JP2011017026A - Resin composition, use of the same, and method for preparing the same - Google Patents
Resin composition, use of the same, and method for preparing the same Download PDFInfo
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本発明は、樹脂組成物およびこれを用いた電気絶縁用のプリプレグ、積層板、プリント配線板、ならびにこれらの製造方法に関する。なお、本発明における積層板は、その片面または両面を金属箔で被覆した積層板、すなわち金属張積層板を含む。 The present invention relates to a resin composition, a prepreg for electrical insulation using the resin composition, a laminated board, a printed wiring board, and methods for producing them. In addition, the laminated board in this invention contains the laminated board which coat | covered the metal foil with the single side | surface or both surfaces, ie, a metal-clad laminated board.
近年、電気絶縁用のプリプレグ、積層板、およびプリント配線板は、環境問題の高まりにより、廃棄時あるいは焼却時に有害物質を環境中に排出しないことが求められている。そのため、燃焼時にいわゆるダイオキシン問題が発生することを避ける目的で、ハロゲン系難燃剤を含有しないことを特徴とした製品が増加している。ハロゲン系難燃剤の代替難燃剤としては、金属水酸化物系、リン系、メラミン変性樹脂系等が用いられているが、特にリン系難燃剤は、少量で高い難燃効果が得られることから有用である。 In recent years, prepregs, laminates, and printed wiring boards for electrical insulation are required not to discharge harmful substances into the environment at the time of disposal or incineration due to increasing environmental problems. Therefore, in order to avoid the so-called dioxin problem at the time of combustion, products characterized by not containing a halogen flame retardant are increasing. Metal flame retardant, phosphorous, melamine modified resin, etc. are used as alternative flame retardants for halogen flame retardants, especially phosphorous flame retardants because high flame retardant effects can be obtained in small amounts. Useful.
しかし、リン系難燃剤として実用に供せられる化合物は、赤リン、リン酸塩、リン酸エステル等であり、これらは燃焼時に有毒なホスフィンガスを放出したり、加水分解により積層板、プリント配線板の耐熱性や耐薬品性を低下させるという問題がある。このような問題に対して、特開平４−１１６６２号公報および特開２０００−８０２５１号公報には、リン酸エステルとは異なる構造を有し、分子内にエポキシ樹脂と容易に反応し得るフェノール性水酸基を有する有機リン化合物とエポキシ樹脂との反応物が例示されている。この反応物は、耐熱性や耐薬品性を低下させることがなく、ハロゲン系難燃剤を含まない難燃性の樹脂組成物および積層板、プリント配線板の製造が可能であるとされている。しかし、これらに示されるフェノール性水酸基を有する有機リン化合物とエポキシ樹脂との反応物は、エポキシ樹脂および有機リン化合物が共に多官能性であり、それゆえに、反応物には架橋構造が生じやすく、反応度を制御することが非常に困難である。また、エポキシ樹脂と有機リン化合物の反応によりエポキシ基が消費されるため、反応物のエポキシ当量が非常に大きくなり硬化性が低下するという問題がある。 However, the compounds that can be put to practical use as phosphorus-based flame retardants are red phosphorus, phosphates, phosphate esters, etc., which release toxic phosphine gas at the time of combustion, or are laminated and printed wiring by hydrolysis. There is a problem of reducing the heat resistance and chemical resistance of the plate. In order to solve this problem, Japanese Patent Application Laid-Open Nos. 4-11662 and 2000-80251 have phenolic structures that have a structure different from that of phosphate esters and can easily react with an epoxy resin in the molecule. A reaction product of an organic phosphorus compound having a hydroxyl group and an epoxy resin is exemplified. This reaction product is said to be capable of producing a flame-retardant resin composition, a laminated board and a printed wiring board that do not contain a halogen-based flame retardant without deteriorating heat resistance and chemical resistance. However, the reaction product of the organophosphorus compound having a phenolic hydroxyl group and the epoxy resin shown in these shows that both the epoxy resin and the organophosphorus compound are multifunctional, and therefore the reaction product is likely to have a crosslinked structure. It is very difficult to control the reactivity. Moreover, since an epoxy group is consumed by reaction of an epoxy resin and an organophosphorus compound, there exists a problem that the epoxy equivalent of a reaction material becomes very large and curability falls.
そこで、本発明は、ハロゲン系難燃剤を含まずに十分な難燃性を有し、耐熱性、耐薬品性が良好で、かつ配合時に、エポキシ樹脂が反応で消費されて反応安定性や硬化性に問題を生じないような樹脂組成物を提供することを目的とする。また、本発明は、この樹脂組成物を使用するプリプレグ、積層板およびプリント配線板およびこれらの製造方法を提供することを目的とする。 Therefore, the present invention has sufficient flame retardancy without containing a halogen-based flame retardant, has good heat resistance and chemical resistance, and at the time of blending, the epoxy resin is consumed in the reaction, resulting in reaction stability and curing. It aims at providing the resin composition which does not produce a problem in property. Moreover, an object of this invention is to provide the prepreg, laminated board, printed wiring board, and these manufacturing methods which use this resin composition.
本発明者らは、上記課題に向けて鋭意検討した結果、以下の発明を見出すに至った。すなわち、本発明は、エポキシ樹脂、アミン系硬化剤、式１に示す構造の有機リン化合物および有機溶剤を含み、前記エポキシ樹脂と前記有機リン化合物とを５０℃以下の温度で配合した樹脂組成物である。また本発明は、この樹脂組成物を用いたプリプレグ、積層板、プリント配線板、ならびにこれらの製造法である。 As a result of intensive studies aimed at the above problems, the present inventors have found the following invention. That is, the present invention includes an epoxy resin, an amine curing agent, an organic phosphorus compound having a structure represented by Formula 1, and an organic solvent, wherein the epoxy resin and the organic phosphorus compound are blended at a temperature of 50 ° C. or lower. It is. Moreover, this invention is a prepreg, a laminated board, a printed wiring board using this resin composition, and these manufacturing methods.
すなわち本発明の樹脂組成物は、プリプレグの作製に供されるまで、エポキシ樹脂と式１に示す有機リン化合物との間の反応を抑制した組成物であることを特徴とする。配合中に、エポキシ樹脂と式１に示す有機リン化合物との間に反応が生じると、エポキシ当量が変化し、樹脂のゲル化時間の変動が大きくなり、硬化性が安定しない。このように、配合時に、両成分の反応性を抑制するためには、配合工程において、温度を５０℃以下に保つ必要がある。なお、エポキシ樹脂と式１に示す有機リン化合物との間で反応が起こっているか否かは、高速液体クロマトグラフィー等の汎用分析機器によって確認できる。 That is, the resin composition of the present invention is a composition in which the reaction between the epoxy resin and the organophosphorus compound represented by Formula 1 is suppressed until the preparation of the prepreg. If a reaction occurs between the epoxy resin and the organophosphorus compound shown in Formula 1 during compounding, the epoxy equivalent changes, the resin gelation time fluctuates greatly, and the curability is not stable. Thus, in order to suppress the reactivity of both components at the time of blending, it is necessary to keep the temperature at 50 ° C. or lower in the blending step. Note that whether or not a reaction is occurring between the epoxy resin and the organophosphorus compound represented by Formula 1 can be confirmed by a general-purpose analytical instrument such as high performance liquid chromatography.
本発明の樹脂組成物は、ハロゲン系難燃剤を含まずに十分な難燃性を有し、耐熱性、耐薬品性が良好で、かつ配合時に、エポキシ樹脂が反応で消費されて反応安定性や硬化性に問題を生じないものである。この樹脂組成物を使用した作製した積層板は、良好な積層板特性を有している。 The resin composition of the present invention does not contain a halogen-based flame retardant, has sufficient flame retardancy, has good heat resistance and chemical resistance, and at the time of compounding, the epoxy resin is consumed in the reaction, and reaction stability And does not cause problems in curability. A laminate produced using this resin composition has good laminate properties.
本発明において樹脂組成物に含有されるエポキシ樹脂としては、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、ビスフェノールＳ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレンジオール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、環状脂肪族エポキシ樹脂、グリシジルエステル樹脂、グリシジルアミン樹脂、複素環式エポキシ樹脂、たとえばトリグリシジルイソシアヌレート、ジグリシジルヒンダトインなど、およびこれらのエポキシ樹脂を種々の反応性モノマーで変性した変性エポキシ樹脂が使用できる。また、テトラキス（グリシジルオキシフェニル）エタンを使用することもできる。 As the epoxy resin contained in the resin composition in the present invention, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalenediol type epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester resins, glycidyl amine resins, heterocyclic epoxy resins such as triglycidyl isocyanurate, diglycidyl hindatoin, and various reactive monomers A modified epoxy resin modified with can be used. Tetrakis (glycidyloxyphenyl) ethane can also be used.
これらのエポキシ樹脂は、単独でも使用でき、また２種類以上のエポキシ樹脂を適宜組み合せて使用することもできる。なかでも、電気電子材料用途に適用するために、高い耐熱性や信頼性が必要であることから、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、およびジシクロペンタジエン変性ノボラックエポキシ樹脂が好ましく、これらの１種以上を全エポキシ樹脂に対して３０重量％以上用いることが好ましい。 These epoxy resins can be used alone, or two or more types of epoxy resins can be used in appropriate combination. Of these, phenol novolac epoxy resins, cresol novolac epoxy resins, and dicyclopentadiene-modified novolac epoxy resins are preferred because high heat resistance and reliability are required for application to electrical and electronic materials. It is preferable to use at least 30% by weight based on the total epoxy resin.
また、アミン系硬化剤としては、鎖状脂肪族アミン、たとえばエチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ヘキサメチレンジアミン、ジエチルアミノプロピルアミン、ジシアンジアミド、テトラメチルグアニジン、トリエタノールアミンなど；環状脂肪族アミン、たとえばイソホロンジアミン、ジアミノジシクロヘキシルメタン、ビス（アミノメチル）シクロヘキサン、ビス（４−アミノ−３−メチルジシクロヘキシル）メタン、Ｎ−アミノエチルピペラジン、３，９−ビス（３−アミノプロピル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカンなど；芳香族アミン、たとえばキシレンジアミン、フェニレンジアミン、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など；を使用することができる。 Examples of amine curing agents include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, dicyandiamide, tetramethylguanidine, and triethanolamine; Group amines such as isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2 4,8,10-tetraoxaspiro [5.5] undecane, etc .; aromatic amines such as xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenyl It may be used; and sulfone.
これらのアミン系硬化剤は、単独でも使用でき、また２種類以上のアミン系硬化剤を適宜組み合せて使用することもできる。なかでも、ジシアンジアミドが硬化性および硬化物の物性の点で好ましい。 These amine curing agents can be used alone, or two or more amine curing agents can be used in appropriate combination. Of these, dicyandiamide is preferable in terms of curability and physical properties of the cured product.
また、式１に示す構造の有機リン化合物としては、１０−（２，５−ジヒドロキシフェニル）−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、１０−（２，５−ジヒドロキシ−６−メチルフェニル）−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、１０−（２，５−ジヒドロキシ−３−メチルフェニル）−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、１０−（２，５−ジヒドロキシ−４−メチルフェニル）−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、１０−（１，４−ジヒドロキシ−２−ナフチル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドなどを使用することができる。なかでも、難燃性の点で、１０−（２，５−ジヒドロキシフェニル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドが好ましい。 Moreover, as an organic phosphorus compound of the structure shown in Formula 1, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-Dihydroxy-6-methylphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxy-3-methylphenyl) -9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxy-4-methylphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (1,4-dihydroxy-2-naphthyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 It can be used, such as oxides. Among these, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is preferable from the viewpoint of flame retardancy.
本発明の樹脂組成物におけるエポキシ樹脂、アミン系硬化剤、式１に示す構造の有機リン化合物および有機溶剤の構成比は、これらを硬化して得られる硬化物の特性、特に耐熱性、吸湿性、難燃性等を良好に保つ観点から定められる。アミン系硬化剤の配合量は、エポキシ樹脂のエポキシ基に対して、０．３〜０．６当量であり、また式１に示す構造の有機リン化合物の配合量は、有機溶剤および無機質成分を除く有機固形分中に５〜３０重量％配合されることが好ましい。 The composition ratio of the epoxy resin, the amine curing agent, the organophosphorus compound having the structure shown in Formula 1 and the organic solvent in the resin composition of the present invention is characteristic of the cured product obtained by curing these, particularly heat resistance and hygroscopicity. It is determined from the viewpoint of maintaining good flame retardancy and the like. The compounding amount of the amine-based curing agent is 0.3 to 0.6 equivalents relative to the epoxy group of the epoxy resin, and the compounding amount of the organophosphorus compound having the structure shown in Formula 1 includes an organic solvent and an inorganic component. It is preferable that 5-30 weight% is mix | blended in the organic solid content except.
なお、アミン系硬化剤の当量とは、硬化剤１モル当りに存在する窒素原子と結合する活性水素のモル数で定義され、たとえばアミン系硬化剤がジシアンジアミドの場合は、１モルで４当量とみなされる。アミン系硬化剤の配合量がこの範囲にあると、硬化物の架橋密度が維持できるとともに、硬化物の吸湿率が抑えられるので、プリント配線板製造工程で回路を形成した金属箔のふくれや層間剥離等の問題を回避できる。 The equivalent of the amine curing agent is defined by the number of moles of active hydrogen bonded to the nitrogen atom present per mole of the curing agent. For example, when the amine curing agent is dicyandiamide, 4 moles per mole It is regarded. If the compounding amount of the amine curing agent is within this range, the crosslink density of the cured product can be maintained and the moisture absorption rate of the cured product can be suppressed. Problems such as peeling can be avoided.
また、式１に示す構造の有機リン化合物の配合量が、上記範囲にあると、難燃性を発揮することができ、また成形硬化過程で未反応生成物が硬化物中に残留することがないので、耐薬品性を維持することができる。 Moreover, when the compounding amount of the organophosphorus compound having the structure shown in Formula 1 is in the above range, flame retardancy can be exhibited, and unreacted products may remain in the cured product during the molding and curing process. Since it is not, chemical resistance can be maintained.
有機溶剤の種類と量については、樹脂組成物を構成するエポキシ樹脂とアミン系硬化剤を均一に溶解し、プリプレグを作製するのに適正な粘度と揮発性を有している溶剤であれば、特に限定されるものではない。なかでも、これらの要件を満たし、かつ、価格、取扱い性、安全性の観点から、メチルエチルケトン、２−メトキシエタノール、２−メトキシプロパノール、１−メトキシ−２−プロパノールなどが好ましく、有機溶剤を含む樹脂組成物総量に対し１０〜５０重量％使用することが好ましい。 Regarding the type and amount of the organic solvent, the epoxy resin and amine curing agent constituting the resin composition are uniformly dissolved, and if the solvent has an appropriate viscosity and volatility for producing a prepreg, It is not particularly limited. Of these, from the viewpoints of price, handleability, and safety, and satisfying these requirements, methyl ethyl ketone, 2-methoxyethanol, 2-methoxypropanol, 1-methoxy-2-propanol, etc. are preferable, and a resin containing an organic solvent. It is preferable to use 10 to 50% by weight based on the total amount of the composition.
また本発明の樹脂組成物は、エポキシ樹脂とアミン系硬化剤の種類によっては、プリプレグ製造時に有機溶剤が揮発した後、両者が相分離しアミン系硬化剤が析出する場合がある。このような場合、そのまま成形硬化を行っても均一な硬化物が製造できない可能性が高い。そのために、組成物を配合する前に、あらかじめ、エポキシ樹脂とアミン系硬化剤とを有機溶剤中で８０〜１４０℃で反応させ、両者を無溶剤下で相溶し得る性状とすることで、均一な硬化物を与える樹脂組成物を得ることができる。エポキシ樹脂のエポキシ基とアミン系硬化剤のアミノ基の間に部分的に結合が生じ、これが両者の相溶化剤として働くことが理由と考えられる。反応温度がこの範囲にあると、反応速度が充分に得られ、かつ制御可能であるので、生産性の点で好ましい。また、この工程では、反応促進剤を適宜添加することもできる。なお、式１に示す構造の有機リン化合物をこのような混合物に加える際は、この反応を先に行った後に、５０℃以下の温度で前記有機リン化合物を混合する。 In the resin composition of the present invention, depending on the types of the epoxy resin and the amine curing agent, after the organic solvent volatilizes during the prepreg production, both of them may phase separate and the amine curing agent may precipitate. In such a case, there is a high possibility that a uniform cured product cannot be produced even if molding and curing are performed as they are. Therefore, before blending the composition, by reacting the epoxy resin and the amine curing agent at 80 to 140 ° C. in an organic solvent in advance, and making them compatible with each other in the absence of a solvent, A resin composition giving a uniform cured product can be obtained. It is considered that a bond is partially formed between the epoxy group of the epoxy resin and the amino group of the amine curing agent, and this acts as a compatibilizer for both. When the reaction temperature is within this range, the reaction rate can be sufficiently obtained and controlled, which is preferable in terms of productivity. In this step, a reaction accelerator can be appropriately added. In addition, when adding the organophosphorus compound of the structure shown to Formula 1 to such a mixture, after performing this reaction previously, the said organophosphorus compound is mixed at the temperature of 50 degrees C or less.
本発明の樹脂組成物は、式１に示す有機リン化合物を配合する工程において、配合温度を５０℃以下に保つことによって製造できる。エポキシ樹脂と式１に示す有機リン化合物の間の反応は、特開平４−１１６６２号公報に示されるように、反応触媒を添加して１００℃以上に加熱することによって進行するが、これより低温であっても、反応は徐々に進む。しかし、両者の配合温度を５０℃以下に保つことにより、両者の反応を実質的にほぼ完全に抑止することができる。両者の反応の有無は、高速液体クロマトグラフィー等の汎用分析機器によって確認でき、本発明に示す製造方法では、反応率、すなわち反応した有機リン化合物量／配合した有機リン化合物の比は０．５％以下である。 The resin composition of the present invention can be produced by maintaining the blending temperature at 50 ° C. or lower in the step of blending the organophosphorus compound represented by Formula 1. The reaction between the epoxy resin and the organophosphorus compound represented by Formula 1 proceeds by adding a reaction catalyst and heating to 100 ° C. or higher as disclosed in Japanese Patent Application Laid-Open No. 4-11662. Even so, the reaction progresses gradually. However, by maintaining the blending temperature of both at 50 ° C. or less, the reaction between the two can be substantially completely inhibited. The presence or absence of the reaction of both can be confirmed by a general-purpose analytical instrument such as high performance liquid chromatography. In the production method shown in the present invention, the reaction rate, that is, the ratio of the reacted organophosphorus compound / the blended organophosphorus compound is 0.5. % Or less.
また、本発明の樹脂組成物は、難燃性をより高める目的や高剛性化、低熱膨張化の目的で、無機質充填剤を含有することもできる。その含有量は、これらの目的を発現させる必要性と、樹脂組成物から製造される積層板やプリント配線板の接着性や加工性を維持するという制約から、有機溶剤を除く固形分、すなわち無機質充填剤を含む樹脂固形分に対して１０〜５０重量％であることが好ましい。また、無機質充填剤には、シリカ、タルク、マイカ、酸化アルミニウム、炭酸マグネシウム、炭酸バリウムなどの非ハロゲン化合物であって、積層板、プリント配線板の特性を劣化させないものであれば特に限定されない。また、無機質充填剤は、単独でも、２種以上を併用して使用することもできる。なかでも、難燃性を向上させる働きを有する水酸化アルミニウムが好ましく、これを１０〜５０重量％添加することが最も好ましい。また、難燃性をさらに向上させるために、含有させる無機質充填剤の一部を、モリブデンまたは亜鉛化合物で被覆処理することが有効であり、両者の利点を併せ持つモリブデン酸亜鉛によって被覆処理を行うことがより好ましい。 In addition, the resin composition of the present invention can also contain an inorganic filler for the purpose of increasing flame retardancy, increasing rigidity, and decreasing thermal expansion. Its content is the solid content excluding organic solvents, that is, inorganic matter, because of the necessity to express these purposes and the constraint of maintaining the adhesiveness and workability of laminates and printed wiring boards produced from resin compositions It is preferable that it is 10 to 50 weight% with respect to the resin solid content containing a filler. The inorganic filler is not particularly limited as long as it is a non-halogen compound such as silica, talc, mica, aluminum oxide, magnesium carbonate, and barium carbonate and does not deteriorate the characteristics of the laminated board and the printed wiring board. The inorganic fillers can be used alone or in combination of two or more. Among these, aluminum hydroxide having a function of improving flame retardancy is preferable, and it is most preferable to add 10 to 50% by weight thereof. In order to further improve the flame retardancy, it is effective to coat a part of the inorganic filler to be contained with molybdenum or a zinc compound, and to carry out the coating treatment with zinc molybdate having both advantages. Is more preferable.
また本発明の樹脂組成物には、これら以外に、他の難燃剤や顔料、接着助剤、酸化防止剤および硬化促進剤などを含有させることができる。それぞれ公知の化合物、たとえば、硬化促進剤では各種イミダゾール類（２−エチル−４−メチルイミダゾールなど）、を使用することができる。非ハロゲン化合物であって、積層板、プリント配線板特性を低下させない化合物、含有量であれば特に限定されない。 In addition to these, the resin composition of the present invention may contain other flame retardants, pigments, adhesion assistants, antioxidants, curing accelerators, and the like. Known compounds, for example, various imidazoles (such as 2-ethyl-4-methylimidazole) can be used as the curing accelerator. It is a non-halogen compound and is not particularly limited as long as it is a compound and content that does not deteriorate the properties of the laminated board and printed wiring board.
本発明の樹脂組成物は、ガラスクロス等の基材に含浸し、乾燥させることによって、プリプレグを作製することができる。また、このプリプレグに金属箔を重ね合せ、加熱・加圧して積層一体化することにより積層板を製造することができる。さらに、この積層板の金属箔の不要な部分をエッチング除去することによって、プリント配線板を製造することもできる。これらプリプレグ、積層板、プリント配線板の製造においては、当該業界における通常の塗工、積層、回路加工工程を適用することができ、これにより高耐熱性、高難燃性、高信頼性でかつハロゲン系難燃剤を含有しない積層板およびプリント配線板が得られる。 The resin composition of the present invention can produce a prepreg by impregnating a substrate such as glass cloth and drying it. Moreover, a laminated sheet can be manufactured by superimposing a metal foil on this prepreg and stacking and integrating by heating and pressing. Furthermore, a printed wiring board can also be manufactured by etching away the unnecessary part of the metal foil of this laminated board. In the production of these prepregs, laminates, and printed wiring boards, ordinary coating, lamination, and circuit processing steps in the industry can be applied, thereby providing high heat resistance, high flame resistance, and high reliability. A laminate and a printed wiring board containing no halogen-based flame retardant can be obtained.
以下に本発明の実施例およびその比較例を用いて、本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.
実施例および比較例において、エポキシ樹脂、アミン系硬化剤、式１に示す有機リン化合物およびその他の配合化合物として、下記に示すものを用いた。積層板、プリプレグを構成するガラス布、銅箔などについては、特に記載したものを除き、化学工業および電子工業分野において一般的に用いられる材料類を用いた。 In Examples and Comparative Examples, epoxy resins, amine-based curing agents, organic phosphorus compounds represented by Formula 1, and other compounding compounds shown below were used. Regarding the laminated sheet, the glass cloth, the copper foil constituting the prepreg, and the like, materials generally used in the chemical industry and the electronic industry field were used except those specifically described.
・エポキシ樹脂Ａ：ジャパン・エポキシ・レジン（株）製、フェノールノボラック型エポキシ樹脂、商品名：１５４（エポキシ当量１７８）
・エポキシ樹脂Ｂ：大日本インキ化学工業（株）製、クレゾールノボラック型エポキシ樹脂、商品名：Ｎ−６７３（エポキシ当量２１０）
・エポキシ樹脂Ｃ：大日本インキ化学工業（株）製、ジシクロペンタジエン変性ノボラック型エポキシ樹脂、商品名：ＨＰ−７２００（エポキシ当量２６０）
・エポキシ樹脂Ｄ：ジャパン・エポキシ・レジン（株）製、ビスフェノールＡ型エポキシ樹脂、商品名：１００１（エポキシ当量４７５）
・アミン系硬化剤Ａ：日本カーバイド（株）製、ジシアンジアミド
・有機リン化合物Ａ：三光（株）製、１０−（２，５−ジヒドロキシフェニル）−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
・有機リン化合物Ｂ：大八化学工業（株）製、トリフェニルホスフェート
・２−エチル−４−メチルイミダゾール：四国化成工業（株）製、商品名：２Ｅ４ＭＺ
・水酸化アルミニウム：住友化学工業（株）製、商品名：ＣＬ-３０３
・モリブデン酸亜鉛処理タルク：日本シャーウィン・ウイリアムス（株）製、商品名：９１１Ｃ
Epoxy resin A: manufactured by Japan Epoxy Resin Co., Ltd., phenol novolac type epoxy resin, trade name: 154 (epoxy equivalent 178)
Epoxy resin B: manufactured by Dainippon Ink & Chemicals, Inc., cresol novolac type epoxy resin, trade name: N-673 (epoxy equivalent 210)
Epoxy resin C: manufactured by Dainippon Ink & Chemicals, Inc., dicyclopentadiene-modified novolac type epoxy resin, trade name: HP-7200 (epoxy equivalent 260)
Epoxy resin D: manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin, product name: 1001 (epoxy equivalent 475)
Amine-based curing agent A: manufactured by Nippon Carbide Co., Ltd., dicyandiamide, organophosphorus compound A: manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide / organic phosphorus compound B: Daihachi Chemical Industry Co., Ltd., triphenyl phosphate 2-ethyl-4-methylimidazole: Shikoku Kasei Kogyo Co., Ltd., trade name: 2E4MZ
Aluminum hydroxide: manufactured by Sumitomo Chemical Co., Ltd., trade name: CL-303
-Zinc molybdate-treated talc: Nippon Sherwin Williams Co., Ltd., trade name: 911C
積層板およびプリント配線板の特性評価は以下にして行った。
難燃性については、ＵＬ−９４垂直法による燃焼時間により評価し、平均燃焼時間５秒以下、かつ最大燃焼時間１０秒以下をＶ−０、平均燃焼時間１０秒以下、かつ最大燃焼時間３０秒以下をＶ−１、それ以上燃焼した場合をＨＢで分類した。
Evaluation of the characteristics of the laminate and the printed wiring board was performed as follows.
The flame retardancy is evaluated by the combustion time according to the UL-94 vertical method, and the average combustion time is 5 seconds or less, the maximum combustion time is 10 seconds or less, V-0, the average combustion time is 10 seconds or less, and the maximum combustion time is 30 seconds. The following was classified by V-1, and the case where it burned more was classified by HB.
その他の積層板特性、たとえば銅箔引き剥がし強さ、ガラス転移温度、絶縁抵抗、吸湿はんだ耐熱性、耐薬品性については、ＪＩＳＣ６４８１に基づき評価した。
吸湿はんだ耐熱性の評価は、○：変化なし、△：ミーズリングまたは目浮き発生、×：ふくれ発生、で判定した。
ワニスの硬化性は、１６０℃のホットプレート上に、０．５ccのワニスを滴下し、直径１mmの棒で攪拌しゲル化するまでの時間（ゲル化時間）で評価した。
Other laminate characteristics such as copper foil peel strength, glass transition temperature, insulation resistance, moisture-absorbing solder heat resistance, and chemical resistance were evaluated based on JISC6481.
The evaluation of the heat resistance of the moisture-absorbing solder was determined by ○: no change, Δ: occurrence of mesling or eye lift, and ×: occurrence of blistering.
The curability of the varnish was evaluated by the time (gelation time) until 0.5 cc of varnish was dropped on a 160 ° C. hot plate, stirred with a 1 mm diameter rod and gelled.
また、ワニス中の有機リン化合物の反応率は、高速液体クロマトグラフィーを用い、以下の条件で、内部標準法により、配合前に対するピーク面積の減少率を求め、これを反応率として評価した。
・カラム：ジーエルサイエンス製ＯＤＳ−２型逆相カラム、
・展開液：水／テトラヒドロフラン（７０／３０）混合液、
・検出器：紫外吸光光度計２８０nm
Moreover, the reaction rate of the organophosphorus compound in the varnish was determined by using high performance liquid chromatography under the following conditions by the internal standard method to determine the reduction rate of the peak area with respect to the pre-formation and evaluating this as the reaction rate.
Column: ODS-2 reverse phase column manufactured by GL Sciences,
Developing solution: water / tetrahydrofuran (70/30) mixture,
Detector: UV absorption photometer 280nm
また、エポキシ樹脂とアミン系硬化剤の無溶剤下での相溶性は、樹脂組成物の配合時に溶剤可溶成分のみを混合した時点で一部を採取し、透明なガラス板上に滴下し、１６０℃１０分乾燥させて有機溶剤を揮発させ、これを光学顕微鏡で１００倍に拡大して観察して、アミン系硬化剤析出物の有無を目視にて確認した。 In addition, the compatibility of the epoxy resin and the amine-based curing agent in the absence of a solvent is partly collected at the time of mixing only the solvent-soluble component at the time of compounding the resin composition, and dropped on a transparent glass plate, The organic solvent was volatilized by drying at 160 ° C. for 10 minutes, and this was magnified 100 times with an optical microscope and observed, and the presence or absence of the amine-based curing agent precipitate was visually confirmed.
実施例１
表１に示す配合により、積層板用樹脂組成物を作製した。配合時の液温度は３５℃であった。室温にて５日間経過後、この樹脂組成物をガラスクロス（厚さ０．２mm）に含浸させ、１６０℃で４分間乾燥してプリプレグを得た。このプリプレグを４枚重ね、その両面に１８μmの銅箔を重ね、１８５℃、圧力４MPaの条件にて８０分間加熱加圧成形して、厚さ０．８mmの両面銅張積層板を作製した。プリプレグ作製直前に樹脂組成物の一部を採取し、ゲル化時間、有機リン化合物の反応率、およびエポキシ樹脂とアミン系硬化剤の無溶剤下での相溶性を測定した。またこの積層板の特性を評価した。これらの結果を表２に示す。
Example 1
The resin composition for laminated boards was produced according to the formulation shown in Table 1. The liquid temperature at the time of blending was 35 ° C. After 5 days at room temperature, this resin composition was impregnated into a glass cloth (thickness 0.2 mm) and dried at 160 ° C. for 4 minutes to obtain a prepreg. Four sheets of this prepreg were stacked, 18 μm copper foil was stacked on both sides, and heated and pressed under conditions of 185 ° C. and a pressure of 4 MPa for 80 minutes to prepare a double-sided copper clad laminate having a thickness of 0.8 mm. A part of the resin composition was collected immediately before the preparation of the prepreg, and the gelation time, the reaction rate of the organic phosphorus compound, and the compatibility of the epoxy resin and the amine curing agent in the absence of solvent were measured. In addition, the characteristics of this laminate were evaluated. These results are shown in Table 2.
実施例２、３
実施例１と同じ配合、同じ工程で、同様にして樹脂組成物を作製した。ゲル化時間および有機リン化合物の反応率を測定し、実施例１と併せてそのバラツキを確認した。
Examples 2 and 3
A resin composition was prepared in the same manner using the same formulation and the same steps as in Example 1. The gelation time and the reaction rate of the organophosphorus compound were measured, and the variation was confirmed together with Example 1.
実施例４、５
表１に示す配合により、実施例１と同様にして積層板用樹脂組成物を作製し、室温にて５日間経過後、樹脂組成物からプリプレグおよび積層板を作製した配合時の液温度、ワニスゲル化時間、有機リン化合物の反応率、エポキシ樹脂とアミン系硬化剤の無溶剤下での相溶性、および積層板特性を表２に示す。
Examples 4 and 5
With the formulation shown in Table 1, a laminate resin composition was prepared in the same manner as in Example 1, and after 5 days at room temperature, a prepreg and a laminate were produced from the resin composition. Table 2 shows the conversion time, the reaction rate of the organophosphorus compound, the compatibility of the epoxy resin and the amine curing agent in the absence of a solvent, and the properties of the laminate.
実施例６〜８
表１に示す配合のうち、まずエポキシ樹脂、アミン系硬化剤、硬化促進剤、有機溶剤のみを配合し、１００℃で２時間反応させた。冷却後、有機リン化合物および無機質充填剤を混合し、樹脂組成物を作製した。さらに、室温にて５日間経過後、この樹脂組成物を用いて、プリプレグおよび積層板を作製した。有機リン化合物配合時の液温度、ワニスゲル化時間、有機リン化合物の反応率、エポキシ樹脂とアミン系硬化剤の無溶剤下での相溶性、および積層板特性を表２に示す。
Examples 6-8
Of the blends shown in Table 1, first, only an epoxy resin, an amine curing agent, a curing accelerator, and an organic solvent were blended and reacted at 100 ° C. for 2 hours. After cooling, an organic phosphorus compound and an inorganic filler were mixed to prepare a resin composition. Further, after 5 days at room temperature, a prepreg and a laminate were prepared using this resin composition. Table 2 shows the liquid temperature, the varnish gelation time, the reaction rate of the organic phosphorus compound, the compatibility of the epoxy resin and the amine curing agent in the absence of a solvent, and the properties of the laminated plate.
実施例９
実施例１と同様にして、表１に示す配合で樹脂組成物を作製した。すなわち、無機質充填剤として、水酸化アルミニウムに加え、モリブデン酸亜鉛処理タルクを配合した。また、室温にて５日間経過後、この樹脂組成物からプリプレグおよび積層板を作製した。配合時の液温度、ワニスゲル化時間、有機リン化合物の反応率、エポキシ樹脂とアミン系硬化剤の無溶剤下での相溶性、および積層板特性を表２に示す。
Example 9
In the same manner as in Example 1, resin compositions were prepared with the formulations shown in Table 1. That is, as an inorganic filler, zinc molybdate-treated talc was blended in addition to aluminum hydroxide. Further, after 5 days at room temperature, a prepreg and a laminate were prepared from this resin composition. Table 2 shows the liquid temperature at the time of blending, the varnish gelation time, the reaction rate of the organophosphorus compound, the compatibility of the epoxy resin and the amine curing agent in the absence of a solvent, and the laminate properties.
実施例１０
実施例１で作製した両面銅張積層板の表面に、サブトラクティブ法により回路形成（テストパターン）を行った。さらに、作製した２枚の回路付き両面銅張積層板表面を、接着性を向上させるために酸化粗化処理し、実施例１で作製したプリプレグ２枚を挟んで重ね合せ、さらにその外側にプリプレグ２枚と１８μm厚さの銅箔を重ねて、実施例１と同様にして積層プレスして内層回路付き６層プリント配線板を作製した。このプリント配線板に、公知の方法を用いて外装回路加工、スルーホール形成、レジストインク印刷、部品実装を行った。このプリント配線板は、通常の製造工程において問題なく製造できることを確認した。
Example 10
Circuit formation (test pattern) was performed on the surface of the double-sided copper-clad laminate produced in Example 1 by a subtractive method. Further, the surface of the two produced double-sided copper-clad laminates with circuits was oxidized and roughened in order to improve adhesion, and the two prepregs produced in Example 1 were sandwiched and overlapped. Two sheets and 18 μm-thick copper foil were stacked and laminated and pressed in the same manner as in Example 1 to prepare a 6-layer printed wiring board with an inner layer circuit. This printed wiring board was subjected to exterior circuit processing, through-hole formation, resist ink printing, and component mounting using known methods. It was confirmed that this printed wiring board can be produced without any problem in a normal production process.
実施例１１〜１６
実施例１０と同様に、実施例４〜９で作製したプリプレグおよび積層板を用いて、プリント配線板を作製した。いずれの場合も、通常のプリント配線板の製造工程において問題なく製造できることを確認した。
Examples 11-16
Similarly to Example 10, a printed wiring board was produced using the prepreg and laminate produced in Examples 4-9. In any case, it was confirmed that it could be produced without any problem in the production process of a normal printed wiring board.
比較例１
表１に示す、実施例１と同じ配合で、かつ使用材料の溶解性を促進し作業効率を高めるために、配合時に９０℃に加熱して樹脂組成物を作製した。また、室温にて５日間経過後、この樹脂組成物を用いて、実施例１と同様にプリプレグおよび積層板を作製した。ゲル化時間、有機リン化合物の反応率、エポキシ樹脂とアミン系硬化剤の無溶剤下での相溶性および積層板の特性を評価し、結果を表２に示す。
Comparative Example 1
In order to promote the solubility of the materials used and increase the working efficiency with the same formulation as in Example 1 shown in Table 1, the resin composition was prepared by heating to 90 ° C. during the formulation. Further, after 5 days at room temperature, a prepreg and a laminate were produced using this resin composition in the same manner as in Example 1. The gelation time, the reaction rate of the organophosphorus compound, the compatibility of the epoxy resin and the amine curing agent in the absence of solvent, and the properties of the laminate were evaluated, and the results are shown in Table 2.
比較例２、３
比較例１と同じ配合、同じ工程により樹脂組成物を作製した。ゲル化時間および有機リン化合物の反応率を測定し、比較例１と併せてそのバラツキを確認した。
Comparative Examples 2 and 3
A resin composition was prepared by the same formulation and the same process as in Comparative Example 1. The gelation time and the reaction rate of the organophosphorus compound were measured, and the variation was confirmed together with Comparative Example 1.
比較例４
表１に示す配合で樹脂組成物を作製したが、有機リン化合物として、式１に示す構造とは異なるトリフェニルホスフェートを使用し、組成物の配合時の温度は３４℃であった。また、室温にて５日経過後、この樹脂組成物からプリプレグおよび積層板を作製した。ワニスゲル化時間、有機リン化合物の反応率、エポキシ樹脂とアミン系硬化剤の無溶剤下での相溶性、および積層板特性を表２に示す。
Comparative Example 4
Although the resin composition was produced with the formulation shown in Table 1, triphenyl phosphate different from the structure shown in Formula 1 was used as the organophosphorus compound, and the temperature at the time of formulation of the composition was 34 ° C. Moreover, the prepreg and the laminated board were produced from this resin composition after 5 days progress at room temperature. Table 2 shows the varnish gelation time, the reaction rate of the organophosphorus compound, the compatibility of the epoxy resin and the amine curing agent in the absence of a solvent, and the properties of the laminate.
表２より、例示した全ての実施例において、十分な難燃性を保持しつつ吸湿はんだ耐熱性、銅箔引き剥がし強さ、ガラス転移温度、絶縁抵抗等の特性が良好な積層板が得られることが確認された。特に、実施例６〜８において優れた積層板特性が得られている。また、実施例１〜３と比較例１〜３のゲル化時間を比較すると、実施例は樹脂組成物のゲル化時間の標準偏差が小さく、樹脂の硬化性が安定していることが確認された。一方、配合時の温度を９０℃に高めた比較例１〜３は、ゲル化時間の標準偏差が大きく、硬化性が安定しないといえる。また、本発明の構造を有しない有機リン化合物を配合した比較例４は、吸湿はんだ耐熱性が目標とする特性を満足していない。 From Table 2, in all the illustrated examples, laminated sheets having good characteristics such as moisture-absorbing solder heat resistance, copper foil peeling strength, glass transition temperature, insulation resistance and the like while maintaining sufficient flame retardancy are obtained. It was confirmed. In particular, excellent laminate characteristics were obtained in Examples 6 to 8. Further, when the gel times of Examples 1 to 3 and Comparative Examples 1 to 3 are compared, it is confirmed that the examples have a small standard deviation of the gel time of the resin composition and the resin curability is stable. It was. On the other hand, it can be said that Comparative Examples 1 to 3 in which the temperature at the time of blending was increased to 90 ° C. have a large standard deviation in gelation time and the curability is not stable. Moreover, the comparative example 4 which mix | blended the organophosphorus compound which does not have the structure of this invention does not satisfy the characteristic for moisture-absorbing solder heat resistance.
Claims (18)
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| JP2012172069A (en) * | 2011-02-22 | 2012-09-10 | Dic Corp | Curable resin composition, cured product thereof, resin composition for printed wiring board, printed wiring board, resin composition for flexible wiring board, resin composition for semiconductor sealing material and resin composition for interlayer insulation material for build-up substrate |
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