剤樹脂組成物及び銅箔より形成されるが、本発明のフレキシブル銅張積層板を形成する方法としては、従来の方法を用いて積層することが可能である。好適な積層方法の例としては、上記接着剤樹脂組成物をメチルエチルケトン等の有機溶剤で希釈して溶液状にした後、ポリイミドフィルムの片面又は両面に塗布し有機溶剤分を乾燥後、熱ロールで銅箔をポリイミドフィルムの片面又は両面に張り合わせた後、加熱硬化することで製造できる。乾燥条件は、使用する溶剤や樹脂組成物によって変化するが、一般的には１３０〜１６０℃、３〜１０分の温度、時間範囲が選定され、硬化条件は、１６０〜１９０℃、１０〜１２０分の温度、時間範囲から選定されるのが一般的である。ポリイミドフィルム層、接着剤層及び銅箔の厚みは、特に限定されないが、ポリイミドフィルム厚５〜２５μｍ、接着剤層１０〜３０μｍ、銅箔厚１０〜３５μｍとするのが一般的である。An object of the present invention is to provide a flame-retardant adhesive resin composition which is excellent in adhesive properties such as peel adhesive strength, solder heat resistance, flowability, etc., and which has been non-halogenated to cope with the environment. Furthermore, it is to provide a flame retardant adhesive film, a coverlay film and a flexible copper clad laminate using such an adhesive resin composition.
As a result of intensive studies to achieve the above object, the present inventors have used the specific resin in the adhesive resin composition and found specific components, thereby completing the present invention.
That is, the present invention includes the following components (a) to (d):
(A) It is represented by the following general formula (1), the phosphorus content is 1% by weight to 6% by weight, and the weight average molecular weight in terms of standard polyethylene oxide measured by gel permeation chromatography is 60,000. A phosphorus-containing phenoxy resin that is ~ 200,000,
(B) an epoxy resin represented by the following general formula (10),
(C) a curing agent, and (2) a curing accelerator,
Is a flame retardant adhesive resin composition characterized by containing an essential component and substantially free of halogen elements.
Figure 2008105563
In the general formula (1), X is selected from the general formula (2), (3), (4) or (5) which essentially requires a divalent group represented by the following general formula (2) or (3) At least one kind of divalent group, Z represents a hydrogen atom or the general formula (6), and n is 21 or more on average.
Figure 2008105563
Figure 2008105563
Here, in the formulas (2) to (5), Y represents a phosphorus-containing group represented by the general formula (7) or (8), and R 1 to R 3 , R 1 to R 4 , R 1 to R 4 , R 1 to R 8 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. A is a single bond or —CH 2 —, —C (CH 3 ) 2 —, —CH (CH 3 ) —, —S—, —SO 2 —, —O—, —CO— or from the general formula (9) The divalent group selected is shown.
Figure 2008105563
Here, in formulas (7) to (9), R 1 to R 8 , R 1 to R 10 , and R 1 to R 8 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. .
Figure 2008105563
Here, in formula, W shows the bivalent group represented by General formula (5), m is an integer greater than or equal to 0, and the average of m is 0.1-15.
Further, in the present invention, in the component (b), the content of the polymerization degree m = 0 isomer in the general formula (10) is 70% or more in terms of the area percentage of the chromatogram measured using gel permeation chromatography. It is a flame retardant adhesive resin composition characterized by the above.
Further, in the present invention, the component (A) is a divalent group represented by the general formulas (2) and (5) in the general formula (1), and R 1 to R in the general formula (2) 3 represents a hydrogen atom, Y represents the general formula (7), and R 1 to R 8 in the general formula (5) represent a hydrogen atom, but A represents —C (CH 3 ) 2 —. Alternatively, the component (A) may be a divalent group represented by the general formulas (3) and (5) in the general formula (1), and R 1 to R in the general formula (3). 3 represents a hydrogen atom, Y represents the general formula (7), and R 1 to R 8 in the general formula (5) represent a hydrogen atom, but A represents —C (CH 3 ) 2 —. Or (i) component may be a divalent group represented by the general formulas (2) and (5) in the general formula (1), (2) R 1 to R 3 in is a hydrogen atom, Y represents a general formula (7), R 1 ~R 8 in the general formula (5) is a hydrogen atom, A is the formula (9 Or the component (A) is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and the general formula (3) R 1 to R 3 in FIG. 2 represent a hydrogen atom, Y represents the general formula (7), R 1 to R 8 in the general formula (5) represent a hydrogen atom, and A represents the general formula (9). This may be a feature.
Furthermore, the flame retardant adhesive resin composition of the present invention may contain 20 to 80 parts by weight of component (A) with respect to 100 parts by weight of the composition.
In addition, the flame retardant adhesive film of the present invention is formed by forming the flame retardant adhesive resin composition of the present invention into a film shape.
Moreover, the coverlay film of this invention has a polyimide film and the layer which consists of a flame retardant adhesive agent resin composition of this invention provided in this polyimide film, It is characterized by the above-mentioned.
Moreover, the flexible copper clad laminate of the present invention comprises a polyimide film, a layer made of the flame retardant adhesive resin composition of the present invention provided on the film, and a copper foil. is there.
Hereinafter, the present invention related to the flame retardant adhesive resin composition will be described, and then the present invention related to the flame retardant adhesive film, the coverlay film and the flexible copper clad laminate will be described. To do. First, each component of the flame retardant adhesive resin composition of the present invention will be described.
The flame-retardant adhesive resin composition of the present invention (sometimes abbreviated as an adhesive resin composition or a resin composition) contains the above components (a) to (d) as essential components. Component (a) is a phosphorus-containing phenoxy resin, Component (b) is an epoxy resin, Component (c) is a curing agent, Component (d) is a curing accelerator, and substantially contains a halogen element. Absent. Here, “substantially not containing a halogen element” means that the halogen element does not contain 900 wtppm or more of halogen and a halogen compound.
(B) The component phosphorus-containing phenoxy resin is represented by the above general formula (1), has a phosphorus content of 1% by weight to 6% by weight, and is converted into standard polyethylene oxide measured using gel permeation chromatography. Those having a weight average molecular weight of 60,000 to 200,000, preferably 70,000 to 130,000, more preferably 80,000 to 125,000 are used. By using a material having a weight average molecular weight within the above range, for example, folding resistance when applied as an adhesive layer of a coverlay film described later can be improved. In the general formula (1), X represents at least one divalent group selected from the above general formulas (2), (3), (4) or (5), and the general formula (2) or (3 A divalent group represented by Advantageously, one or both of the divalent groups represented by the general formula (2) or (3) may be contained in X in an amount of 20 mol% or more, preferably 50 mol% or more. Z represents a hydrogen atom or a glycidyl group represented by the above formula (6). n is an average value of 21 or more, preferably in the range of 30 to 5,000. Such a phosphorus-containing phenoxy resin can be produced by, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2001-310939.
In the general formulas (2), (3), (4) and (5), Y represents a phosphorus-containing group represented by the general formula (7) or (8). A in Formula (5) is a single bond or —CH 2 —, —C (CH 3 ) 2 —, —CH (CH 3 ) —, —S—, —SO 2 —, —O—, —CO— or A divalent group selected from the above general formula (9) is shown. In formulas (2) to (5) and (7) to (9), R 1 to R 10 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Preferably, they are a hydrogen atom or a methyl group, and the number of methyl groups is 4 or less.
In addition, the component (A) is the divalent group represented by the general formulas (2) and (5) in the general formula (1), and R 1 to R 3 in the general formula (2) are While a hydrogen atom, Y represents a general formula (7), R 1 ~R 8 in the general formula (5) is a hydrogen atom, a is -C (CH 3) 2 - may be those shown.
In addition, the component (A) is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and R 1 to R 3 in the general formula (3) are hydrogen atoms. Y represents general formula (7), and R 1 to R 8 in general formula (5) represent a hydrogen atom, but A may represent —C (CH 3 ) 2 —.
In addition, the component (A) is a divalent group represented by the general formulas (2) and (5) in the general formula (1), and R 1 to R 3 in the general formula (2) are hydrogen atoms. Where Y represents the general formula (7) and R 1 to R 8 in the general formula (5) represent a hydrogen atom, but A may represent the general formula (9).
In addition, the component (A) is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and R 1 to R 3 in the general formula (3) are hydrogen atoms. Where Y represents the general formula (7) and R 1 to R 8 in the general formula (5) represent a hydrogen atom, but A may represent the general formula (9).
The (b) component epoxy resin is an epoxy resin represented by the general formula (10). In the formula (10), W represents a divalent group represented by the general formula (5), m is an integer of 0 or more, and the average of m is 0.1 to 15. Examples of the epoxy resin represented by the general formula (10) include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a cresol novolak type epoxy resin, a biphenyl type epoxy resin, and the like. Can be used as a mixture. The epoxy resin is preferably substantially free of halogen elements.
Considering the improvement in crack resistance of a dried product or a film (hereinafter also referred to as B-stage state composition) obtained by drying the resin composition, the degree of polymerization m = 0 in the general formula (10) is The area percentage of the chromatogram measured using the area percentage of gel permeation chromatography is preferably 70% or more, more preferably 80% or more. And it is preferable that it is liquid at normal temperature.
In 100 parts by weight of the flame retardant adhesive resin composition of the present invention, the component (ii) is blended in an amount of 20 to 80 parts by weight, preferably 30 to 70 parts by weight, more preferably 40 to 60 parts by weight. . If the amount is less than 20 parts by weight, the adhesive strength is not expressed due to a decrease in flexibility and an increase in internal stress. If the amount exceeds 80 parts by weight, the soldering heat resistance is reduced due to a decrease in the ratio of the crosslinking component, and the performance as an adhesive. Damage. Moreover, it is preferable to mix | blend (b) component in 20-70 weight part. (B) If the component is less than this range, the crosslink density is reduced and the heat resistance of the adhesive is reduced. Conversely, if it is too much, the flexibility of the adhesive is reduced and the adhesive is peeled off. The problem arises that the adhesive strength is reduced.
As the (C) component curing agent, those known as the (B) component epoxy resin curing agent can be used. Acid anhydrides can be used. When (imidazole) is used as the component (c), it is also calculated as the component (d) because it is also the component (d). The amount of component (c) is preferably blended so that the equivalent ratio ((c) / (b)) is 0.5 to 1.5 with respect to the epoxy resin of component (b). Generally, when using a phenol resin-type hardening | curing agent, it is good to set it as 0.8-1.2, when using an amine-type hardening | curing agent.
As the component (2) curing accelerator, organic phosphorus compounds such as triphenylphosphine, imidazoles such as 2-phenylimidazole and 2-ethyl-4-methylimidazole, tertiary amines, and Lewis acids can be used. The blending ratio is appropriately selected according to the required curing time, but is generally used in the range of 0.01 to 3.0% by weight with respect to the flame retardant adhesive resin composition. Is good.
Moreover, the glass transition temperature (Tg) of the hardened | cured material obtained by thermosetting the flame-retardant adhesive resin composition of this invention becomes like this. Preferably it is 100 degreeC or more, More preferably, it exists in the range of 100-170 degreeC. Good. When the glass transition temperature of the cured product after thermosetting is less than 100 ° C., the migration resistance decreases. The glass transition temperature after curing of the resin composition can be adjusted mainly by the type and blending amount of the (b) component epoxy resin and the (c) component curing agent.
Here, the measurement of the glass transition temperature of hardened | cured material is based on the conditions of the characteristic evaluation method mentioned later: <hardened | cured material characteristic> [glass transition temperature (Tg)].
The flame retardant adhesive resin composition of the present invention is an extender such as aluminum hydroxide and magnesium hydroxide as inorganic flame retardant, silica as reinforcing agent or extender, calcium carbonate, etc. as components other than the above essential components The polymer elastomer can be blended as a flexibility imparting agent, or additives such as a viscosity modifier and a coupling agent can be blended. The addition rate is appropriately selected according to the required characteristics.
The flame retardant adhesive resin composition of the present invention is used as an adhesive resin solution dissolved or dispersed in an organic solvent such as methyl ethyl ketone, dimethylformamide, 2-ethoxyethanol. In this case, the solid content concentration is appropriately selected depending on the use conditions, but is generally 20 to 60% by weight. In addition, a solvent is understood not as a component which comprises the flame-retardant adhesive resin composition of this invention but the component used in order to make a flame-retardant adhesive resin composition into a solution. Therefore, in calculating the compounding amount of each component in the flame retardant adhesive resin composition, the solvent is excluded from the calculation.
The flame retardant adhesive resin composition of the present invention can be used after being formed into a film. In this case, it is possible to form a film using a conventionally known method, but as an example of a suitable molding method, a flame retardant adhesive resin composition is diluted with an organic solvent such as methyl ethyl ketone to form a solution. After that, the obtained adhesive resin solution is applied on a base material such as a metal foil, a polyester film, a polyimide film, etc., whose surface has been subjected to a release treatment, by evaporating the solvent to make it tack-free, And the composition which comprises an adhesive resin layer is dried on the temperature and time conditions which do not carry out a curing reaction, an adhesive film layer is formed, this is peeled from a base material, and it is set as a flame-retardant adhesive film. Although this drying condition changes with the solvent and resin composition to be used, generally 130-160 degreeC, the temperature for 3 to 10 minutes, and a time range are selected. Moreover, when using as a bonding sheet which consists of release films, such as polyester, and an adhesive film layer, ratio of the thickness of a release film and an adhesive film layer is although it does not specifically limit, Release film thickness is 12.5 micrometers. Those having an adhesive layer of 15 to 30 μm can be suitably used.
Examples of the method of using the flame retardant adhesive film of the present invention include, for example, a flexible printed wiring board, a glass fiber-epoxy wiring board, a paper-phenol wiring board, or various printed wiring boards obtained by processing these circuits, metals, Suitable for adhesion of adherends such as resin substrates. A printed wiring board can be obtained by bonding a metal foil and a resin base material, and a multilayer printed wiring board or printed wiring board can be obtained by bonding printed wiring boards or printed wiring boards together. By bonding the board and the cover lay, a printed wiring board with a cover lay can be obtained. In addition, it can be used as an adhesive film for connecting a printed wiring board or a printed wiring board. In any case, it is advantageously used in the process of manufacturing or processing a printed circuit board.
The flame retardant adhesive resin composition of the present invention can also be applied to the adhesive layer of the coverlay film. In that case, the cover lay film is formed from the polyimide film and the adhesive resin composition, but as a method of forming the cover lay film of the present invention, it is possible to form a film using a conventional method. . As an example of a suitable molding method, the adhesive resin composition is diluted with an organic solvent such as methyl ethyl ketone to form a solution, and then the obtained adhesive resin solution is applied onto a polyimide film, and the solvent is evaporated. There is a method in which the adhesive resin composition constituting the adhesive layer is made to be tack-free and dried at a temperature and time conditions that do not cause a curing reaction to form a coverlay film. The polyimide film is coated with a thickness of 2 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm, and then dried. Although this drying condition changes with the solvent and resin composition to be used, generally 130-160 degreeC, the temperature for 3 to 10 minutes, and a time range are selected. In addition, the polyimide film is necessary to increase heat resistance and flame retardancy, and the thickness of the polyimide film may be an appropriate thickness as required, preferably 3 to 50 μm, More preferably, 5-30 micrometers is good. The ratio of the thickness of the polyimide film and the adhesive layer is not limited, but a coverlay film provided with an adhesive layer of 15 to 20 μm with a film thickness of 12.5 μm, an adhesive layer of 25 to 35 μm with a film thickness of 25 μm, respectively, is common. is there.
The flame-retardant adhesive resin composition of the present invention can also be applied to an adhesive layer of a flexible copper-clad laminate (hereinafter also referred to as a three-layer copper-clad laminate). In that case, the flexible copper clad laminate is formed from a polyimide film, the adhesive resin composition, and the copper foil. As a method of forming the flexible copper clad laminate of the present invention, the conventional method is used. Is possible. As an example of a suitable lamination method, the adhesive resin composition is diluted with an organic solvent such as methyl ethyl ketone to form a solution, and then applied to one or both sides of a polyimide film, and the organic solvent content is dried, and then heated with a hot roll. It can manufacture by sticking copper foil on the single side | surface or both surfaces of a polyimide film, and then heat-hardening. Although drying conditions change with the solvent and resin composition to be used, generally, a temperature and a time range of 130 to 160 ° C. and 3 to 10 minutes are selected, and curing conditions are 160 to 190 ° C. and 10 to 120. Generally, it is selected from the temperature and time range of minutes. Although the thickness of a polyimide film layer, an adhesive bond layer, and copper foil is not specifically limited, It is common to set it as polyimide film thickness 5-25 micrometers, adhesive layer 10-30 micrometers, and copper foil thickness 10-35 micrometers.

次に、合成例、実施例及び比較例により本発明を具体的に説明する。硬化物特性およびＦＰＣ用材料特性である、カバーレイフィルム、ボンディングシートおよび３層銅張積層板の特性評価方法は、以下の通りである。
＜硬化物特性＞
［ガラス転移温度（Ｔｇ）］
接着剤樹脂組成物をメチルエチルケトン溶剤に溶解して３５重量％接着剤溶液とした後、縦×横×厚さ＝５０×１５０×１ｍｍのフッ素樹脂シート上に塗布し、１３５℃で５分間乾燥して溶剤を蒸発後、接着剤塗布面に同一形状の別のフッ素樹脂シートを重ね、１７０℃で１時間、真空加熱プレスを行って、試料となる接着剤硬化物フィルムを調製した。この試料の温度分散ｔａｎδ曲線を動的粘弾性測定装置（セイコーインスツルメンツ株式会社製、ＤＭＳ−６１００）を用い、周波数１０Ｈｚ、温度範囲−１５０〜２００℃、昇温速度２℃／分の条件で測定し、得られた温度−ｔａｎδ曲線のピーク温度をガラス転移温度（Ｔｇ）とした。
［線膨張係数（α１、α２）］
試料および装置は、上記と同じものを用い、温度範囲−１５０〜２００℃、昇温速度２℃／分の条件下でＴＭＡ曲線を作成し、前記Ｔｇより低い温度領域の曲線の傾きからガラス状態の線膨張係数α１を、前記Ｔｇより高い温度領域の曲線の傾きからゴム状態の線膨張係数α２をおのおの算出した。
［引張り特性（強度、伸び）］
上記接着剤硬化物フィルムをＪＩＳ Ｋ ６２５１ １号ダンベル片の形状に型抜きしたものを試料とした。この試料を引張り試験機（株式会社島津製作所製、ＡＧＳ−５００）にセットし、ＪＩＳ Ｋ ７１６１の手順に従い、室温下、クロスヘッドスピード１ｍｍ／分で引張り試験を行い、試料破断時の強度および伸びを測定した。
＜ＦＰＣ用材料特性及びカバーレイフィルム特性＞
［耐割れ性］
上記３５重量％接着剤溶液を、縦×横×厚さ＝２００ｍｍ×３００ｍｍ×２５μｍのポリイミドフィルム（株式会社カネカ製、アピカルＮＰＩ）の片面に接着剤溶液を塗布し、１３５℃で５分間乾燥を行い、接着剤層厚さ２５μｍのカバーレイフィルムを調製後、カバーレイフィルムの接着剤塗布面が内側になるように、指でカバーレイフィルムを折り曲げた時、接着剤に割れが発生するかどうかを目視観察し、割れ発生がほとんど認められない場合を「良」、割れ発生が全く認められない場合を「優」と判定した。［耐燃性］上記と同じ条件でカバーレイフィルムを調製後、ＪＰＣＡ−ＢＭ０２−１９９１の７．７記載の寸法に切り取った２枚のカバーレイフィルムを接着剤面で貼り合わせ、その後、１７０℃で１時間、加熱プレスを行い、その後１９０℃で２時間、後硬化を行って試料調製を行った。続いて、ＪＰＣＡ−ＢＭ０２−１９９１の７．７の手順に従って耐燃性試験耐燃性測定を行い、ＵＬ規格９４の判定基準である、「ＶＴＭ−０」、「耐燃性なし」の２水準で耐燃性を判定した。「ＶＴＭ−０」は耐燃性があることを意味する。
［引きはがし強さ］
上記と同じ条件でカバーレイフィルムを調製後、ＪＰＣＡ−ＢＭ０２−１９９１の７．５の引きはがし強さに従って、テストピースの作製及び引きはがし強さの測定を実施した。テストピースの接着剤熱硬化条件は、同様に１７０℃で１時間、加熱プレスを行った後、１９０℃で２時間、後硬化とした。
［はんだ耐熱性（乾燥）］
上記と同じ条件でカバーレイフィルムを調製後、ＪＰＣＡ−ＢＭ０２−１９９１−７．９のはんだ耐熱性（外観）に従って、テストピースの作製及びはんだ耐熱性試験を実施した。テストピース作製時の接着剤熱硬化条件は前記同様、１７０℃で１時間の加熱プレス後、１９０℃で２時間の後硬化とした。このテストピースを１０５℃で１時間乾燥させた後、各評価温度に設定した半田浴中に５秒間浮かせて、その接着状態を観察、発泡、ふくれ、剥離等の不具合の有無を確認した。表中の「３００℃」は、３００℃の半田浴中で評価して、不具合が認められないことを意味する。
［はんだ耐熱性（耐湿）］
上記と同じ条件でカバーレイフィルムを調製後、４０℃、相対湿度９０％で２４時間放置した後、各評価温度に設定した半田浴中に５秒間浮かせて、その接着状態を観察、発泡、ふくれ、剥離等の不具合の有無を確認した。表中の「２６０℃」は、２６０℃の半田浴中で評価して、不具合が認められないことを意味する。
［耐折性］
上記と同じ条件でカバーレイフィルムを調製した後、銅張積層板（新日鐵化学株式会社製、ＭＢ１２−２５−１２ＲＥＱ）を用いて、ＪＰＣＡ−ＢＭ０２−１９９１−７．６．１のＡ法耐折性試験に従って、テストピースの作製及び耐折性試験を実施した。硬化条件は、同様に１７０℃、１時間のカバーレイフィルムの加熱プレス後、１９０℃、２時間の後硬化とした。曲率半径は０．３８ｍｍとした。判定は、試料銅回路が断線し、通電不能になるまでの屈曲回数を測定し、断線までの屈曲回数が１０００回以上３０００回未満の場合を「可」、３０００回以上の場合を「良」と判定した。
［接着剤のフロー］
上記と同じ条件でカバーレイフィルムを調製後、ＪＰＣＡ−ＢＭ０２−１９９１−７．１０に従って、テストピースの作製及び接着剤のフロー試験を実施した。判定は、接着剤の染み出した長さを測定した。
［耐マイグレーション性］
上記と同じ条件でカバーレイフィルムを調製後、回路のライン／スペースが１００μｍ／２００μｍとなるように片面銅張り積層板の銅箔をエッチング加工した櫛型回路パターンにカバーレイフィルムを、１７０℃で１時間、加熱プレス後、１９０℃で２時間、後硬化させ試料を調製した。同試料を８５℃−８５ＲＨ％に温湿度調節した恒温恒湿槽中に入れ、試料中の櫛型回路に直流５０Ｖを５００時間通電した後、試料を取り出し、櫛型回路とその周辺を顕微鏡観察し、デンドライト発生が認められた場合を「不可」、認められなかった場合を「良」と判定した。
＜ボンディングシート特性＞
［耐燃性］
上記３５重量％接着剤溶液を、縦×横×厚さ＝２００ｍｍ×３００ｍｍ×２５μｍのポリエステル剥離フィルムの片面に接着剤溶液を塗布し、１３５℃で５分間乾燥を行い、接着剤層厚さ２５μｍのボンディングシートを調製後、１７０℃で１時間の前硬化、その後１９０℃で２時間、後硬化を行って試料調製を行った。続いて、ＪＩＳ Ｃ ６４７１の手順に従って耐燃性試験を行い、ＵＬ規格９４の判定基準である、「Ｖ−０」、「耐燃性なし」の２水準で耐燃性を判定した。「Ｖ−０」は耐燃性があることを意味する。
［引きはがし強さ］
上記と同じ条件でボンディングシートを調製後、ボンディングシートを剥離フィルムからはがした後、縦×横×厚さ＝２００ｍｍ×３００ｍｍ×２５μｍの２枚の銅箔の光沢面の間に挟み、１７０℃で１時間加熱プレスを行った後、１９０℃で２時間、後硬化を行って試料を作製、引きはがし強さを、ＪＩＳ Ｃ ６４７１に従って測定した。
［スルーホールメッキ導通性］
上記と同じ条件でボンディングシートを調製後、ボンディングシートを剥離フィルムからはがした、１７０℃で１時間の前硬化、１９０℃で２時間の後硬化を行い硬化シートを調製した。この硬化シートにドリリングによって直径０．３ｍｍのスルーホールを開け、同ホールの内側に無電解銅メッキ法にて、２０〜２５μｍの銅メッキ層を形成し、試料とした。試料に−４０℃・１５分、１５０℃・１５分の冷熱サイクル暴露を施し、導通不良を生じるまでのサイクル数を測定し、５００サイクル以下を「不可」、２０００サイクル以上を「良」と判定した。
＜３層銅張積層板特性＞
［耐燃性］
上記３５重量％接着剤溶液を、縦×横×厚さ＝２００ｍｍ×３００ｍｍ×２５μｍのポリイミドフィルムの片面に接着剤溶液を塗布し、１３５℃で５分間乾燥を行い、接着剤層厚さ２５μｍの絶縁樹脂層を形成後、縦×横×厚さ＝２００ｍｍ×３００ｍｍ×１８μｍの銅箔を粗化面で重ね、１７０℃で１時間の熱プレス後、１９０℃で２時間の後硬化を行って３層銅張積層板を調製した。続いて、ＪＩＳ Ｃ ６４７１の手順に従って耐燃性試験を行い、ＵＬ規格９４の判定基準である、「Ｖ−０」、「耐燃性なし」の２水準で耐燃性を判定した。「Ｖ−０」は耐燃性があることを意味する。
［引きはがし強さ］
上記と同じ条件で調製した３層銅張積層板における銅箔層と絶縁樹脂層の引きはがし強さを、ＪＩＳ Ｃ ６４７１に従って測定した。
［耐折性］
上記と同じ条件で調製した３層銅張積層板の耐折性を、ＪＩＳ Ｃ ６４７１に従って測定した。曲率半径は０．８ｍｍとした。判定は、試料銅回路が断線し、通電不能になるまでの屈曲回数を測定した。Next, the present invention will be specifically described with reference to synthesis examples, examples and comparative examples. The characteristics evaluation method of the coverlay film, the bonding sheet, and the three-layer copper-clad laminate, which are the cured product characteristics and the FPC material characteristics, is as follows.
<Hardened product characteristics>
[Glass transition temperature (Tg)]
After dissolving the adhesive resin composition in a methyl ethyl ketone solvent to form a 35 wt% adhesive solution, it was applied on a fluororesin sheet of length × width × thickness = 50 × 150 × 1 mm and dried at 135 ° C. for 5 minutes. After evaporating the solvent, another fluororesin sheet having the same shape was stacked on the adhesive-coated surface, and vacuum heated pressing was performed at 170 ° C. for 1 hour to prepare a cured adhesive film as a sample. The temperature dispersion tan δ curve of this sample was measured using a dynamic viscoelasticity measuring device (Seiko Instruments Co., Ltd., DMS-6100) at a frequency of 10 Hz, a temperature range of −150 to 200 ° C., and a temperature increase rate of 2 ° C./min. The peak temperature of the obtained temperature-tan δ curve was defined as the glass transition temperature (Tg).
[Linear expansion coefficient (α 1 , α 2 )]
Using the same sample and apparatus as described above, a TMA curve was created under the conditions of a temperature range of −150 to 200 ° C. and a heating rate of 2 ° C./min, and the glass state was determined from the slope of the curve in the temperature region lower than the Tg. the coefficient of linear expansion alpha 1, were each calculated coefficient of linear expansion alpha 2 of the rubbery state from the slope of the curve in the temperature range higher than the Tg.
[Tensile properties (strength, elongation)]
A sample obtained by punching the cured adhesive film into a JIS K 6251 No. 1 dumbbell piece was used as a sample. This sample was set in a tensile tester (manufactured by Shimadzu Corporation, AGS-500), and a tensile test was performed at room temperature under a crosshead speed of 1 mm / min according to the procedure of JIS K 7161. Was measured.
<FPC material characteristics and coverlay film characteristics>
[Crack resistance]
The 35 wt% adhesive solution is applied to one side of a polyimide film (manufactured by Kaneka Corporation, Apical NPI) of length x width x thickness = 200 mm x 300 mm x 25 µm, and dried at 135 ° C for 5 minutes. After the coverlay film with a thickness of 25 μm is prepared, whether or not the adhesive cracks when the coverlay film is folded with a finger so that the adhesive-coated surface of the coverlay film is on the inside The case where almost no crack was observed was judged as “good”, and the case where no crack was found was judged as “excellent”. [Flame resistance] After preparing a coverlay film under the same conditions as above, two coverlay films cut to the dimensions described in 7.7 of JPCA-BM02-1991 were bonded together on the adhesive surface, and then at 170 ° C. A sample was prepared by performing a heat press for 1 hour and then post-curing at 190 ° C. for 2 hours. Subsequently, the flame resistance test is performed according to the procedure of 7.7 of JPCA-BM02-1991, and the flame resistance is measured at two levels, “VTM-0” and “no flame resistance”, which are the criteria of UL standard 94. Was judged. “VTM-0” means flame resistance.
[Stripping strength]
After preparing the coverlay film under the same conditions as described above, the test piece was prepared and the peel strength was measured according to the peel strength of 7.5 of JPCA-BM02-1991. Similarly, the test piece adhesive was thermally cured at 170 ° C. for 1 hour, followed by heat pressing at 190 ° C. for 2 hours.
[Solder heat resistance (dry)]
After preparing the coverlay film under the same conditions as described above, a test piece was prepared and a solder heat resistance test was performed according to the solder heat resistance (appearance) of JPCA-BM02-1991-7.9. The adhesive thermosetting conditions at the time of test piece preparation were the same as described above: after heat pressing at 170 ° C. for 1 hour and after curing at 190 ° C. for 2 hours. After drying this test piece at 105 ° C. for 1 hour, it was floated in a solder bath set to each evaluation temperature for 5 seconds, and the adhesion state was observed and the presence or absence of defects such as foaming, blistering, and peeling was confirmed. “300 ° C.” in the table means that no defect is observed when evaluated in a solder bath at 300 ° C.
[Solder heat resistance (moisture resistance)]
After preparing the coverlay film under the same conditions as described above, it was allowed to stand for 24 hours at 40 ° C. and 90% relative humidity, and then floated in a solder bath set at each evaluation temperature for 5 seconds to observe the adhesive state, foam, and blister. The presence or absence of defects such as peeling was confirmed. “260 ° C.” in the table means that no defect is observed when evaluated in a solder bath at 260 ° C.
[Folding resistance]
After preparing a coverlay film under the same conditions as above, a copper-clad laminate (manufactured by Nippon Steel Chemical Co., Ltd., MB12-25-12REQ) was used, and method A of JPCA-BM02-1991-7.6.1 According to the bending resistance test, a test piece was prepared and a bending resistance test was performed. Similarly, the curing conditions were 170 ° C. for 1 hour after heat-pressing the coverlay film, and 190 ° C. for 2 hours after curing. The radius of curvature was 0.38 mm. Judgment is performed by measuring the number of bendings until the sample copper circuit is disconnected and cannot be energized. When the number of bendings until the disconnection is 1000 times or more and less than 3000 times, “Yes”, and when the number of bending times is 3000 times or more, “Good”. It was determined.
[Adhesive flow]
After preparing a coverlay film under the same conditions as described above, a test piece was prepared and an adhesive flow test was performed according to JPCA-BM02-1991-7.10. The determination was made by measuring the length of the adhesive that oozed out.
[Migration resistance]
After preparing the coverlay film under the same conditions as above, the coverlay film was applied to a comb-shaped circuit pattern in which the copper foil of the single-sided copper-clad laminate was etched so that the circuit line / space was 100 μm / 200 μm at 170 ° C. A sample was prepared by post-curing at 190 ° C. for 2 hours after hot pressing for 1 hour. The sample is placed in a thermo-hygrostat whose temperature and humidity are adjusted to 85 ° C. to 85 RH%, and a 50 V DC current is passed through the comb circuit in the sample for 500 hours. Then, the sample is taken out, and the comb circuit and its surroundings are observed with a microscope. A case where dendrite was observed was judged as “impossible”, and a case where dendrite was not found was judged as “good”.
<Bonding sheet characteristics>
[Flame resistance]
The 35 wt% adhesive solution was applied to one side of a polyester peel film of length × width × thickness = 200 mm × 300 mm × 25 μm, dried at 135 ° C. for 5 minutes, and an adhesive layer thickness of 25 μm. After preparing the bonding sheet, a sample was prepared by pre-curing at 170 ° C. for 1 hour and then post-curing at 190 ° C. for 2 hours. Subsequently, a flame resistance test was performed in accordance with the procedure of JIS C 6471, and the flame resistance was determined based on two standards of “V-0” and “no flame resistance”, which are UL standard 94 criteria. “V-0” means flame resistance.
[Stripping strength]
After preparing the bonding sheet under the same conditions as above, the bonding sheet was peeled off from the release film, and then sandwiched between the glossy surfaces of two copper foils of length × width × thickness = 200 mm × 300 mm × 25 μm, 170 ° C. The sample was heated and pressed at 190 ° C. for 2 hours and then cured at 190 ° C. for 2 hours to prepare a sample. The peel strength was measured in accordance with JIS C 6471.
[Through hole plating conductivity]
After preparing the bonding sheet under the same conditions as above, the bonding sheet was peeled off from the release film, precured at 170 ° C. for 1 hour, and post-cured at 190 ° C. for 2 hours to prepare a cured sheet. A through hole having a diameter of 0.3 mm was formed in the cured sheet by drilling, and a 20 to 25 μm copper plating layer was formed inside the hole by an electroless copper plating method to prepare a sample. Samples are exposed to -40 ° C / 15 min and 150 ° C / 15 min cooling cycles, and the number of cycles until poor continuity is measured. 500 cycles or less are judged as “impossible” and 2000 cycles or more are judged as “good”. did.
<Three layer copper clad laminate characteristics>
[Flame resistance]
The 35 wt% adhesive solution was applied to one side of a polyimide film of length × width × thickness = 200 mm × 300 mm × 25 μm, dried at 135 ° C. for 5 minutes, and an adhesive layer thickness of 25 μm After forming the insulating resin layer, the copper foil of length × width × thickness = 200 mm × 300 mm × 18 μm was laminated on the roughened surface, hot-pressed at 170 ° C. for 1 hour, and then post-cured at 190 ° C. for 2 hours. A three-layer copper clad laminate was prepared. Subsequently, a flame resistance test was performed in accordance with the procedure of JIS C 6471, and the flame resistance was determined based on two standards of “V-0” and “no flame resistance”, which are UL standard 94 criteria. “V-0” means flame resistance.
[Stripping strength]
The peel strength between the copper foil layer and the insulating resin layer in the three-layer copper-clad laminate prepared under the same conditions as described above was measured according to JIS C 6471.
[Folding resistance]
The folding resistance of the three-layer copper-clad laminate prepared under the same conditions as described above was measured according to JIS C 6471. The curvature radius was 0.8 mm. The determination was made by measuring the number of bendings until the sample copper circuit was disconnected and could not be energized.

合成例１
下記式（１１）で示されるリン含有フェノールである、１０−（２，５−ジヒドロキシフェニル）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０Ｈ−９−オキサイド（三光化学株式会社製、ＨＣＡ−ＨＱ、水酸基当量１６２ｇ／ｅｑ、リン含有量９．５重量％）を１６２部、ビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５、エポキシ当量１７１．６ｇ／ｅｑ）を１７５部、シクロヘキサノンを１４４部、触媒として、２−エチル−４−メチルイミダゾール（四国化成工業株式会社製、２Ｅ４ＭＺ）の０．１３部を、攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた４つ口のガラス製セパラブルフラスコに仕込み、常圧、１５０℃〜１７０℃の温度で８時間反応させた後、シクロヘキサノン１５６部、Ｎ，Ｎ−ジメチルホルムアミド３００部を加えて、リン含有フェノキシ樹脂Ａの固形分濃度３６重量％の溶液９３７部を得た。本樹脂溶液をポリエステル離型フィルムの上に塗布後、１６５℃で５分間乾燥して溶剤を蒸発させ、リン含有率４．６％のリン含有フェノキシ樹脂Ａを得た。

Figure 2008105563
カラムとしてＳｈｏｄｅｘ ＡＤ−８００Ｐ＋ＴＳＫｇｅｌＳｕｐｅｒＨＭ−Ｈ＋ＳｕｐｅｒＨＭ−Ｈ＋ＳｕｐｅｒＨ２０００を、溶離液としてＮ，Ｎ−ジメチルホルムアミド（２０ｍＭ臭化リチウム含有品）を使用してリン含有フェノキシ樹脂ＡのＧＰＣ分析を行った結果、同樹脂の標準ポリエチレンオキサイド換算重量平均分子量は、７７，３００であった。
合成例２
合成例１における反応時間を８時間から１０時間に変更したこと以外は、合成例１と同様にして、リン含有フェノキシ樹脂の合成を行って、リン含有率４．６％のリン含有フェノキシ樹脂Ｂを得た。同様の条件でＧＰＣ分析を行った結果、同樹脂の標準ポリエチレンオキサイド換算重量平均分子量は、１０９，７００であった。
合成例３
合成例１における反応時間を８時間から２０時間に変更したこと以外は、合成例１と同様にして、リン含有フェノキシ樹脂の合成を行って、リン含有率４．６％のリン含有フェノキシ樹脂Ｃを得た。同様の条件でＧＰＣ分析を行った結果、同樹脂の標準ポリエチレンオキサイド換算重量平均分子量は、１９８，４００であった。
合成例４
合成例１における上記式（１１）で示されるリン含有フェノールの代わりに、下記式（１２）で示されるリン含有ナフトール（水酸基当量２２１．６ｇ／ｅｑ、リン含有率８．２％）を２２２ｇ用いたこと、および合成例１における反応時間を８時間から１０時間に変更したこと以外は、合成例１と同様にして、リン含有フェノキシ樹脂の合成を行って、リン含有率４．０％のリン含有フェノキシ樹脂Ｄを得た。同様の条件でＧＰＣ分析を行った結果、同樹脂の標準ポリエチレンオキサイド換算重量平均分子量は、１２２，４７０であった。
Figure 2008105563
合成例５
合成例１におけるビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、ＹＤ−８１２５、エポキシ当量１７１．６ｇ／ｅｑ）を１７５部の代わりに、下記式（１３）で示されるビスフェノールフルオレン型エポキシ樹脂（新日鐵化学株式会社製、ＥＲＦ−３００、エポキシ当量２３１ｇ／ｅｑ）の２３１部を用いたこと、および合成例１における反応時間を８時間から１０時間に変更したこと以外は、合成例１と同様にして、リン含有フェノキシ樹脂の合成を行って、リン含有率４．４％のリン含有フェノキシ樹脂Ｅを得た。同様の条件でＧＰＣ分析を行った結果、同樹脂の標準ポリエチレンオキサイド換算重量平均分子量は、１１７，９００であった。
Figure 2008105563
合成例６
合成例１における反応時間を８時間から５時間に変更したこと以外は、合成例１と同様にして、リン含有フェノキシ樹脂の合成を行って、リン含有率４．６％のリン含有フェノキシ樹脂Ｆを得た。同様の条件でＧＰＣ分析を行った結果、同樹脂の標準ポリエチレンオキサイド換算重量平均分子量は、３９，２００であった。
合成例７
合成例４における反応時間を１０時間から５時間に変更したこと以外は、合成例４と同様にして、リン含有フェノキシ樹脂の合成を行って、リン含有率４．０％のリン含有フェノキシ樹脂Ｇを得た。同様の条件でＧＰＣ分析を行った結果、同樹脂の標準ポリエチレンオキサイド換算重量平均分子量は、４１，５００であった。
接着剤樹脂組成物を調製するために使用した各成分の略号を次に示す。
ＹＤ−１２８：ビスフェノールＡ型エポキシ樹脂（東都化成株式会社製）
ＹＤＦ−１７０：ビスフェノールＦ型エポキシ樹脂（東都化成株式会社製）
ＢＲＧ−５５５：ノボラック型フェノール樹脂（昭和高分子株式会社製）
ＤＩＣＹ：ジシアンジアミド（日本カーバイド工業株式会社製）
ＤＤＭ：ジアミノジフェニルメタン
ＤＤＳ：ジアミノジフェニルスルホン
樹脂Ａ：合成例１のリン含有フェノキシ樹脂Ａ（重量平均分子量７７，３００）
樹脂Ｂ：合成例２のリン含有フェノキシ樹脂Ｂ（重量平均分子量１０９，７００）
樹脂Ｃ：合成例３のリン含有フェノキシ樹脂Ｃ（重量平均分子量１９８，４００）
樹脂Ｄ：合成例４のリン含有フェノキシ樹脂Ｄ（重量平均分子量１２２，４７０）
樹脂Ｅ：合成例５のリン含有フェノキシ樹脂Ｅ（重量平均分子量１１７，９００）
樹脂Ｆ：合成例６のリン含有フェノキシ樹脂Ｆ（重量平均分子量３９，２００）
樹脂Ｇ：合成例７のリン含有フェノキシ樹脂Ｇ（重量平均分子量４１，５００）
ＹＰ−５０ＳＣ：フェノキシ樹脂（東都化成株式会社製）（重量平均分子量５０，５００）
ＰＮＲ１Ｈ：カルボキシル基含有ＮＢＲ（株式会社ＪＳＲ製）
ＳＰＥ−１００：シクロフェノキシキホスファゼン（大塚化学株式会社製）
２Ｅ４ＭＺ：２−エチル−４−メチルイミダゾール（四国化成工業株式会社製）
エポキシ樹脂のＧＰＣ分析は以下の条件で行った。
装置；東ソー株式会社製ＨＬＣ−８１２０ＧＰＣ
カラム；東ソー株式会社製、ＴＳＫ−ＧＥＬ：ＳＵＰＥＲ ＨＺ２０００×１、ＳＵＰＥＲ ＨＺ３０００×１、ＳＵＰＥＲ ＨＺ４０００×１
カラム温度；４０℃
移動相；テトラヒドロフラン（ＴＨＦ）
流量；０．３５ｍｌ／ｍｉｎ
検出器；組み込み型
試料濃度；０．０３ｇ／ＴＨＦ１０ｍｌ
ｍ＝０成分の含有量は、得られたＧＰＣクロマトグラフから得られるｍ＝０成分のピークの面積を全成分のピーク面積で除した面積％を含有量（％）とした。
ＹＤ−１２８のＧＰＣ分析の結果、重合度ｍ＝０体の含有量は８２％であった。
ＹＤＦ−１７０のＧＰＣ分析の結果、重合度ｍ＝０体の含有量は７８％であった。
実施例１〜実施例１６
表１〜３記載の割合（重量％）で各成分を配合して接着剤樹脂組成物を調製した。この接着剤樹脂組成物について、硬化物特性、ＦＰＣ用材料特性（カバーレイフィルム特性、ボンディングシート特性、３層銅張積層板特性）を評価した。結果を表１〜３に示す。
比較例１〜５
表４記載の割合で各成分を配合して接着剤樹脂組成物を調製した。この接着剤樹脂組成物について、硬化物特性、ＦＰＣ用材料特性（カバーレイフィルム特性、ボンディングシート特性、３層銅張積層板特性）を評価した。結果を表４に示す。
以上の結果から、本発明の接着剤樹脂組成物を用いた実施例１〜１６では、カバーレイフィルム特性における耐燃性はＶＴＭ−０、ボンディングシート特性及び３層銅張積層板特性における耐燃性はＶ−０であり、いずれも難燃性があることが確認された。また、カバーレイフィルム特性におけるはんだ耐熱性（乾燥）は３００℃以上、はんだ耐熱性（耐湿）は２５０℃以上、耐折性は２８００回以上であり、３層銅張積層板特性における耐折性は１５０回以上であり、いずれも良好な物性を示す。更に、カバーレイフィルム特性における接着剤のフローは０．１８ｍｍ以下であり、良好な物性を示し、耐マイグレーション性も問題はなく、またボンディングシート特性におけるスルーホールメッキ導通性は優れている。実施例１〜１６の中でも、特に、分子量１０９，７００の樹脂Ｂ、分子量１２２，４７０の樹脂Ｄ又は分子量１１７，９００の樹脂Ｅを用いたＦＰＣ用材料特性は、はんだ耐熱性及び耐折性共に優れている。
一方、比較例１〜２では、ＦＰＣ用材料特性における難燃性は示すものの、カバーレイフィルム特性におけるはんだ耐熱性及び耐折性は低く、接着剤のフロー性も０．８ｍｍ以上となり、実用性に欠ける。比較例３〜５では、ＦＰＣ用材料特性における耐燃性が認められない。
以上の結果をまとめて、実施例１〜６を表１、実施例７〜１２を表２、実施例１３〜１６を表３、及び比較例１〜５を表４に示す。
Figure 2008105563
Figure 2008105563
Figure 2008105563
Figure 2008105563
 Synthesis example 1
10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10H-9-oxide (manufactured by Sanko Chemical Co., Ltd., HCA), which is a phosphorus-containing phenol represented by the following formula (11) -HQ, hydroxyl group equivalent 162 g / eq, phosphorus content 9.5 wt%) 162 parts, bisphenol A type epoxy resin (manufactured by Tohto Kasei Co., Ltd., YD-8125, epoxy equivalent 171.6 g / eq), 175 parts, 144 parts of cyclohexanone as a catalyst, 0.13 part of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2E4MZ), 4 equipped with a stirrer, thermometer, cooling pipe and nitrogen gas introducing device After charging into a glass-separable flask with a neck and reacting at normal pressure and a temperature of 150 ° C. to 170 ° C. for 8 hours, cyclohexanone 15 Parts, N, added 300 parts of N- dimethylformamide to obtain a solution 937 parts of a solid concentration of 36 wt% of the phosphorus-containing phenoxy resin A. After applying this resin solution on the polyester release film, it was dried at 165 ° C. for 5 minutes to evaporate the solvent, and a phosphorus-containing phenoxy resin A having a phosphorus content of 4.6% was obtained.
Figure 2008105563
As a result of GPC analysis of phosphorus-containing phenoxy resin A using Shodex AD-800P + TSKgelSuperHM-H + SuperHM-H + SuperH2000 as a column and N, N-dimethylformamide (containing 20 mM lithium bromide) as an eluent. The weight average molecular weight in terms of polyethylene oxide was 77,300.
Synthesis example 2
A phosphorus-containing phenoxy resin B having a phosphorus content of 4.6% was synthesized by synthesizing a phosphorus-containing phenoxy resin in the same manner as in Synthesis Example 1, except that the reaction time in Synthesis Example 1 was changed from 8 hours to 10 hours. Got. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 109,700.
Synthesis example 3
A phosphorus-containing phenoxy resin C having a phosphorus content of 4.6% was synthesized by synthesizing a phosphorus-containing phenoxy resin in the same manner as in Synthesis Example 1, except that the reaction time in Synthesis Example 1 was changed from 8 hours to 20 hours. Got. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 198,400.
Synthesis example 4
In place of the phosphorus-containing phenol represented by the above formula (11) in Synthesis Example 1, 222 g of phosphorus-containing naphthol represented by the following formula (12) (hydroxyl equivalent: 221.6 g / eq, phosphorus content: 8.2%) The phosphorus-containing phenoxy resin was synthesized in the same manner as in Synthesis Example 1 except that the reaction time in Synthesis Example 1 was changed from 8 hours to 10 hours, and a phosphorus content of 4.0% was obtained. The containing phenoxy resin D was obtained. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 122,470.
Figure 2008105563
Synthesis example 5
Instead of 175 parts of bisphenol A type epoxy resin (manufactured by Tohto Kasei Co., Ltd., YD-8125, epoxy equivalent 171.6 g / eq) in Synthesis Example 1, bisphenol fluorene type epoxy resin (new) The same as Synthesis Example 1 except that 231 parts of ERF-300 manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent of 231 g / eq) were used, and the reaction time in Synthesis Example 1 was changed from 8 hours to 10 hours. In this way, a phosphorus-containing phenoxy resin E was synthesized to obtain a phosphorus-containing phenoxy resin E having a phosphorus content of 4.4%. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 117,900.
Figure 2008105563
Synthesis Example 6
A phosphorus-containing phenoxy resin F having a phosphorus content of 4.6% was synthesized in the same manner as in Synthesis Example 1, except that the reaction time in Synthesis Example 1 was changed from 8 hours to 5 hours. Got. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 39,200.
Synthesis example 7
A phosphorus-containing phenoxy resin G having a phosphorus content of 4.0% was synthesized in the same manner as in Synthesis Example 4 except that the reaction time in Synthesis Example 4 was changed from 10 hours to 5 hours. Got. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 41,500.
The abbreviations of each component used for preparing the adhesive resin composition are shown below.
YD-128: Bisphenol A type epoxy resin (manufactured by Tohto Kasei Co., Ltd.)
YDF-170: Bisphenol F type epoxy resin (manufactured by Tohto Kasei Co., Ltd.)
BRG-555: Novolac type phenolic resin (made by Showa Polymer Co., Ltd.)
DICY: Dicyandiamide (Nippon Carbide Industries, Ltd.)
DDM: diaminodiphenylmethane DDS: diaminodiphenyl sulfone resin A: phosphorus-containing phenoxy resin A of Synthesis Example 1 (weight average molecular weight 77,300)
Resin B: Phosphorus-containing phenoxy resin B of Synthesis Example 2 (weight average molecular weight 109,700)
Resin C: Phosphorus-containing phenoxy resin C of Synthesis Example 3 (weight average molecular weight 198,400)
Resin D: Phosphorus-containing phenoxy resin D of Synthesis Example 4 (weight average molecular weight 122,470)
Resin E: Phosphorus-containing phenoxy resin E of Synthesis Example 5 (weight average molecular weight 117,900)
Resin F: Phosphorus-containing phenoxy resin F of Synthesis Example 6 (weight average molecular weight 39,200)
Resin G: Phosphorus-containing phenoxy resin G of Synthesis Example 7 (weight average molecular weight 41,500)
YP-50SC: Phenoxy resin (manufactured by Toto Kasei Co., Ltd.) (weight average molecular weight 50,500)
PNR1H: NBR containing carboxyl group (manufactured by JSR Corporation)
SPE-100: Cyclophenoxy phosphazene (Otsuka Chemical Co., Ltd.)
2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
The GPC analysis of the epoxy resin was performed under the following conditions.
Equipment: HLC-8120GPC manufactured by Tosoh Corporation
Column; manufactured by Tosoh Corporation, TSK-GEL: SUPER HZ2000 × 1, SUPER HZ3000 × 1, SUPER HZ4000 × 1
Column temperature: 40 ° C
Mobile phase: tetrahydrofuran (THF)
Flow rate: 0.35 ml / min
Detector; Built-in sample concentration; 0.03 g / THF 10 ml
The content of m = 0 component was defined as area (%) obtained by dividing the area of the peak of m = 0 component obtained from the obtained GPC chromatograph by the peak area of all components.
As a result of GPC analysis of YD-128, the content of polymerization degree m = 0 isomer was 82%.
As a result of GPC analysis of YDF-170, the content of polymerization degree m = 0 isomer was 78%.
Examples 1 to 16
Each component was mix | blended in the ratio (weight%) of Tables 1-3, and the adhesive resin composition was prepared. The adhesive resin composition was evaluated for cured product characteristics and FPC material characteristics (coverlay film characteristics, bonding sheet characteristics, three-layer copper-clad laminate characteristics). The results are shown in Tables 1-3.
Comparative Examples 1-5
Each component was mix | blended in the ratio of Table 4, and the adhesive agent resin composition was prepared. The adhesive resin composition was evaluated for cured product characteristics and FPC material characteristics (coverlay film characteristics, bonding sheet characteristics, three-layer copper-clad laminate characteristics). The results are shown in Table 4.
From the above results, in Examples 1 to 16 using the adhesive resin composition of the present invention, the flame resistance in the coverlay film characteristics is VTM-0, the flame resistance in the bonding sheet characteristics and the three-layer copper clad laminate characteristics is V-0, both of which were confirmed to be flame retardant. Moreover, the solder heat resistance (dry) in the coverlay film characteristics is 300 ° C. or higher, the solder heat resistance (moisture resistance) is 250 ° C. or higher, and the folding resistance is 2800 times or more. Is 150 times or more, and all show good physical properties. Furthermore, the flow of the adhesive in the coverlay film characteristics is 0.18 mm or less, exhibits good physical properties, no problem with migration resistance, and has excellent through-hole plating conductivity in the bonding sheet characteristics. Among Examples 1 to 16, the FPC material characteristics using resin B with molecular weight 109,700, resin D with molecular weight 122,470 or resin E with molecular weight 117,900 are both solder heat resistance and folding resistance. Are better.
On the other hand, in Comparative Examples 1 and 2, although the flame retardancy in the FPC material characteristics is shown, the solder heat resistance and folding resistance in the coverlay film characteristics are low, and the flowability of the adhesive is 0.8 mm or more. Lack. In Comparative Examples 3-5, the flame resistance in the material characteristic for FPC is not recognized.
The above results are summarized, and Examples 1 to 6 are shown in Table 1, Examples 7 to 12 are shown in Table 2, Examples 13 to 16 are shown in Table 3, and Comparative Examples 1 to 5 are shown in Table 4.
Figure 2008105563
Figure 2008105563
Figure 2008105563
Figure 2008105563

本発明の接着剤樹脂組成物及びそれを用いたカバーレイフィルム、ボンディングシートおよび３層銅張積層板は、非ハロゲン且つ難燃性であるため環境問題対策に有効である上、耐折性、耐マイグレーション性およびスルーホールメッキ導通信頼性等のＦＰＣ特性にも優れる。   The adhesive resin composition of the present invention and a coverlay film, a bonding sheet and a three-layer copper-clad laminate using the same are effective for countermeasures against environmental problems because they are non-halogen and flame retardant, Excellent FPC characteristics such as migration resistance and through-hole plating conduction reliability.

Claims (10)

下記（イ）〜（ニ）成分、
（イ）下記一般式（１）で表され、リン含有率が１重量％〜６重量％であり、且つゲルパーミエーミッションクロマトグラフィーを用いて測定した標準ポリエチレンオキサイド換算重量平均分子量が６０，０００〜２００，０００であるリン含有フェノキシ樹脂、
（ロ）下記一般式（１０）で表されるエポキシ樹脂、
（ハ）硬化剤、及び
（二）硬化促進剤、
を必須成分として含有し、実質的にハロゲン元素を含まないことを特徴とする難燃性接着剤樹脂組成物。
Figure 2008105563
（式中、Ｘは下記一般式（２）又は（３）で表される２価の基を必須とする一般式（２）、（３）、（４）又は（５）から選ばれる少なくとも１種の２価の基を示し、Ｚは水素原子又は一般式（６）を示し、ｎは平均値で２１以上である。）
Figure 2008105563
Figure 2008105563
（式（２）〜（５）中、Ｙは下記一般式（７）又は（８）で表されるリン含有基を示し、Ｒ１〜Ｒ３、Ｒ１〜Ｒ４、Ｒ１〜Ｒ４、Ｒ１〜Ｒ８は独立に、水素原子、炭素数１〜４のアルキル基又はフェニル基を示す。Ａは単結合又は−ＣＨ２−、−Ｃ（ＣＨ３）２−、−ＣＨ（ＣＨ３）−、−Ｓ−、−ＳＯ２−、−Ｏ−、−ＣＯ−若しくは一般式（９）から選ばれる２価の基を示す。）
Figure 2008105563
（式（７）〜（９）中、Ｒ１〜Ｒ８、Ｒ１〜Ｒ１０、Ｒ１〜Ｒ８は独立に水素原子、炭素数１〜４のアルキル基又はフェニル基を示す。）
Figure 2008105563
（式中、Ｗは一般式（５）で表される２価の基を示し、ｍは０以上の整数であり、ｍの平均は０．１〜１５である。）The following (i) to (d) ingredients,
(A) It is represented by the following general formula (1), the phosphorus content is 1% by weight to 6% by weight, and the weight average molecular weight in terms of standard polyethylene oxide measured by gel permeation chromatography is 60,000. A phosphorus-containing phenoxy resin that is ~ 200,000,
(B) an epoxy resin represented by the following general formula (10),
(C) a curing agent, and (2) a curing accelerator,
Is a flame retardant adhesive resin composition characterized by containing an essential component and substantially not containing a halogen element.
Figure 2008105563
(In the formula, X is at least 1 selected from the general formula (2), (3), (4) or (5) which essentially requires a divalent group represented by the following general formula (2) or (3) A divalent group of the species, Z represents a hydrogen atom or general formula (6), and n is an average value of 21 or more.)
Figure 2008105563
Figure 2008105563
(In the formulas (2) to (5), Y represents a phosphorus-containing group represented by the following general formula (7) or (8), and R 1 to R 3 , R 1 to R 4 , R 1 to R 4. , R 1 to R 8 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, A represents a single bond, —CH 2 —, —C (CH 3 ) 2 —, —CH (CH 3) -, - S -, - SO 2 -, - O -, - represents a divalent group selected CO- or from the general formula (9)).
Figure 2008105563
(In formulas (7) to (9), R 1 to R 8 , R 1 to R 10 , and R 1 to R 8 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)
Figure 2008105563
(Wherein, W represents a divalent group represented by the general formula (5), m is an integer of 0 or more, and the average of m is 0.1 to 15.) （ロ）成分において、一般式（１０）における重合度ｍ＝０体の含有率が、ゲルパーミエーションクロマトグラフィーを用いて測定したクロマトグラムの面積パーセントで７０％以上であることを特徴とする請求項１記載の難燃性接着剤組成物。 In the component (b), the content of the polymerization degree m = 0 isomer in the general formula (10) is 70% or more in terms of the area percentage of the chromatogram measured using gel permeation chromatography. Item 2. A flame retardant adhesive composition according to Item 1. （イ）成分が、一般式（１）において、Ｘが一般式（２）及び（５）で示される２価の基であり、一般式（２）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが−Ｃ（ＣＨ３）２−を示すことを特徴とする請求項１又は２記載の難燃性接着剤樹脂組成物。(I) The component is a divalent group represented by the general formulas (2) and (5) in the general formula (1), and R 1 to R 3 in the general formula (2) each represent a hydrogen atom. Wherein Y represents the general formula (7), R 1 to R 8 in the general formula (5) represent a hydrogen atom, and A represents —C (CH 3 ) 2 —. Or the flame-retardant adhesive agent resin composition of 2. （イ）成分が、一般式（１）において、Ｘが一般式（３）及び（５）で示される２価の基であり、一般式（３）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが−Ｃ（ＣＨ３）２−を示すことを特徴とする請求項１又は２記載の難燃性接着剤樹脂組成物。(I) The component is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and R 1 to R 3 in the general formula (3) represent a hydrogen atom. Wherein Y represents the general formula (7), R 1 to R 8 in the general formula (5) represent a hydrogen atom, and A represents —C (CH 3 ) 2 —. Or the flame-retardant adhesive agent resin composition of 2. （イ）成分が、一般式（１）において、Ｘが一般式（２）及び（５）で示される２価の基であり、一般式（２）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが一般式（９）を示すことを特徴とする請求項１又は２記載の難燃性接着剤樹脂組成物。(I) The component is a divalent group represented by the general formulas (2) and (5) in the general formula (1), and R 1 to R 3 in the general formula (2) each represent a hydrogen atom. Wherein Y represents the general formula (7), R 1 to R 8 in the general formula (5) represent a hydrogen atom, and A represents the general formula (9). Flame retardant adhesive resin composition. （イ）成分が、一般式（１）において、Ｘが一般式（３）及び（５）で示される２価の基であり、一般式（３）におけるＲ１〜Ｒ３は水素原子を示すが、Ｙが一般式（７）を示し、一般式（５）におけるＲ１〜Ｒ８は水素原子を示すが、Ａが一般式（９）を示すことを特徴とする請求項１又は２記載の難燃性接着剤樹脂組成物。(I) The component is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and R 1 to R 3 in the general formula (3) represent a hydrogen atom. Wherein Y represents the general formula (7), R 1 to R 8 in the general formula (5) represent a hydrogen atom, and A represents the general formula (9). Flame retardant adhesive resin composition. 難燃性接着剤組成物１００重量部に対し、（イ）成分を２０〜８０重量部配合することを特徴とする請求項１〜６のいずれかに記載の難燃性接着剤樹脂組成物。 The flame-retardant adhesive resin composition according to any one of claims 1 to 6, wherein 20 to 80 parts by weight of the component (A) is blended with 100 parts by weight of the flame-retardant adhesive composition. 請求項１〜６のいずれかに記載の難燃性接着剤樹脂組成物を、フィルム状に形成してなることを特徴とする難燃性接着剤フィルム。 A flame retardant adhesive film, wherein the flame retardant adhesive resin composition according to claim 1 is formed into a film. ポリイミドフィルムと、該ポリイミドフィルムに設けられた請求項１〜６のいずれかに記載の難燃性接着剤樹脂組成物からなる層とを有することを特徴とするカバーレイフィルム。 A coverlay film comprising: a polyimide film; and a layer made of the flame retardant adhesive resin composition according to claim 1, which is provided on the polyimide film. ポリイミドフィルムと、該ポリイミドフィルムに設けられた請求項１〜６のいずれかに記載の難燃性接着剤樹脂組成物からなる層と、銅箔とを有することを特徴とするフレキシブル銅張積層板。 A flexible copper-clad laminate comprising: a polyimide film; a layer made of the flame-retardant adhesive resin composition according to any one of claims 1 to 6 provided on the polyimide film; and a copper foil. .
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