JP2008239675A - Flame retardant resin composition, and adhesive sheet, cover lay film and copper-clad laminate using the same - Google Patents
Flame retardant resin composition, and adhesive sheet, cover lay film and copper-clad laminate using the same Download PDFInfo
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本発明は、難燃性樹脂組成物に関する。より詳しくは、難燃化手法としてハロゲンを用いず、燃焼時に有害ガスである臭化水素を発生することのない非ハロゲン系難燃性樹脂組成物、それを用いた接着剤シート、カバーレイフィルムおよび銅張り積層板に関する。 The present invention relates to a flame retardant resin composition. More specifically, a non-halogen flame retardant resin composition that does not use halogen as a flame retardant method and does not generate hydrogen bromide, which is a harmful gas during combustion, an adhesive sheet using the same, and a coverlay film And a copper-clad laminate.
接着剤シート、カバーレイフィルム、銅張り積層板等のフレキシブルプリント配線板材料（以下、ＦＰＣという。）に用いられる難燃性樹脂組成物は、近年の電子機器の高機能化のために、難燃性、電気特性、耐熱特性、接着特性、機械特性等が要求されている。 Flame retardant resin compositions used for flexible printed wiring board materials (hereinafter referred to as FPC) such as adhesive sheets, cover lay films, copper-clad laminates, etc. are difficult due to the high functionality of electronic devices in recent years. Flammability, electrical characteristics, heat resistance characteristics, adhesion characteristics, mechanical characteristics, etc. are required.
これらの難燃性樹脂組成物は、エポキシ樹脂を主成分としたものが一般的に使用されている。従来、ＵＬ９４Ｖ−０の難燃性の規格を達成するために、臭素化エポキシ樹脂を中心とするハロゲン系有機化合物が難燃剤として使用されてきた。しかし、この方法では燃焼時に有害ガスである腐食性のハロゲンガスや猛毒性のダイオキシンを発生する問題があり、近年その使用が抑制されつつある。このような理由から、ハロゲン系難燃剤の代わりとして、ハロゲンを含まないハロゲンフリーの難燃剤を用いるようになった。 These flame retardant resin compositions generally use an epoxy resin as a main component. Conventionally, halogen-based organic compounds centered on brominated epoxy resins have been used as flame retardants in order to achieve the flame resistance standard of UL94V-0. However, in this method, there is a problem that corrosive halogen gas, which is a harmful gas during combustion, or highly toxic dioxin is generated, and its use is being suppressed in recent years. For these reasons, a halogen-free flame retardant containing no halogen has been used in place of the halogen flame retardant.
ハロゲンフリー難燃剤としては、リン化合物（特にリン酸エステル化合物）が知られている。ハロゲンフリー難燃剤を含む接着剤組成物として、例えば、エポキシ樹脂、リン酸エステルやリン含有エポキシ樹脂などのリン化合物、硬化剤およびＮＢＲゴムを主成分とする樹脂組成物（例えば、特許文献１参照）が提案されている。しかしながら、リン酸エステルは水分により加水分解が容易に起こり、分解物により電気特性や接着特性が著しく低下する課題があった。また、リン含有エポキシ樹脂は樹脂中のリン含有量が少ないため、難燃性を満足させるためには難燃性樹脂組成物中に多量のリン含有エポキシ樹脂を含むことが必要となり、難燃性と、電気特性や接着特性とを両立できる接着剤組成物は得られなかった。 As halogen-free flame retardants, phosphorus compounds (particularly phosphate ester compounds) are known. As an adhesive composition containing a halogen-free flame retardant, for example, a resin composition mainly composed of an epoxy resin, a phosphorus compound such as a phosphate ester or a phosphorus-containing epoxy resin, a curing agent, and NBR rubber (see, for example, Patent Document 1) ) Has been proposed. However, the phosphoric acid ester is easily hydrolyzed by moisture, and there is a problem that the electrical properties and adhesive properties are remarkably deteriorated by the decomposed product. In addition, since the phosphorus-containing epoxy resin has a low phosphorus content in the resin, it is necessary to include a large amount of the phosphorus-containing epoxy resin in the flame-retardant resin composition in order to satisfy the flame retardancy. In addition, an adhesive composition that can achieve both electrical properties and adhesive properties could not be obtained.
一方、反応性リン化合物を用いてリン原子を結合したリン含有エポキシ樹脂、熱可塑性樹脂および／または合成ゴム、硬化剤および硬化促進剤を含む難燃性接着剤組成物（例えば、特許文献２参照）が提案されている。この方法により加水分解は防止できるものの、リン含有エポキシ樹脂は樹脂中のリン含有量が少ないため、難燃性を満足させるためには難燃性樹脂組成物中に多量のリン含有エポキシ樹脂を含むことが必要となり、難燃性と、電気特性や接着特性とを両立できる接着剤組成物は得られていなかった。
本発明は、難燃性、電気特性、接着特性に優れた難燃性樹脂組成物およびそれを用いた接着剤シート、カバーレイフィルム、銅張り積層板を提供することを目的とする。 An object of this invention is to provide the flame-retardant resin composition excellent in a flame retardance, an electrical property, and an adhesive property, and an adhesive sheet, a coverlay film, and a copper clad laminated board using the same.
本発明は、（Ａ）リン含有ポリエステル樹脂、（Ｂ）エポキシ樹脂および（Ｃ）硬化剤を含有することを特徴とする難燃性樹脂組成物である。 The present invention is a flame retardant resin composition comprising (A) a phosphorus-containing polyester resin, (B) an epoxy resin, and (C) a curing agent.
本発明の難燃性樹脂組成物によれば、難燃性、電気特性、接着特性に優れた難燃性樹脂組成物を提供することができる。 According to the flame retardant resin composition of the present invention, it is possible to provide a flame retardant resin composition excellent in flame retardancy, electrical properties, and adhesive properties.
以下、本発明の詳細について説明する。本発明の難燃性樹脂組成物は、（Ａ）リン含有ポリエステル樹脂、（Ｂ）エポキシ樹脂および（Ｃ）硬化剤を含有する。（Ａ）リン含有ポリエステル樹脂を含有することにより、従来のリン化合物ではなし得なかった、難燃性、電気特性、接着特性等の物性バランスを実現することができる。 Details of the present invention will be described below. The flame-retardant resin composition of the present invention contains (A) a phosphorus-containing polyester resin, (B) an epoxy resin, and (C) a curing agent. (A) By containing a phosphorus-containing polyester resin, it is possible to achieve a balance of physical properties such as flame retardancy, electrical properties, and adhesive properties that cannot be achieved with conventional phosphorus compounds.
本発明に用いられる（Ａ）リン含有ポリエステル樹脂は、特に限定されるものではないが、例えば、下記一般式（１）または（２）で表されるリン含有カルボン酸またはそのエステル化物の共重合体が挙げられる。 The (A) phosphorus-containing polyester resin used in the present invention is not particularly limited. For example, the phosphorus-containing carboxylic acid represented by the following general formula (1) or (2) or a co-polymerized ester thereof Coalescence is mentioned.
上記一般式（１）中、Ｒ１およびＲ２は炭化水素基を示す。Ｒ３およびＲ４は炭化水素基またはヒドロキシ基置換炭化水素基を示す。共重合体のリン含有率を高め、難燃性をより向上させるために、Ｒ１〜Ｒ４の炭素数は１〜５が好ましい。ｌおよびｍは０〜４の整数を示す。 In the general formula (1), R 1 and R 2 represent a hydrocarbon group. R 3 and R 4 represent a hydrocarbon group or a hydroxy group-substituted hydrocarbon group. In order to increase the phosphorus content of the copolymer and further improve the flame retardancy, the carbon number of R 1 to R 4 is preferably 1 to 5. l and m represent an integer of 0-4.
上記一般式（２）中、Ｒ５は水素原子または炭化水素基を示す。Ｒ６およびＲ７は水素原子、炭化水素基またはヒドロキシ基置換炭化水素基を示す。共重合体のリン含有率を高め、難燃性をより向上させるために、Ｒ６〜Ｒ７の炭素数は０〜５が好ましい。 In the general formula (2), R 5 represents a hydrogen atom or a hydrocarbon group. R 6 and R 7 represent a hydrogen atom, a hydrocarbon group or a hydroxy group-substituted hydrocarbon group. In order to increase the phosphorus content of the copolymer and further improve the flame retardancy, the carbon number of R 6 to R 7 is preferably 0 to 5.
（Ａ）リン含有ポリエステル樹脂の含有量は、難燃性樹脂組成物中２０重量％以上５０重量％以下が好ましい。（Ａ）成分を２０重量％以上含むことにより、難燃性をより向上させることができる。また、難燃性と接着特性、電気特性のバランスをより高いレベルで両立するためには、５０重量％以下が好ましい。 (A) As for content of phosphorus containing polyester resin, 20 to 50 weight% is preferable in a flame-retardant resin composition. By including 20% by weight or more of the component (A), flame retardancy can be further improved. Moreover, in order to achieve a higher level of balance between flame retardancy, adhesive properties, and electrical properties, 50% by weight or less is preferable.
（Ａ）リン含有ポリエステル樹脂中のリン含有率は、難燃性をより向上させるため、３．０重量％以上が好ましい。上限は特に限定されないが、製造時の安定性を考慮すると５．０重量％以下が好ましい。このようなリン含有ポリエステル樹脂として、具体的には、“バイロン”（登録商品）６３７（東洋紡績（株）製 リン含有率３．７重量％）が例示できる。 (A) The phosphorus content in the phosphorus-containing polyester resin is preferably 3.0% by weight or more in order to further improve the flame retardancy. The upper limit is not particularly limited, but is preferably 5.0% by weight or less in consideration of stability during production. A specific example of such a phosphorus-containing polyester resin is “Byron” (registered product) 637 (phosphorus content 3.7% by Toyobo Co., Ltd.).
本発明に用いられる（Ｂ）エポキシ樹脂は、エポキシ基を分子中に少なくとも２個以上含むものであれば特に限定されないが、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノ−ルＳ、レゾルシノ−ル、ジヒドロキナフタレン、ジシクロペンタジエンジフェノ−ル等のジグリシジルエ−テル、エポキシ化フェノ−ルノボラック、エポキシ化クレゾ−ルノボラック、エポキシ化トリスフェニロ−ルメタン、エポキシ化テトラフェニロ−ルエタン等の脂環式エポキシ樹脂、ビフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂などが挙げられる。 The (B) epoxy resin used in the present invention is not particularly limited as long as it contains at least two epoxy groups in the molecule. For example, bisphenol A, bisphenol F, bisphenol S, resorcinol, dihydro Diglycidyl ethers such as quinaphthalene and dicyclopentadiene diphenol, epoxidized phenol novolac, epoxidized cresol novolac, epoxidized trisphenylol methane, epoxidized tetraphenylol ethane and other alicyclic epoxy resins, biphenol type epoxy Examples thereof include resins and novolac type epoxy resins.
また、難燃性をより向上させるためには、リンを含有するエポキシ樹脂等を含有してもよい。その種類は特に限定されるものではないが、例えば、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドやその誘導体と、１，４−ベンゾキノン、１，２−ベンゾキノン、トルキノン、１，４−ナフトキノン等が反応して得られる化合物に、上記エポキシ樹脂を反応させたリン含有エポキシ樹脂等が挙げられる。具体的には、ＦＸ２８９ＢＥＫ７５（東都化成（株）製、リン含有率２重量％）が例示できる。 Moreover, in order to improve a flame retardance more, you may contain the epoxy resin etc. which contain phosphorus. Although the kind is not particularly limited, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof, 1,4-benzoquinone, 1,2-benzoquinone, The phosphorus-containing epoxy resin etc. which made the said epoxy resin react with the compound obtained by reacting tolquinone, 1, 4- naphthoquinone, etc. are mentioned. Specifically, FX289BEK75 (manufactured by Toto Kasei Co., Ltd., phosphorus content 2% by weight) can be exemplified.
本発明に用いられる（Ｃ）硬化剤は、特に限定されるものではないが、例えば、芳香族ポリアミンである３，３’，５，５’−テトラメチル−４，４’−ジアミノジフェニルメタン、３，３’５，５’−テトラエチル−４，４’−ジアミノジフェニルメタン、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジアミノジフェニルメタン、３，３’−ジクロロ−４，４’−ジアミノジフェニルメタン、２，２’３，３’−テトラクロロ−４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルフィド、３，３’−ジアミノベンゾフェノン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、３，４’−ジアミノジフェニルスルホン、４，４’−ジアミノベンゾフェノン、３，４，４’−トリアミノジフェニルスルホンなどやフェノールノボラック樹脂、ジシアンジアミド、酸無水物などが挙げられる。 The (C) curing agent used in the present invention is not particularly limited. For example, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, which is an aromatic polyamine, , 3′5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dichloro-4,4 '-Diaminodiphenylmethane, 2,2'3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylsulfone 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminobenzophenone, 3,4,4 ′ Triamino diphenyl sulfone, phenol novolak resins, dicyandiamide, and acid anhydrides thereof.
本発明の難燃性樹脂組成物は、硬化促進剤を含有してもよい。硬化促進剤としては、三フッ化ホウ素トリエチルアミン錯体などの三フッ化ホウ素のアミン錯体、２−アルキル−４−メチルイミダゾール、２−フェニル−４−アルキルイミダゾールなどのイミダゾール誘導体、無水フタル酸、無水トリメリット酸などの有機酸などが挙げられる。これらを２種類以上用いてもよい。 The flame retardant resin composition of the present invention may contain a curing accelerator. Curing accelerators include boron trifluoride amine complexes such as boron trifluoride triethylamine complex, imidazole derivatives such as 2-alkyl-4-methylimidazole and 2-phenyl-4-alkylimidazole, phthalic anhydride, And organic acids such as merit acid. Two or more of these may be used.
本発明の難燃性樹脂組成物は、必要に応じて無機粒子剤を含有してもよい。無機粒子剤としては、水酸化アルミニウム、水酸化マグネシウム、カルシウム・アルミネート水和物等の金属水酸化物、酸化亜鉛、酸化マグネシウム等の金属酸化物が挙げられ、これらを２種以上用いてもよい。無機粒子剤の平均粒子径は透明性と分散安定性を考慮すると、０．２〜５μｍが好ましい。また、含有量は（Ａ）リン含有ポリエステル樹脂１００重量部に対して４０〜１００重量部が適当である。また、以上の成分以外に、接着剤の特性を損なわない範囲で酸化防止剤、イオン捕捉剤、窒素系難燃剤（メラミン変性フェノール樹脂等）などの有機、無機成分を含有することは何ら制限されるものではない。 The flame retardant resin composition of the present invention may contain an inorganic particle agent as necessary. Examples of the inorganic particles include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium aluminate hydrate, and metal oxides such as zinc oxide and magnesium oxide. Good. In consideration of transparency and dispersion stability, the average particle size of the inorganic particulate agent is preferably 0.2 to 5 μm. Moreover, 40-100 weight part is suitable with respect to 100 weight part of (A) phosphorus containing polyester resin. In addition to the above components, it is not limited to contain organic and inorganic components such as antioxidants, ion scavengers, nitrogen flame retardants (melamine modified phenolic resin, etc.) within the range that does not impair the properties of the adhesive. It is not something.
本発明の接着シートは、前記難燃性樹脂組成物から形成される接着剤層と、少なくとも１層の剥離可能な保護フィルムを有する。接着剤層の両面に剥離可能な保護フィルムを有するものでもよい。また、本発明のカバーレイフィルムは、絶縁性フィルム、前記難燃性樹脂組成物から形成される接着剤層および剥離可能な保護フィルムをこの順に有する。また、本発明の銅張り積層板は、絶縁性フィルム、前記難燃性樹脂組成物から形成される接着剤層および銅箔をこの順に有する。 The adhesive sheet of the present invention has an adhesive layer formed from the flame retardant resin composition and at least one peelable protective film. You may have a protective film which can peel on both surfaces of an adhesive bond layer. Moreover, the coverlay film of this invention has an insulating film, the adhesive bond layer formed from the said flame-retardant resin composition, and the peelable protective film in this order. Moreover, the copper clad laminated board of this invention has an adhesive film formed from an insulating film, the said flame-retardant resin composition, and copper foil in this order.
絶縁性フィルムとしては、ポリイミド、ポリエステル、ポリフェニレンスルフィド、ポリエーテルスルホン、ポリエーテルエーテルケトン、アラミド、ポリカーボネート、ポリアリレート等のプラスチックフィルムが挙げられる。これらから選ばれる複数のフィルムを積層して用いてもよい。絶縁性フィルムの厚さは５〜２００μｍが好ましい。また必要に応じて、加水分解、コロナ放電、低温プラズマ、物理的粗面化、易接着コーティング処理等の表面処理を施すことができる。 Examples of the insulating film include plastic films such as polyimide, polyester, polyphenylene sulfide, polyethersulfone, polyetheretherketone, aramid, polycarbonate, and polyarylate. A plurality of films selected from these may be laminated and used. The thickness of the insulating film is preferably 5 to 200 μm. If necessary, surface treatments such as hydrolysis, corona discharge, low temperature plasma, physical roughening, and easy adhesion coating treatment can be applied.
銅箔としては、用途に応じて圧延箔及び電解銅箔のいずれも好適に用いることができる。銅箔の厚みや表面粗度も特に限定されない。 As the copper foil, either a rolled foil or an electrolytic copper foil can be suitably used depending on the application. The thickness and surface roughness of the copper foil are not particularly limited.
本発明の難燃性樹脂組成物、接着剤シート、カバーレイフィルム、銅張り積層板の用途は特に限定されるものではなく、電子機器、半導体集積回路接続用基板、半導体装置に好適に使用することができる。例えばフレキシブルプリント配線板材料（ＦＰＣ）、テープオートメーティッドボンディング（ＴＡＢ）、各種パーケージ用途（ＣＳＰ、ＢＧＡ）などが挙げられる。 The uses of the flame-retardant resin composition, adhesive sheet, coverlay film, and copper-clad laminate of the present invention are not particularly limited, and are suitably used for electronic devices, semiconductor integrated circuit connection substrates, and semiconductor devices. be able to. Examples include flexible printed wiring board materials (FPC), tape automated bonding (TAB), and various package applications (CSP, BGA).
以下に実施例をあげて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。実施例の説明に入る前に評価の方法について述べる。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Prior to the description of the examples, the evaluation method will be described.
Ａ．評価用サンプル作製方法（片面銅張り積層板（ＣＣＬ））
１２．５μｍ厚のポリイミドフィルム“カプトン”（登録商標）５０ＥＮに、接着剤溶液をバーコーターで塗布し、硬化して、１０μｍ厚の接着剤層を形成した。次に、接着剤層に１／３ｏｚの電解銅箔（三井金属（株）製、３ＥＣ−Ｍ３Ｓ−ＨＴＥ箔、１２μｍ厚）の非光沢面を合わせるように、１００℃、２．７ＭＰａでラミネートした後、熱風循環式エアーオーブンで１５０℃、５時間の熱処理を行って、接着剤層の硬化度が９０％以上である片面ＣＣＬを作製した。
A. Sample preparation method for evaluation (single-sided copper-clad laminate (CCL))
An adhesive solution was applied to a polyimide film “Kapton” (registered trademark) 50EN having a thickness of 12.5 μm with a bar coater and cured to form an adhesive layer having a thickness of 10 μm. Next, the adhesive layer was laminated at 100 ° C. and 2.7 MPa so that the non-glossy surface of 1/3 oz electrolytic copper foil (manufactured by Mitsui Kinzoku Co., Ltd., 3EC-M3S-HTE foil, 12 μm thickness) was matched. Thereafter, heat treatment was performed at 150 ° C. for 5 hours in a hot-air circulating air oven, and a single-sided CCL having an adhesive layer with a degree of cure of 90% or more was produced.
Ｂ．評価用サンプル作製方法（両面ＣＣＬ）
前記Ａに記載の方法で得られた片面ＣＣＬのポリイミドフィルム面に、さらに接着剤溶液をバーコーターで塗布し、硬化して、１／３ｏｚの電解銅箔（三井金属（株）製、３ＥＣ−Ｍ３Ｓ−ＨＴＥ箔、１２μｍ厚）の非光沢面を同様の条件でラミネートした。これに熱風循環式エアーオーブンで１５０℃、５時間の熱処理を行って、接着剤層の硬化度が９０％以上である両面ＣＣＬを作製した。
B. Sample preparation method for evaluation (double-sided CCL)
An adhesive solution was further applied to the polyimide film surface of the single-sided CCL obtained by the method described in A above with a bar coater and cured to 1/3 oz electrolytic copper foil (Mitsui Metals Co., Ltd., 3EC- The non-glossy surface of M3S-HTE foil (thickness 12 μm) was laminated under the same conditions. This was subjected to heat treatment at 150 ° C. for 5 hours in a hot-air circulating air oven to produce a double-sided CCL with an adhesive layer having a curing degree of 90% or more.
Ｃ．接着力評価方法
上記Ａに記載の方法で作製した片面ＣＣＬサンプルを用いて、ＪＩＳ−Ｃ６４８１に準拠して行った。すなわち片面側の銅箔をエッチングにより２ｍｍ幅の銅箔パターンを作製し、テンシロンを用いて２ｍｍ幅の銅箔のみを９０度方向に引き剥がした場合の強度を測定し、接着力とした（引張速度：５０ｍｍ／分）。接着力は、１０Ｎ／ｃｍ以上であれば良好、１２Ｎ／ｃｍ以上であれば極めて良好と判断した。
C. Adhesive strength evaluation method Using the single-sided CCL sample produced by the method described in A above, it was performed according to JIS-C6481. In other words, a copper foil pattern with a width of 2 mm was prepared by etching the copper foil on one side, and the strength when only 2 mm width of the copper foil was peeled in the 90-degree direction using Tensilon was measured to determine the adhesive strength (tensile Speed: 50 mm / min). The adhesive strength was judged to be good if it was 10 N / cm or more, and very good if it was 12 N / cm or more.
Ｄ．電気特性評価方法
上記Ａに記載の方法で作製した片面ＣＣＬサンプルを用いて、ＪＩＳ−Ｃ６４７１ ９．３に準拠して行った。すなわち片面側の銅箔をエッチングによりライン／スペースが２．５ｍｍ／１ｍｍの銅箔パターンを作製し、直流電圧５００Ｖ印加時の線間絶縁抵抗値を測定した。電気特性は１×１０１２Ω以上であれば良好と判断した。
D. Electrical property evaluation method Using the single-sided CCL sample produced by the method described in A above, it was performed in accordance with JIS-C6471 9.3. That is, a copper foil pattern with a line / space of 2.5 mm / 1 mm was prepared by etching the copper foil on one side, and the line insulation resistance value when a DC voltage of 500 V was applied was measured. The electrical characteristics were judged to be good if they were 1 × 10 12 Ω or higher.
Ｅ．半田耐熱性評価方法
ＪＩＳ−Ｃ６４８１に準拠した方法で行った。上記Ａに記載の方法で作製した片面ＣＣＬサンプルを２０ｍｍ角にカットし、４０℃、９０％ＲＨの雰囲気下で２４時間調湿した後、すみやかに所定の温度の半田浴上に３０秒間浮かべ、ポリイミドフィルムの膨れおよび剥がれのない最高温度を測定した。半田耐熱性は、２６０℃以上であれば良好、２８０℃以上であれば極めて良好と判断した。
E. Solder heat resistance evaluation method It was performed by the method based on JIS-C6481. A single-sided CCL sample prepared by the method described in A above is cut into a 20 mm square, conditioned for 24 hours in an atmosphere of 40 ° C. and 90% RH, and immediately floated on a solder bath at a predetermined temperature for 30 seconds. The maximum temperature at which the polyimide film did not swell and peel was measured. The solder heat resistance was judged to be good if it was 260 ° C. or higher, and very good if it was 280 ° C. or higher.
Ｆ．難燃性評価方法
上記Ｂに記載の方法で作製した両面ＣＣＬの銅箔を両面全面エッチングしたサンプルを作製し、ＵＬ９４Ｖ−０に準拠して測定した。
F. Flame Retardancy Evaluation Method A sample was prepared by etching a double-sided CCL copper foil produced by the method described in B above on both sides, and measured according to UL94V-0.
実施例１
リン含有ポリエステル樹脂（東洋紡（株）製、“バイロン”（登録商標）６３７）５０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）７０重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１０重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Example 1
Phosphorus-containing polyester resin (Toyobo Co., Ltd., “Byron” (registered trademark) 637) 50 parts by weight, epoxy resin (Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250) 70 weights Part and a curing agent (Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) 10 parts by weight are dissolved in methyl isobutyl ketone, and stirred and mixed at 30 ° C. to prepare a 25 wt% adhesive solution. did.
実施例２
リン含有ポリエステル樹脂（東洋紡（株）製“バイロン”（登録商標）６３７）５０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）１６０重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）３０重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Example 2
50 parts by weight of a phosphorus-containing polyester resin (“Byron” (registered trademark) 637 manufactured by Toyobo Co., Ltd.), 160 parts by weight of an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250) , And 30 parts by weight of a curing agent (Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) were dissolved in methyl isobutyl ketone, stirred at 30 ° C., and mixed to prepare a 25 wt% adhesive solution. .
実施例３
リン含有ポリエステル樹脂（東洋紡（株）製“バイロン”（登録商標）６３７）５０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）４６重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）５重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Example 3
50 parts by weight of a phosphorus-containing polyester resin (Toyobo Co., Ltd. “Byron” (registered trademark) 637), epoxy resin (Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250) 46 parts by weight And 5 parts by weight of a curing agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) were dissolved in methyl isobutyl ketone and stirred and mixed at 30 ° C. to prepare a 25 wt% adhesive solution. .
実施例４
リン含有ポリエステル樹脂（東洋紡（株）製“バイロン”（登録商品）６３７）５０重量部、リン含有エポキシ樹脂（東都化成（株）製、ＦＸ２８９ＢＥＫ７５、リン含有率２重量％）６０重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）６重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Example 4
Phosphorus-containing polyester resin (Toyobo Co., Ltd. “Byron” (registered product) 637) 50 parts by weight, Phosphorus-containing epoxy resin (Toto Kasei Co., Ltd., FX289BEK75, phosphorus content 2% by weight) 60 parts by weight, and curing 6 parts by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) was dissolved in methyl isobutyl ketone, and stirred and mixed at 30 ° C. to prepare a 25 wt% adhesive solution.
実施例５
リン含有ポリエステル樹脂（東洋紡（株）製“バイロン”（登録商標）６３７）５０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）６０重量部、硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１０重量部、及び硬化促進剤（日鉱金属（株）製、イミダゾールシラン、ＩＳ−１０００）２重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Example 5
50 parts by weight of a phosphorus-containing polyester resin (“Byron” (registered trademark) 637 manufactured by Toyobo Co., Ltd.), 60 parts by weight of an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250) , 10 parts by weight of a curing agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) and 2 parts by weight of a curing accelerator (manufactured by Nikko Metal Co., Ltd., imidazolesilane, IS-1000) Then, the mixture was stirred and mixed at 30 ° C. to prepare a 25 wt% adhesive solution.
実施例６
無機フィラー（昭和電工（株）製、水酸化アルミニウム、Ｈ−４２Ｉ）２０重量部をトルエンに分散させ、サンドミル処理して水酸化アルミニウム分散液を作製した。この分散液に、リン含有ポリエステル樹脂（東洋紡（株）製“バイロン”（登録商標）６３７）５０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）５０重量部、硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１０重量部、及び硬化促進剤（日鉱金属（株）製、イミダゾールシラン、ＩＳ−１０００）２重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Example 6
20 parts by weight of an inorganic filler (manufactured by Showa Denko KK, aluminum hydroxide, H-42I) was dispersed in toluene, and sand milled to prepare an aluminum hydroxide dispersion. In this dispersion, 50 parts by weight of a phosphorus-containing polyester resin (“Byron” (registered trademark) 637 manufactured by Toyobo Co., Ltd.), an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent) 250) 50 parts by weight, curing agent (Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) 10 parts by weight, and curing accelerator (Nikko Metal Co., Ltd., imidazolesilane, IS-1000) 2 parts by weight A portion was dissolved in methyl isobutyl ketone, stirred and mixed at 30 ° C. to prepare a 25 wt% adhesive solution.
実施例７
リン含有ポリエステル樹脂（東洋紡（株）製“バイロン”（登録商標）６３７）５０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）３０重量部、リン含有エポキシ樹脂（東都化成（株）製、ＦＸ２８９ＢＥＫ７５、リン含有率２重量％）３０重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１０重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Example 7
50 parts by weight of a phosphorus-containing polyester resin (Toyobo Co., Ltd. "Byron" (registered trademark) 637), epoxy resin (Japan Epoxy Resin Co., Ltd., "jER" (registered trademark) 834, epoxy equivalent 250) 30 parts by weight 30 parts by weight of a phosphorus-containing epoxy resin (manufactured by Tohto Kasei Co., Ltd., FX289BEK75, phosphorus content 2% by weight) and 10 parts by weight of a curing agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) Dissolved in methyl isobutyl ketone and stirred and mixed at 30 ° C. to prepare a 25 wt% adhesive solution.
実施例８
無機フィラー（昭和電工（株）製、水酸化アルミニウム、Ｈ−４２Ｉ）３０重量部をトルエンに分散させ、サンドミル処理して水酸化アルミニウム分散液を作製した。この分散液に、リン含有ポリエステル樹脂（東洋紡（株）製“バイロン”（登録商標）６３７）５０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）４０重量部、リン含有エポキシ樹脂（東都化成（株）製、ＦＸ２８９ＢＥＫ７５、リン含有率２重量％）３０重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１２重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Example 8
30 parts by weight of an inorganic filler (Showa Denko Co., Ltd., aluminum hydroxide, H-42I) was dispersed in toluene, and sand milled to prepare an aluminum hydroxide dispersion. In this dispersion, 50 parts by weight of a phosphorus-containing polyester resin (“Byron” (registered trademark) 637 manufactured by Toyobo Co., Ltd.), an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent) 250) 40 parts by weight, phosphorus-containing epoxy resin (manufactured by Tohto Kasei Co., Ltd., FX289BEK75, phosphorus content 2% by weight), and curing agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) ) 12 parts by weight was dissolved in methyl isobutyl ketone and stirred and mixed at 30 ° C. to prepare a 25% by weight adhesive solution.
実施例９
無機フィラー（昭和電工（株）製、水酸化アルミニウム、Ｈ−４２Ｉ）５０重量部をトルエンに分散させ、サンドミル処理して水酸化アルミニウム分散液を作製した。この分散液に、リン含有ポリエステル樹脂（東洋紡（株）製“バイロン”（登録商標）６３７）５０重量部、リン含有エポキシ樹脂（東都化成（株）製、ＦＸ２８９ＢＥＫ７５、リン含有率２重量％）５０重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１０重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Example 9
50 parts by weight of an inorganic filler (manufactured by Showa Denko KK, aluminum hydroxide, H-42I) was dispersed in toluene, and sand milled to prepare an aluminum hydroxide dispersion. To this dispersion, 50 parts by weight of a phosphorus-containing polyester resin (Toyobo Co., Ltd. “Byron” (registered trademark) 637), phosphorus-containing epoxy resin (Toto Kasei Co., Ltd., FX289BEK75, phosphorus content 2% by weight) 50 Part by weight and 10 parts by weight of a curing agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) are dissolved in methyl isobutyl ketone, and stirred and mixed at 30 ° C. to obtain a 25 wt% adhesive solution. Produced.
比較例１
ポリエステル樹脂（東洋紡（株）“バイロン”（登録商標）３０ＳＳ） ２０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）８０重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１０重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
比較例２
ポリエステル樹脂（東洋紡（株）“バイロン”（登録商標）３０ＳＳ）６０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）３０重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１０重量部をメチルイソブチルケトンに溶解し、３０℃で撹拌、混合して２５重量％の接着剤溶液を作製した。
Comparative Example 1
20 parts by weight of a polyester resin (Toyobo Co., Ltd. “Byron” (registered trademark) 30SS), 80 parts by weight of an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250), and curing 10 parts by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) was dissolved in methyl isobutyl ketone, and stirred and mixed at 30 ° C. to prepare a 25 wt% adhesive solution.
Comparative Example 2
60 parts by weight of a polyester resin (Toyobo Co., Ltd. “Byron” (registered trademark) 30SS), 30 parts by weight of an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250), and curing 10 parts by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) was dissolved in methyl isobutyl ketone, and stirred and mixed at 30 ° C. to prepare a 25 wt% adhesive solution.
比較例３
ＮＢＲ（ＪＳＲ（株）製、ＰＮＲ−１Ｈ）４０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）４０重量部、及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１０重量部をメチルエチルケトンに溶解し、３０℃で撹拌、混合して２８重量％の接着剤溶液を作製した。
Comparative Example 3
40 parts by weight of NBR (manufactured by JSR Corporation, PNR-1H), 40 parts by weight of epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250), and curing agent (Sumitomo Chemical) 10 parts by weight of 4,4′-diaminodiphenylsulfone (manufactured by Co., Ltd.) was dissolved in methyl ethyl ketone, and stirred and mixed at 30 ° C. to prepare a 28 wt% adhesive solution.
比較例４
ＮＢＲ（ＪＳＲ（株）製、ＰＮＲ−１Ｈ）４０重量部、リン含有エポキシ樹脂（東都化成（株）製、ＦＸ２８９ＢＥＫ７５、リン含有率２重量％）６０重量部、硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１２重量部、及び硬化促進剤（日鉱金属（株）製、イミダゾールシラン、ＩＳ−１０００）２重量部をメチルエチルケトンに溶解し、３０℃で撹拌、混合して２８重量％の接着剤溶液を作製した。
Comparative Example 4
NBR (manufactured by JSR Corporation, PNR-1H) 40 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX289BEK75, phosphorus content 2% by weight), 60 parts by weight, curing agent (manufactured by Sumitomo Chemical Co., Ltd.) , 4,4′-diaminodiphenylsulfone) and 2 parts by weight of a curing accelerator (manufactured by Nikko Metal Co., Ltd., imidazolesilane, IS-1000) are dissolved in methyl ethyl ketone, and stirred and mixed at 30 ° C. A 28 wt% adhesive solution was prepared.
比較例５
無機フィラー（昭和電工（株）製、水酸化アルミニウム、Ｈ−４２Ｉ）２０重量部をトルエンに分散させ、サンドミル処理して水酸化アルミニウム分散液を作製した。この分散液に、ＮＢＲ（ＪＳＲ（株）製、ＰＮＲ−１Ｈ）４０重量部、エポキシ樹脂（ジャパンエポキシレジン（株）製、“ｊＥＲ”（登録商標）８３４、エポキシ当量２５０）２０重量部、リン含有エポキシ樹脂（東都化成（株）製、ＦＸ２８９ＢＥＫ７５、リン含有率２重量％）２０重量部及び硬化剤（住友化学（株）製、４，４’−ジアミノジフェニルスルホン）１０重量部をメチルエチルケトンに溶解し、３０℃で撹拌、混合して２８重量％の接着剤溶液を作製した。
Comparative Example 5
20 parts by weight of an inorganic filler (manufactured by Showa Denko KK, aluminum hydroxide, H-42I) was dispersed in toluene, and sand milled to prepare an aluminum hydroxide dispersion. To this dispersion, 40 parts by weight of NBR (manufactured by JSR Corporation, PNR-1H), 20 parts by weight of epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250), phosphorus 20 parts by weight of epoxy resin containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX289BEK75, phosphorus content 2% by weight) and 10 parts by weight of curing agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) are dissolved in methyl ethyl ketone. Then, the mixture was stirred and mixed at 30 ° C. to prepare a 28 wt% adhesive solution.
実施例１〜９、比較例１〜５に記載の接着剤溶液を用いて評価用サンプルを作製し、接着力、電気特性、半田耐熱性、難燃性について評価した結果を表１〜２に示す。 The sample for evaluation was produced using the adhesive agent solution of Examples 1-9 and Comparative Examples 1-5, and the result evaluated about adhesive force, an electrical property, solder heat resistance, and a flame retardance is shown to Tables 1-2. Show.
Claims (6)
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| JP2007078612A JP2008239675A (en) | 2007-03-26 | 2007-03-26 | Flame retardant resin composition, and adhesive sheet, cover lay film and copper-clad laminate using the same |
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| JP2007078612A JP2008239675A (en) | 2007-03-26 | 2007-03-26 | Flame retardant resin composition, and adhesive sheet, cover lay film and copper-clad laminate using the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010098154A1 (en) * | 2009-02-24 | 2010-09-02 | 住友電気工業株式会社 | Adhesive resin compositions, and laminates and flexible printed wiring boards using same |
| JP2011144308A (en) * | 2010-01-18 | 2011-07-28 | Hien Electric Industries Ltd | Flame-retardant laminate adhesive and shield tape for flat cable using the same |
| WO2014091750A1 (en) * | 2012-12-13 | 2014-06-19 | 日本ゼオン株式会社 | Curable resin composition, insulating film, prepreg, cured product, composite, and substrate for electronic material |
| JP2014117823A (en) * | 2012-12-13 | 2014-06-30 | Nippon Zeon Co Ltd | Insulating film, prepreg and cure product |
| JP5637418B1 (en) * | 2013-06-10 | 2014-12-10 | Dic株式会社 | Phosphorus atom-containing active ester resin, epoxy resin composition, cured product thereof, prepreg, circuit board, and build-up film |
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2007
- 2007-03-26 JP JP2007078612A patent/JP2008239675A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010098154A1 (en) * | 2009-02-24 | 2010-09-02 | 住友電気工業株式会社 | Adhesive resin compositions, and laminates and flexible printed wiring boards using same |
| JP2010195887A (en) * | 2009-02-24 | 2010-09-09 | Sumitomo Electric Ind Ltd | Adhesive resin composition, and laminate and flexible printed wiring board using the same |
| CN102333836A (en) * | 2009-02-24 | 2012-01-25 | 住友电气工业株式会社 | Adhesive resin compositions, and laminates and flexible printed wiring boards using same |
| US9181464B2 (en) | 2009-02-24 | 2015-11-10 | Sumitomo Electric Industries, Ltd. | Adhesive resin compositions, and laminates and flexible printed wiring boards using same |
| JP2011144308A (en) * | 2010-01-18 | 2011-07-28 | Hien Electric Industries Ltd | Flame-retardant laminate adhesive and shield tape for flat cable using the same |
| WO2014091750A1 (en) * | 2012-12-13 | 2014-06-19 | 日本ゼオン株式会社 | Curable resin composition, insulating film, prepreg, cured product, composite, and substrate for electronic material |
| JP2014117823A (en) * | 2012-12-13 | 2014-06-30 | Nippon Zeon Co Ltd | Insulating film, prepreg and cure product |
| JP5637418B1 (en) * | 2013-06-10 | 2014-12-10 | Dic株式会社 | Phosphorus atom-containing active ester resin, epoxy resin composition, cured product thereof, prepreg, circuit board, and build-up film |
| KR20160018507A (en) * | 2013-06-10 | 2016-02-17 | 디아이씨 가부시끼가이샤 | Active ester resin containing phosphorus atom, epoxy resin composition and cured product thereof, prepreg, circuit board, and build-up film |
| KR102046767B1 (en) | 2013-06-10 | 2019-11-20 | 디아이씨 가부시끼가이샤 | Active ester resin containing phosphorus atom, epoxy resin composition and cured product thereof, prepreg, circuit board, and build-up film |
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