JP2016017090A - Thermosetting resin composition for laminate, prepreg using the same, laminate for printed circuit board, printed circuit board, and multilayer printed circuit board - Google Patents
Thermosetting resin composition for laminate, prepreg using the same, laminate for printed circuit board, printed circuit board, and multilayer printed circuit board Download PDFInfo
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本発明は、電気部品を電気的に接続させるためのプリント配線板を製造するのに用いる積層板用熱硬化性樹脂組成物、及びそれを用いたプリプレグ、プリント配線板用積層板、プリント配線板、多層プリント配線板に関するものである。 The present invention relates to a thermosetting resin composition for a laminated board used for manufacturing a printed wiring board for electrically connecting electrical components, a prepreg using the same, a laminated board for a printed wiring board, and a printed wiring board. The present invention relates to a multilayer printed wiring board.
プリント配線板用積層板は、環境汚染等の面から、使用物質規制の動きが世界的に強まってきていることもあり、ハロゲン含有物質の低減、削減といった、いわゆるハロゲンフリー化が強く求められている。プリント配線板用積層板におけるハロゲンフリー化の方法の１つとして、特許文献１に示されるように，ジヒドロベンゾオキサジン環を有する熱硬化性樹脂と、フェノール類とトリアジン環を有する化合物をベースとした樹脂が使われており、高耐熱、高耐燃、低誘電正接といった特徴を有する。 Laminated boards for printed wiring boards are increasingly required to be so-called halogen-free, such as the reduction and reduction of halogen-containing substances, as the movement of regulations on substances used has been strengthened worldwide in terms of environmental pollution. Yes. As one of the halogen-free methods in the laminate for printed wiring boards, as shown in Patent Document 1, based on a thermosetting resin having a dihydrobenzoxazine ring and a compound having a phenol and a triazine ring. Resin is used and has the characteristics of high heat resistance, high flame resistance, and low dielectric loss tangent.
しかし、耐燃性ＵＬ−９４Ｖ−０の確保には、多量の水酸化アルミニウムの添加を必要としており、そのため打ち抜き加工後の粉落ち量が多く、清掃時間の増大や、実装工程での不良の原因となっている。
プリント配線板用積層板は、ゲーム機や携帯電話等多岐にわたり使用されており、それらの製品に至るまでの工程で、プリント配線板の外形をかたどるため、パワープレスによる打抜加工が実施されている。実情では、打抜加工後の基板クズ・粉が多量に打抜金型上、及びプリント配線板上に落ち、清掃時間の増大、プリント配線板上に載った粉がその後の実装工程で不良を起こすなどの問題がある。
本発明はジヒドロベンゾオキサジン環を有する熱硬化性樹脂とフェノール類とトリアジン環を有する化合物をベース樹脂とした樹脂系の特徴を維持し、耐燃性ＵＬ９４Ｖ−０を確保した上で、プリント配線板の打抜加工後の粉落ち量を低減できる積層板用熱硬化性樹脂組成物及びそれを用いたプリプレグ、プリント配線板用積層板、プリント配線板、多層プリント配線板を提供するものである。
However, in order to ensure the flame resistance UL-94V-0, it is necessary to add a large amount of aluminum hydroxide, so that the amount of powder falling after punching is large, increasing the cleaning time and causing defects in the mounting process. It has become.
Laminated boards for printed wiring boards are used in a wide variety of game machines and mobile phones, and in the process leading up to these products, punching with a power press is performed to shape the outer shape of the printed wiring board. Yes. In fact, a large amount of substrate scrap and powder after punching falls on the punching die and printed wiring board, increasing the cleaning time, and the powder placed on the printed wiring board becomes defective in the subsequent mounting process. There are problems such as waking up.
The present invention maintains the characteristics of a resin system based on a thermosetting resin having a dihydrobenzoxazine ring, a phenol and a compound having a triazine ring as a base resin, and ensures flame resistance UL94V-0. The present invention provides a thermosetting resin composition for laminated boards that can reduce the amount of powder falling after punching, a prepreg using the same, a laminated board for printed wiring boards, a printed wiring board, and a multilayer printed wiring board.
本発明は、[１] （Ａ）ジヒドロベンゾオキサジン環を有する熱硬化性樹脂と、（Ｂ）フェノール類とトリアジン環を有する化合物とアルデヒド類の縮重合物と、（Ｃ）フェノールノボラック型エポキシ樹脂と、（Ｄ）縮合リン酸エステル系難燃剤と、（Ｅ）フェノキシ樹脂と、（Ｆ）無機充填剤とを含む積層板用熱硬化性樹脂組成物であって、
前記積層板用熱硬化性樹脂組成物の総量中に、（Ａ）２０〜４０質量％、（Ｂ）１０〜３０質量％、（Ｃ）２０〜４０質量％、（Ｄ）５〜３５質量％、（Ｅ）１〜１５質量％を含み、（Ａ）〜（Ｅ）の総量１００質量部に対して、（Ｇ）を１０〜１００質量部含む積層板用熱硬化性樹脂組成物に関する。
また、本発明は、［２］ 上記［１］に記載の積層板用熱硬化性樹脂組成物の配合比率が、（Ａ）３０〜３５質量％、（Ｂ）１０〜２５質量％，（Ｃ）２０〜３０質量％、（Ｅ）１〜１０質量％である積層板用熱硬化性樹脂組成物に関する。
また、本発明は、［３］ 上記［１］または［２］に記載の積層板用熱硬化性樹脂組成物をワニスとして基材に含浸、乾燥してなるプリプレグに関する。
また、本発明は、［４］ 上記［３］に記載のプリプレグを少なくとも１枚以上用いて、その片面、または両面に金属箔を積層し、加熱加圧成形することで作製されるプリント配線板用積層板に関する。
また、本発明は、［５］ 上記［４］に記載のプリント配線板用積層板を用いて作製されるプリント配線板に関する。
また、本発明は、［６］ 上記［３］に記載のプリプレグの異種又は同種と、上記［４］に記載のプリント配線板用積層板、上記［５］に記載のプリント配線板を用いて多層化して作製される多層プリント配線板に関する。
The present invention provides: [1] (A) a thermosetting resin having a dihydrobenzoxazine ring, (B) a polycondensation product of a phenol and a compound having a triazine ring and an aldehyde, and (C) a phenol novolac epoxy resin. And (D) a condensed phosphate ester flame retardant, (E) a phenoxy resin, and (F) a thermosetting resin composition for a laminate including an inorganic filler,
In the total amount of the thermosetting resin composition for laminates, (A) 20-40% by mass, (B) 10-30% by mass, (C) 20-40% by mass, (D) 5-35% by mass. , (E) relates to a thermosetting resin composition for a laminate including 1 to 15% by mass and 10 to 100 parts by mass of (G) with respect to 100 parts by mass of the total amount of (A) to (E).
Moreover, this invention is [2] The compounding ratio of the thermosetting resin composition for laminated boards as described in said [1] is (A) 30-35 mass%, (B) 10-25 mass%, (C ) 20-30% by mass, (E) relates to a thermosetting resin composition for laminates of 1-10% by mass.
The present invention also relates to [3] a prepreg obtained by impregnating a substrate with the thermosetting resin composition for laminates according to [1] or [2] above and drying it.
The present invention also provides [4] a printed wiring board produced by using at least one prepreg according to [3] above, laminating a metal foil on one side or both sides, and heating and pressing. The present invention relates to a laminated board.
Moreover, this invention relates to the printed wiring board produced using the laminated board for printed wiring boards as described in [5] said [4].
Moreover, this invention uses the different kind or the same kind of prepreg as described in [6] said [3], the laminated board for printed wiring boards as described in said [4], and the printed wiring board as described in said [5]. The present invention relates to a multilayer printed wiring board produced by multilayering.
本発明の積層板用熱硬化性樹脂組成物は、ジヒドロベンゾオキサジン環を有する熱硬化性樹脂とフェノール類とトリアジン環を有する化合物をベース樹脂とした樹脂系の特徴を維持し、耐燃性ＵＬ９４Ｖ−０を確保した上で、プリント配線板の打抜加工後の粉落ち量を低減できるものである。
本発明により得られるプリプレグ、プリント配線板用積層板、プリント配線板、多層プリント配線板を用いることで、従来に比べて、打抜加工後の粉落ち量が低減でき、清掃時間の短縮、実装工程での不良を大幅に削減することができる。
The thermosetting resin composition for laminates of the present invention maintains the characteristics of a resin system based on a thermosetting resin having a dihydrobenzoxazine ring, a phenol and a compound having a triazine ring, and has flame resistance UL94V- It is possible to reduce the amount of powder falling after the punching process of the printed wiring board while ensuring 0.
By using the prepreg, laminated board for printed wiring board, printed wiring board, and multilayer printed wiring board obtained by the present invention, the amount of powder falling after punching can be reduced compared to the prior art, shortening the cleaning time, and mounting. Defects in the process can be greatly reduced.
（（Ａ）成分：ジヒドロベンゾオキサジン環を有する熱硬化性樹脂）
本発明の積層板用熱硬化性樹脂組成物の主成分である（Ａ）成分のジヒドロベンゾオキサジン環を有する熱硬化性樹脂としては、ジヒドロベンゾオキサジン環を有し、ジヒドロベンゾオキサジン環の開環反応により硬化する樹脂であれば特に限定されるものではなく、フェノール性水酸基を有する化合物、ホルマリン、１級アミンから下記の式により合成される。
((A) component: thermosetting resin having a dihydrobenzoxazine ring)
The thermosetting resin having a dihydrobenzoxazine ring as component (A), which is the main component of the thermosetting resin composition for laminates of the present invention, has a dihydrobenzoxazine ring, and the dihydrobenzoxazine ring is opened. The resin is not particularly limited as long as it is a resin that cures by reaction, and is synthesized from a compound having a phenolic hydroxyl group, formalin, and a primary amine according to the following formula.
フェノール性水酸基を有する化合物として、多官能フェノール、ビフェニル化合物、ビスフェノール化合物、トリスフェノール化合物、テトラフェノール化合物、フェノール樹脂等が挙げられる。多官能フェノールとしては、カテコール、ヒドロキノン、レゾルシノールがあげられる。ビスフェノール化合物としては、ビスフェノールＡ、ビスフェノールＦ及びその位置異性体、ビスフェノールＳ等が挙げられる。またフェノール樹脂としては、レゾール樹脂、フェノールノボラック樹脂、フェノール変性キシレン樹脂、アルキルフェノール樹脂、メラミンフェノール樹脂、ベンゾグアナミンフェノール樹脂、フェノール変性ポリブタジエン等が挙げられる。この中では、特にビスフェノール化合物が望ましい。
Examples of the compound having a phenolic hydroxyl group include polyfunctional phenols, biphenyl compounds, bisphenol compounds, trisphenol compounds, tetraphenol compounds, and phenol resins. Examples of the polyfunctional phenol include catechol, hydroquinone, and resorcinol. Examples of the bisphenol compound include bisphenol A, bisphenol F and its positional isomer, and bisphenol S. Examples of the phenol resin include resole resin, phenol novolac resin, phenol-modified xylene resin, alkylphenol resin, melamine phenol resin, benzoguanamine phenol resin, and phenol-modified polybutadiene. Of these, bisphenol compounds are particularly desirable.
１級アミンとしては、具体的にメチルアミン、シクロヘキシルアミン、アニリン、置換アニリンが挙げられ、特に、熱安定性や価格の点でアニリンが望ましい。 Specific examples of the primary amine include methylamine, cyclohexylamine, aniline, and substituted aniline. In particular, aniline is desirable in terms of thermal stability and cost.
（（Ｂ）成分：フェノール類とトリアジン環を有する化合物とアルデヒド類との縮重合物）
本発明で用いる（Ｂ）成分のフェノール類とトリアジン環を有する化合物とアルデヒド類との縮重合物において使用するフェノール類としては、フェノ−ル、ビスフェノ−ルＡ、ビスフェノ−ルＦ、ビスフェノ−ルＳ等の多価フェノール類、クレゾール、キシレノール、エチルフェノール、ブチルフェノール等のアルキルフェノール類、アミノフェノール、フェニルフェノール等が挙げられ、これらを１種又は２種以上併用することができる。
((B) component: polycondensation product of phenols, compounds having a triazine ring and aldehydes)
The phenols used in the polycondensation product of the (B) component phenols and compounds having a triazine ring and aldehydes used in the present invention include phenol, bisphenol A, bisphenol F, and bisphenol. Examples thereof include polyhydric phenols such as S, alkylphenols such as cresol, xylenol, ethylphenol and butylphenol, aminophenols and phenylphenols, and these can be used alone or in combination of two or more.
また、トリアジン環を有する化合物としてはメラミン、ベンゾグアナミン、アセトグアナミン等のグアナミン誘導体、シアヌル酸、メチルシアヌレート、エチルシアヌレート等のシアヌル酸誘導体、イソシアヌル酸、メチルイソシアヌレート、エチルシアヌレート等のイソシアヌル酸誘導体等が挙げられ、特にメラミンが望ましい。 The compounds having a triazine ring include guanamine derivatives such as melamine, benzoguanamine and acetoguanamine, cyanuric acid derivatives such as cyanuric acid, methyl cyanurate and ethyl cyanurate, and isocyanuric acids such as isocyanuric acid, methyl isocyanurate and ethyl cyanurate. Derivatives and the like, and melamine is particularly desirable.
アルデヒド類としては、ホルムアルデヒド、パラホルムアルデヒド、トリオキサン、テトラオキシメチレン等が挙げられ、これらに限定されるものではないが、取扱いの容易さから、ホルムアルデヒドが好ましく、特にホルマリン、パラホルムアルデヒドが好ましい。 Examples of aldehydes include formaldehyde, paraformaldehyde, trioxane, tetraoxymethylene, and the like, but are not limited to these, but formaldehyde is preferable from the viewpoint of ease of handling, and formalin and paraformaldehyde are particularly preferable.
（（Ｃ）成分：フェノールノボラック型エポキシ樹脂）
本発明で用いる（Ｃ）成分のフェノールノボラック型エポキシ樹脂は、フェノールノボラック樹脂とエピクロルヒドリンから得られるものであれば、特に限定されないが、反応性や取扱いの容易さの点で、中程度の分子量を有するフェノールノボラック樹脂から製造されるものが望ましい。
((C) component: phenol novolac type epoxy resin)
The (C) component phenol novolac type epoxy resin used in the present invention is not particularly limited as long as it is obtained from a phenol novolac resin and epichlorohydrin, but has a moderate molecular weight in terms of reactivity and ease of handling. What is manufactured from the phenol novolak resin which has is desirable.
（（Ｄ）成分：縮合リン酸エステル系難燃剤）
本発明で用いる（Ｄ）成分の縮合リン酸エステル系難燃剤は、例えば下記式
((D) component: condensed phosphate ester flame retardant)
The condensed phosphate ester flame retardant of component (D) used in the present invention is, for example, the following formula
（（Ｅ）成分：フェノキシ樹脂）
本発明で用いる（Ｅ）成分のフェノキシ樹脂は、一般にビスフェノールＡとエピクロロヒドリンとを重縮合反応させる一段法によって、または２官能エポキシ樹脂と２官能フェノール、例えば、ビスフェノールＡとを重付加させる二段法によって製造されるものであり、具体例としては、東都化成株式会社製「フェノトートＹＰ−５０、フェノトートＹＰ−５５、フェノトートＹＰ−７０」（いずれも商品名）、特開平４−１２０１２４号公報、特開平４−１１２２７１４号公報、および特開平４−３３９８５２号公報に記載のものなどが挙げられる。
市販されているフェノキシ樹脂は、ビスフェノールＡ型フェノキシ樹脂としては、フェノトートＹＰ５０（商品名、東都化成株式会社製）、Ｅ−１２５６（商品名、三菱化学株式会社製）、フルオレン型フェノキシ樹脂としては、ＦＸ２８０、ＦＸ２９３（商品名、東都化成株式会社製）、ビフェニル型フェノキシ樹脂としては、ＹＸ８１００、ＹＬ６９５４、ＹＬ６９７４（商品名、三菱化学株式会社製）等が挙げられる。
フェノキシ樹脂の中でも、ビスフェノールＡ型エポキシ樹脂の直鎖状高分子重合体は、高い耐熱性を有するために好ましく、この直鎖状高分子重合体であるフェノキシ樹脂としては、下記式に示す構造を有し、エポキシ当量２０００〜５０００ｇ／ｅｑ、平均分子量２００００〜２０００００のものが望ましい。
((E) component: phenoxy resin)
The phenoxy resin of component (E) used in the present invention is generally a one-step method in which bisphenol A and epichlorohydrin are subjected to a polycondensation reaction, or a bifunctional epoxy resin and a bifunctional phenol such as bisphenol A are polyadded. Specific examples include “Phenotote YP-50, Phenototo YP-55, Phenototo YP-70” (all trade names), manufactured by Toto Kasei Co., Ltd. -120124, JP-A-4-112714, and JP-A-4-339852.
Commercially available phenoxy resins include phenoto YP50 (trade name, manufactured by Tohto Kasei Co., Ltd.), E-1256 (trade name, manufactured by Mitsubishi Chemical Corporation), and fluorene type phenoxy resin as bisphenol A type phenoxy resins. FX280, FX293 (trade name, manufactured by Toto Kasei Co., Ltd.), and biphenyl type phenoxy resin include YX8100, YL6954, YL6974 (trade name, manufactured by Mitsubishi Chemical Corporation), and the like.
Among phenoxy resins, a linear polymer of a bisphenol A type epoxy resin is preferable because of its high heat resistance, and the phenoxy resin that is a linear polymer is a structure represented by the following formula: And having an epoxy equivalent of 2000 to 5000 g / eq and an average molecular weight of 20000 to 200000.
フェノキシ樹脂の中でも、ビスフェノールＡ又はビスフェノールＡ型エポキシ化合物若しくはそれらの誘導体、及びビスフェノールＦ又はビスフェノールＦ型エポキシ化合物若しくはそれらの誘導体を共重合成分の構成単位として含むものは、耐熱性、密着性及び溶解性に優れるため好ましい。ビスフェノールＡ／ビスフェノールＦ共重合型フェノキシ樹脂の具体例としては、東都化成株式会社製「フェノトートＹＰ−７０」（商品名）が挙げられる。
フェノキシ樹脂は、直鎖状であってもよく、分枝鎖状であってもよいが、直鎖状にして熱可塑性を持たせた高分子量フェノキシ樹脂は、プリプレグを構成する樹脂の靭性および接着性を向上させることができるため好ましい。したがって、（Ａ）高分子量フェノキシ樹脂としては、ビスフェノールＡのジグリシジルエーテルとビスフェノールＡが重合したような構造を持つ高分子量エポキシ樹脂の１種で、熱可塑性樹脂として知られているフェノキシ樹脂を使用することが好ましい。
Among phenoxy resins, those containing bisphenol A or a bisphenol A type epoxy compound or a derivative thereof, and bisphenol F or a bisphenol F type epoxy compound or a derivative thereof as a constituent unit of a copolymer component are heat resistant, adhesive and soluble. It is preferable because of its excellent properties. Specific examples of the bisphenol A / bisphenol F copolymer type phenoxy resin include “Phenotote YP-70” (trade name) manufactured by Tohto Kasei Co., Ltd.
The phenoxy resin may be linear or branched, but the high molecular weight phenoxy resin that is linear and has thermoplasticity is the toughness and adhesion of the resin that constitutes the prepreg. It is preferable because the property can be improved. Therefore, (A) high molecular weight phenoxy resin is a kind of high molecular weight epoxy resin having a structure in which diglycidyl ether of bisphenol A and bisphenol A are polymerized, and a phenoxy resin known as a thermoplastic resin is used. It is preferable to do.
（（Ｆ）成分：無機充填剤）
本発明で用いる（Ｆ）成分の無機充填剤としては、水酸化アルミニウム、水酸化マグネシウム、ゼオライト、ハイドロタルサイト等の無機水和物、クレー、タルク、ワラストナイト、マイカ、炭酸カルシウム、炭酸マグネシウム、アルミナ、シリカ、ガラス粉等の汎用される無機充填剤、ホウ酸亜鉛、スズ酸亜鉛、ヒドロキシスズ酸亜鉛等のＢ、Ｓｎ系充填剤、酸化亜鉛、酸化スズ等の金属酸化物、赤リン等の無機リン系材料、銅や亜鉛等の硝酸塩等が挙げられ、目的に応じて使用可能であり、またこれら無機充填剤をシランカップリング剤やチタネートカップリング剤、モリブデン酸亜鉛等により、コート又は処理して、有機成分との接着性、耐熱性、温湿度に対する安定性や安全性を向上させることが好ましい。
((F) component: inorganic filler)
As the inorganic filler of the component (F) used in the present invention, inorganic hydrates such as aluminum hydroxide, magnesium hydroxide, zeolite, hydrotalcite, clay, talc, wollastonite, mica, calcium carbonate, magnesium carbonate Inorganic fillers such as alumina, silica, glass powder, etc., B such as zinc borate, zinc stannate, zinc hydroxystannate, metal oxides such as Sn oxide, zinc oxide, tin oxide, red phosphorus Inorganic phosphorous materials such as copper, zinc and other nitrates can be used depending on the purpose, and these inorganic fillers can be coated with silane coupling agents, titanate coupling agents, zinc molybdate, etc. Or it is preferable to process and to improve the adhesiveness with an organic component, heat resistance, stability with respect to temperature and humidity, and safety | security.
（積層板用熱硬化性樹脂組成物）
本発明に用いる（Ａ）成分のジヒドロベンゾオキサジン環を有する化合物（熱硬化性樹脂）は、積層板用熱硬化性樹脂組成物の総量中（（Ｆ）無機充填剤を除く（Ａ）〜（Ｅ）の総計）に、２０〜４０質量％を配合する。好ましくは、３０〜３５質量％である。ジヒドロベンゾオキサジン環は官能基が嵩高く、立体障害が大きい等の理由から、架橋密度が低くなる傾向を示す。よって、４０質量％以上では基材としての剛性が低くなり、反りが起き易くなる。（Ａ）成分は、ハロゲンフリーで十分な難燃性とプリント配線板材料としての一般特性を両立させる必須成分でもあるため、性能発現のためには２０質量％以上必要である。
(Thermosetting resin composition for laminates)
The compound (thermosetting resin) having a dihydrobenzoxazine ring as the component (A) used in the present invention is the total amount of the thermosetting resin composition for laminates ((F) excluding inorganic fillers (A) to ( 20-40 mass% is mix | blended with the sum total of E). Preferably, it is 30-35 mass%. The dihydrobenzoxazine ring tends to have a low crosslinking density because of its bulky functional group and large steric hindrance. Therefore, if it is 40 mass% or more, the rigidity as a base material becomes low, and warpage tends to occur. The component (A) is an essential component that achieves both halogen-free and sufficient flame retardancy and general characteristics as a printed wiring board material.
本発明で用いる（Ｂ）フェノール類とトリアジン環を有する化合物とアルデヒド類の縮重合物は、積層板用熱硬化性樹脂組成物の総量中に、１０〜３０質量％を配合する。好ましくは、１０〜２５質量％である。（Ｂ）成分は、ハロゲンフリー材の重要な特性の１つである難燃性に寄与しており、性能発現のために１０質量％以上必要である。また、（Ｂ）成分は、硬化剤であるため、３０質量％を超える場合、硬化速度の制御が困難になり、プリプレグの保存安定性に問題が発生する。 The polycondensation product of (B) the phenols, the compound having a triazine ring and the aldehyde used in the present invention is blended in an amount of 10 to 30% by mass in the total amount of the thermosetting resin composition for laminates. Preferably, it is 10-25 mass%. Component (B) contributes to flame retardancy, which is one of the important characteristics of the halogen-free material, and is required to be 10% by mass or more for performance. Moreover, since (B) component is a hardening | curing agent, when it exceeds 30 mass%, control of a cure rate becomes difficult and a problem generate | occur | produces in the storage stability of a prepreg.
本発明で用いる（Ｃ）成分のフェノールノボラック型エポキシ樹脂は、積層板用熱硬化性樹脂組成物の総量中に、２０〜４０質量％を配合する。好ましくは、２０〜３０質量％である。この範囲は、実用的反応性（硬化速度）の観点から、（Ａ）成分、（Ｂ）成分の配合量が決まると、相対的に決定される。 The phenol novolac type epoxy resin of component (C) used in the present invention is blended in an amount of 20 to 40% by mass in the total amount of the thermosetting resin composition for laminates. Preferably, it is 20-30 mass%. This range is relatively determined when the blending amounts of the component (A) and the component (B) are determined from the viewpoint of practical reactivity (curing speed).
本発明で用いる（Ｄ）成分の縮合リン酸エステル系難燃剤は、積層板用熱硬化性樹脂組成物の総量中に、５〜３５質量％を配合する。難燃性の点、及び過剰に加えた場合の積層板特性低下を防ぐ観点から、前記の範囲とする。 The condensed phosphate ester flame retardant of component (D) used in the present invention is blended in an amount of 5 to 35% by mass in the total amount of the thermosetting resin composition for laminates. From the viewpoint of flame retardancy, and from the viewpoint of preventing deterioration of laminated sheet characteristics when excessively added, the above range is adopted.
本発明で用いる（Ｅ）成分のフェノキシ樹脂は、積層板用熱硬化性樹脂組成物の総量中に、１〜１５質量％を配合する。好ましくは、１〜１０質量％である。
また、本発明で用いる（Ｆ）成分の無機充填剤は、（Ａ）〜（Ｅ）成分の総量１００質量部に対して、１０〜１００質量部を配合する。無機充填剤の配合量が１０質量部未満の場合、基板材料自体の剛性が下がり、配合量が１００質量部を超えると、銅箔との密着力が下がるといった問題が発生する恐れがある。
(E) component phenoxy resin used by this invention mix | blends 1-15 mass% in the total amount of the thermosetting resin composition for laminated boards. Preferably, it is 1-10 mass%.
Moreover, the inorganic filler of the (F) component used by this invention mix | blends 10-100 mass parts with respect to 100 mass parts of total amounts of (A)-(E) component. When the compounding amount of the inorganic filler is less than 10 parts by mass, the rigidity of the substrate material itself is lowered, and when the compounding amount exceeds 100 parts by mass, there is a possibility that a problem that the adhesive strength with the copper foil decreases.
本発明の積層板用熱硬化性樹脂組成物は、これらの（Ａ）〜（Ｆ）成分の他に、熱硬化性樹脂の硬化剤や変性剤、または着色剤、酸化防止剤、還元剤、紫外線不透過剤等を配合することができ、これらは通常使用されているもので良く、特に限定されない。 In addition to these components (A) to (F), the thermosetting resin composition for a laminated board of the present invention is a thermosetting resin curing agent or modifier, or a colorant, antioxidant, reducing agent, A UV-opaque agent or the like can be blended, and these may be those usually used and are not particularly limited.
本発明の積層板用熱硬化性樹脂組成物は、有機溶剤に溶解又は分散させたワニスとして使用することが好ましい。有機溶剤としては、特に制限するものではないが、ケトン系、芳香族炭化水素系、エステル系、アミド系、アルコール系等を用いることがきる。
ケトン系溶剤として、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等が、芳香族炭化水素系としては、トルエン、キシレン等が、エステル系溶剤としては、メトキシエチルアセテート、エトキシエチルアセテート、ブトキシエチルアセテート、プロピレングリコールモノメチルエーテルアセテート、酢酸エチル等が、アミド系溶剤としては、Ｎ−メチルピロリドン、ホルムアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等が、アルコール系溶剤としては、メタノール、エタノール、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノプロピルエーテル等が挙げられる。これらの溶剤は１種又は２種以上を混合して用いることができる。
The thermosetting resin composition for laminated boards of the present invention is preferably used as a varnish dissolved or dispersed in an organic solvent. The organic solvent is not particularly limited, but ketone type, aromatic hydrocarbon type, ester type, amide type, alcohol type and the like can be used.
Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are used as ketone solvents, toluene, xylene, etc. are used as aromatic hydrocarbons, and methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene are used as ester solvents. Glycol monomethyl ether acetate, ethyl acetate, etc., as amide solvents, N-methylpyrrolidone, formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc., as alcohol solvents, Methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, and the like. These solvents can be used alone or in combination of two or more.
（プリプレグ）
本発明のプリプレグは、上記の積層板用熱硬化性樹脂組成物をワニスとして、基材に含浸、乾燥して得られる。プリプレグに用いる基材としては、紙、コットンリンターのような天然繊維基材、アラミド、ポリビニルアルコール、ポリエステル、アクリルのような有機合成繊維基材、ガラス、アスベストのような無機繊維基材が使用される。耐燃性の見地から、ガラス繊維基材が好ましい。ガラス繊維基材としては、Ｅガラス、Ｃガラス、Ｄガラス、Ｓガラス等を用いた織布や短繊維を有機バインダーで接着したガラス織布、更に、ガラス繊維とセルロース繊維とを混沙したものが挙げられ、より好ましくは，Ｅガラスを使用したガラス織布である。基材の厚さは、特に制限されず、例えば、約０．０３〜０．５ｍｍを使用することができ、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性や耐湿性、加工性の面から好適である。
積層板用熱硬化性樹脂組成物を基材に含浸、塗布する方法は、特に限定するものではなく、一般の方法が適用可能であり、基材に含浸、塗布した後、乾燥炉中を通過させることによって加熱乾燥させ、プリプレグを得ことができる。
基材に対する積層板用熱硬化性樹脂組成物の付着量は、乾燥後のプリプレグの樹脂含有率で、２０〜９０質量％となるように、基材に含浸又は塗工した後、通常、１００〜２００℃の温度で１〜３０分加熱乾燥し、半硬化（Ｂステージ化）させて、本発明のプリプレグを得ることができる。
(Prepreg)
The prepreg of the present invention is obtained by impregnating and drying a base material using the above-mentioned thermosetting resin composition for laminates as a varnish. As the base material used for the prepreg, natural fiber base materials such as paper and cotton linter, organic synthetic fiber base materials such as aramid, polyvinyl alcohol, polyester and acrylic, and inorganic fiber base materials such as glass and asbestos are used. The From the viewpoint of flame resistance, a glass fiber substrate is preferred. Glass fiber base materials include woven fabrics using E glass, C glass, D glass, S glass, etc., glass woven fabrics made by bonding short fibers with an organic binder, and glass fibers mixed with cellulose fibers. More preferred is a glass woven fabric using E glass. The thickness of the base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability.
The method of impregnating and applying the thermosetting resin composition for laminates to the substrate is not particularly limited, and general methods can be applied. After impregnating and applying to the substrate, the substrate passes through a drying furnace. By carrying out, it can heat-dry and can obtain a prepreg.
The amount of adhesion of the thermosetting resin composition for laminates to the substrate is usually 100 after impregnating or coating the substrate so that the resin content of the prepreg after drying is 20 to 90% by mass. The prepreg of the present invention can be obtained by heating and drying at a temperature of ˜200 ° C. for 1 to 30 minutes and semi-curing (B-stage).
（プリント配線板用積層板、プリント配線板、多層プリント配線板）
上記のようにして得られる本発明のプリプレグは、少なくとも１枚以上、必要に応じて所定枚数を重ね合わせ、その片面、または両面に銅箔等の金属箔を構成後、加圧、加熱プレスすることにより、プリント配線板用積層板が得られる。
成形条件は、例えば、電気絶縁材料用積層板及び多層板の手法が適用でき、例えば多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用し、温度１００〜２５０℃、圧力０．２〜２０ＭＰa、加熱時間０．１〜５時間の範囲で成形することができる。
(Laminated boards for printed wiring boards, printed wiring boards, multilayer printed wiring boards)
As for the prepreg of the present invention obtained as described above, at least one sheet is laminated as necessary, a predetermined number of sheets are laminated, and a metal foil such as a copper foil is formed on one side or both sides, and then pressed and heated. Thereby, the laminated board for printed wiring boards is obtained.
As the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. It can be molded in a range of ˜20 MPa and a heating time of 0.1 to 5 hours.
また、上記プリント配線板用積層板において、金属箔に回路加工を施すことによりプリント配線板とすることができる。回路加工は、定法により行えば良く、例えば、銅箔表面にレジストパターンを形成後、エッチングにより不要部分の銅箔を除去し、レジストパターンを剥離後、ドリルまたはレーザ加工により必要なスルーホールを形成し、再度レジストパターンを形成後、スルーホールに導通させるためのメッキを施し、最後にレジストパターンを剥離することにより行うことができる。このようにして得られたプリント配線板の表面に更に上記のプリプレグを積層し、上記と同様にして回路加工して多層プリント配線板とすることもできる。この場合，必ずしもスルーホールを形成する必要はなく，ＩＶＨ（インターステシャルビアホール）を形成しても良く、また、両方を形成することができる。多層プリント配線板に用いるプリプレグが、本発明のプリプレグと同種でも異種でもよく、目的に応じて選択することができる。 Moreover, in the printed wiring board laminate, a printed wiring board can be obtained by subjecting a metal foil to circuit processing. Circuit processing may be performed by a regular method. For example, after forming a resist pattern on the copper foil surface, unnecessary portions of the copper foil are removed by etching, and after removing the resist pattern, necessary through holes are formed by drilling or laser processing. Then, after forming the resist pattern again, plating for conducting to the through hole is performed, and finally the resist pattern is peeled off. The prepreg may be further laminated on the surface of the printed wiring board thus obtained, and a circuit may be processed in the same manner as described above to obtain a multilayer printed wiring board. In this case, it is not always necessary to form a through hole, and an IVH (interstitial via hole) may be formed, or both can be formed. The prepreg used for the multilayer printed wiring board may be the same as or different from the prepreg of the present invention, and can be selected according to the purpose.
以下、本発明の実施例及びその比較例によって本発明を更に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。
実施例１〜３、比較例１に用いた材料を下記に示した。
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.
The materials used in Examples 1 to 3 and Comparative Example 1 are shown below.
（Ａ）成分：ジヒドロベンゾオキサジン環を有する熱硬化性樹脂
温度計、撹拌機、冷却管、滴下装置を備えた５Ｌフラスコに、ビスフェノールＦ １０００ｇとメタノール９２０ｇを加え、撹拌しながら、５０℃で溶解した。そこに、パラホルムアルデヒド ６５２ｇを添加した。更に、撹拌しながら、アニリン ９３０ｇを１時間かけて滴下し、１時間後に７８〜８０℃になるようにした。還流下７時間反応させた後、減圧し、圧力３６０ｍｍＨｇで減圧濃縮した。この減圧度を保ったまま、濃縮を継続し、樹脂の温度が１１０℃になった時点で、減圧度を高めて、９０ｍｍＨｇにした。流出液がなくなったことを確認した後、樹脂をバットに取り出し、樹脂の軟化点が７８℃であるジヒドロベンゾオキサジン環を有する熱硬化性樹脂（Ａ）を得た。
Component (A): Thermosetting resin having dihydrobenzoxazine ring Add 5 g of bisphenol F and 920 g of methanol to a 5 L flask equipped with a thermometer, stirrer, condenser, and dropping device, and dissolve at 50 ° C. with stirring. did. Thereto, 652 g of paraformaldehyde was added. Further, 930 g of aniline was added dropwise over 1 hour with stirring so that the temperature became 78 to 80 ° C. after 1 hour. After reacting under reflux for 7 hours, the pressure was reduced, and the mixture was concentrated under reduced pressure at a pressure of 360 mmHg. Concentration was continued while maintaining the degree of vacuum, and when the temperature of the resin reached 110 ° C., the degree of vacuum was increased to 90 mmHg. After confirming that the effluent disappeared, the resin was taken out into a vat to obtain a thermosetting resin (A) having a dihydrobenzoxazine ring having a resin softening point of 78 ° C.
（Ｂ）成分：フェノール類とトリアジン環を有する化合物とアルデヒド類の縮重合物
フェノール ９４質量部に４１．５質量％ホルマリン２９質量部、及びトリエチルアミン０．４７質量部を加え、８０℃にて３時間反応させた。そして、メラミンを１９質量部加え、更に１時間反応させた後、常圧下にて水を除去しながら１２０℃まで昇温し、温度を保持したまま２時間反応させた。次に常圧下にて水を除去しながら１８０℃まで昇温し、減圧下にて未反応のフェノールを除去し、軟化点１３６℃のフェノール、メラミン及びホルマリンの縮重合物を得た。
Component (B): a polycondensation product of phenols and compounds having a triazine ring and aldehydes Phenols 94 parts by mass 41.5% by mass formalin 29 parts by mass and triethylamine 0.47 parts by mass Reacted for hours. And after adding 19 mass parts of melamine and making it react for 1 hour, it heated up to 120 degreeC, removing water under a normal pressure, and was made to react for 2 hours, keeping temperature. Next, the temperature was raised to 180 ° C. while removing water under normal pressure, and unreacted phenol was removed under reduced pressure to obtain a polycondensation product of phenol, melamine and formalin having a softening point of 136 ° C.
（Ｃ）成分：フェノールノボラック型エポキシ樹脂
ＥＰＩＣＬＯＮ Ｎ-７７０（ＤＩＣ株式会社、商品名）エポキシ当量１７０〜１８０ｇ／ｅｑ
（Ｄ）成分：縮合リン酸エステル系難燃剤
ＰＸ−２００（芳香族縮合リン酸エステル、大八化学工業株式会社商品名）
（Ｅ）成分：フェノキシ樹脂
ＨＭ−１０１（ビスフェノールＡタイプエポキシ樹脂、エポキシ当量３９００ｇ／ｅｑ、軟化点１５０℃、ＤＩＣ株式会社商品名）
（Ｆ）無機充填剤
水酸化アルミニウム ＣＬ−３０３（平均粒径４μｍ、住友化学株式会社商品名）
(C) Component: Phenol novolac type epoxy resin EPICLON N-770 (DIC Corporation, trade name) Epoxy equivalent 170-180 g / eq
Component (D): condensed phosphate ester flame retardant PX-200 (aromatic condensed phosphate ester, trade name of Daihachi Chemical Industry Co., Ltd.)
(E) component: Phenoxy resin HM-101 (Bisphenol A type epoxy resin, epoxy equivalent 3900 g / eq, softening point 150 ° C., trade name of DIC Corporation)
(F) Inorganic filler Aluminum hydroxide CL-303 (average particle size 4 μm, Sumitomo Chemical Co., Ltd. trade name)
（実施例１）
表１に示したように、（Ａ）ジヒドロベンゾオキサジン環を有する熱硬化性樹脂３３．３質量％、（Ｂ）フェノール類とトリアジン環を有する化合物とアルデヒド類の縮重合物１４．６質量％、（Ｃ）フェノールノボラック型エポキシ樹脂２０．８質量％、（Ｄ）縮合リン酸エステル系難燃剤１５．４質量％、（Ｅ）フェノキシ樹脂１０．０質量％から成る樹脂組成物に、この樹脂組成物１００質量部当たり（Ｆ）無機充填剤を５０．０質量部添加した積層板用熱硬化性樹脂組成物をワニス（溶剤；ＭＥＫ）とし、基材（ＩＰＣ-４４１２ シャープ７６２９タイプ、厚み１８０μｍ）に含浸塗布、乾燥し（温度１６５℃、５分）、半硬化させてプリプレグを作製した。次に、このプリプレグを５枚積層し、両面を１８μｍの銅箔ではさみ、所定の条件（温度１８５℃、圧力４ＭＰa、時間９０分）で加熱加圧を行い、プリント配線板用積層板を得た。更に、得られた積層板を、エッチングし、銅箔を取り除いた状態で打抜加工を実施し、打抜加工後の粉落ち量を測定した。また、Ｔｇ、耐燃焼性の評価を実施した。
Example 1
As shown in Table 1, (A) 33.3% by mass of a thermosetting resin having a dihydrobenzoxazine ring, (B) 14.6% by mass of a polycondensation product of a compound having a phenol and a triazine ring and an aldehyde. (C) 20.8% by mass of a phenol novolac type epoxy resin, (D) 15.4% by mass of a condensed phosphate ester flame retardant, and (E) 10.0% by mass of a phenoxy resin. A thermosetting resin composition for a laminated board to which 50.0 parts by mass of (F) inorganic filler is added per 100 parts by mass of the composition is a varnish (solvent; MEK), and a base material (IPC-4412 Sharp 7629 type, thickness 180 μm). ) Was impregnated, dried (temperature 165 ° C., 5 minutes) and semi-cured to prepare a prepreg. Next, 5 sheets of this prepreg are laminated, and both sides are sandwiched between 18 μm copper foils and heated and pressurized under predetermined conditions (temperature 185 ° C., pressure 4 MPa, time 90 minutes) to obtain a laminated board for printed wiring board. It was. Further, the obtained laminated plate was etched and punched in a state where the copper foil was removed, and the amount of powder falling after the punching was measured. In addition, Tg and combustion resistance were evaluated.
（実施例２）
表１に示したように、（Ａ）ジヒドロベンゾオキサジン環を有する熱硬化性樹脂３３．３質量％、（Ｂ）フェノール類とトリアジン環を有する化合物とアルデヒド類の縮重合物２２．１質量％、（Ｃ）フェノールノボラック型エポキシ樹脂２０．８質量％、（Ｄ）縮合リン酸エステル系難燃剤１７．０質量％、（Ｅ）フェノキシ樹脂１０．０質量％から成る樹脂組成物に、この樹脂組成物１００質量部当たり（Ｆ）無機充填剤を５０．０質量部添加した積層板用熱硬化性樹脂組成物をワニスとし、基材に含浸塗布、乾燥し、半硬化させてプリプレグを作製した。次に、このプリプレグを５枚積層し、両面を１８μｍの銅箔ではさみ、所定の条件で加熱加圧を行い、プリント配線板用積層板を得た。更に、得られた積層板を、エッチングし、銅箔を取り除いた状態で打抜加工を実施し、打抜加工後の粉落ち量を測定した。また、Ｔｇ、耐燃焼性の評価を実施した。
(Example 2)
As shown in Table 1, (A) thermosetting resin having a dihydrobenzoxazine ring 33.3% by mass, (B) 22.1% by mass of a polycondensation product of a compound having a phenol and a triazine ring and an aldehyde (C) 20.8% by mass of a phenol novolac type epoxy resin, (D) 17.0% by mass of a condensed phosphate ester flame retardant, and (E) 10.0% by mass of a phenoxy resin. A prepreg was prepared by impregnating, drying, and semi-curing a base plate with a thermosetting resin composition for laminates to which 50.0 parts by mass of (F) inorganic filler was added per 100 parts by mass of the composition. . Next, 5 sheets of this prepreg were laminated, and both sides were sandwiched between 18 μm copper foils, and heated and pressurized under predetermined conditions to obtain a laminated board for printed wiring board. Further, the obtained laminated plate was etched and punched in a state where the copper foil was removed, and the amount of powder falling after the punching was measured. In addition, Tg and combustion resistance were evaluated.
（実施例３）
表１に示したように、（Ａ）ジヒドロベンゾオキサジン環を有する熱硬化性樹脂３３．３質量％、（Ｂ）フェノール類とトリアジン環を有する化合物とアルデヒド類の縮重合物１４．６質量％、（Ｃ）フェノールノボラック型エポキシ樹脂２０．８質量％、（Ｄ）縮合リン酸エステル系難燃剤１５．４質量％、（Ｅ）フェノキシ樹脂５．０質量％から成る樹脂組成物に、この樹脂組成物１００質量部当たり（Ｆ）無機充填剤を５０．０質量部添加した積層板用熱硬化性樹脂組成物をワニスとし、基材に含浸塗布、乾燥し、半硬化させてプリプレグを作製した。次に、このプリプレグを５枚積層し、両面を１８μｍの銅箔ではさみ、所定の条件で加熱加圧を行い、プリント配線板用積層板を得た。更に、得られた積層板を、エッチングし、銅箔を取り除いた状態で打抜加工を実施し、打抜加工後の粉落ち量を測定した。また、Ｔｇ、耐燃焼性の評価を実施した。
(Example 3)
As shown in Table 1, (A) 33.3% by mass of a thermosetting resin having a dihydrobenzoxazine ring, (B) 14.6% by mass of a polycondensation product of a compound having a phenol and a triazine ring and an aldehyde. (C) 20.8% by mass of a phenol novolac-type epoxy resin, (D) 15.4% by mass of a condensed phosphate ester flame retardant, and (E) 5.0% by mass of a phenoxy resin. A prepreg was prepared by impregnating, drying, and semi-curing a base plate with a thermosetting resin composition for laminates to which 50.0 parts by mass of (F) inorganic filler was added per 100 parts by mass of the composition. . Next, 5 sheets of this prepreg were laminated, and both sides were sandwiched between 18 μm copper foils, and heated and pressurized under predetermined conditions to obtain a laminated board for printed wiring board. Further, the obtained laminated plate was etched and punched in a state where the copper foil was removed, and the amount of powder falling after the punching was measured. In addition, Tg and combustion resistance were evaluated.
（比較例１）
表１に示したように、（Ａ）ジヒドロベンゾオキサジン環を有する熱硬化性樹脂３３．３質量％、（Ｂ）フェノール類とトリアジン環を有する化合物とアルデヒド類の縮重合物１４．６質量％、（Ｃ）フェノールノボラック型エポキシ樹脂２０．８質量％、（Ｄ）縮合リン酸エステル系難燃剤１５．４質量％から成る樹脂組成物に、この樹脂組成物１００質量部当たり（Ｆ）無機充填剤を５０．０質量部添加した積層板用熱硬化性樹脂組成物をワニスとし、基材に含浸塗布、乾燥し、半硬化させてプリプレグを作製した。次に、このプリプレグを５枚積層し，両面を１８μｍの銅箔ではさみ、所定の条件で加熱加圧を行い、プリント配線板用積層板を得た。更に、得られた積層板を、エッチングし、銅箔を取り除いた状態で打抜加工を実施し、打抜加工後の粉落ち量を測定した。また、Ｔｇ、耐燃焼性の評価を実施した。
(Comparative Example 1)
As shown in Table 1, (A) 33.3% by mass of a thermosetting resin having a dihydrobenzoxazine ring, (B) 14.6% by mass of a polycondensation product of a compound having a phenol and a triazine ring and an aldehyde. (F) Inorganic filling per 100 parts by mass of this resin composition into a resin composition comprising (C) 20.8% by mass of a phenol novolac type epoxy resin and (D) 15.4% by mass of a condensed phosphate ester flame retardant A prepreg was prepared by impregnating, drying, and semi-curing a base material with a thermosetting resin composition for a laminated board to which 50.0 parts by mass of an agent was added. Next, 5 sheets of this prepreg were laminated, both sides were sandwiched between 18 μm copper foils, and heated and pressed under predetermined conditions to obtain a laminated board for printed wiring board. Further, the obtained laminated plate was etched and punched in a state where the copper foil was removed, and the amount of powder falling after the punching was measured. In addition, Tg and combustion resistance were evaluated.
（比較例２）
表１に示したように、（Ａ）ジヒドロベンゾオキサジン環を有する熱硬化性樹脂３３．３質量％、（Ｂ）フェノール類とトリアジン環を有する化合物とアルデヒド類の縮重合物１４．６質量％、（Ｃ）フェノールノボラック型エポキシ樹脂２０．８質量％、（Ｄ）縮合リン酸エステル系難燃剤１７．０質量％、（Ｅ）フェノキシ樹脂２０．０質量％から成る樹脂組成物に、この樹脂組成物１００質量部当たり（Ｆ）無機充填剤を５０．０質量部添加した積層板用熱硬化性樹脂組成物をワニスとし、基材に含浸塗布、乾燥し、半硬化させてプリプレグを作製した。次に、このプリプレグを５枚積層し、両面を１８μｍの銅箔ではさみ、所定の条件で加熱加圧を行い、プリント配線板用積層板を得た。更に、得られた積層板を、エッチングし、銅箔を取り除いた状態で打抜加工を実施し、打抜加工後の粉落ち量を測定した。また、Ｔｇ、耐燃焼性の評価を実施した。
(Comparative Example 2)
As shown in Table 1, (A) 33.3% by mass of a thermosetting resin having a dihydrobenzoxazine ring, (B) 14.6% by mass of a polycondensation product of a compound having a phenol and a triazine ring and an aldehyde. (C) 20.8% by mass of a phenol novolac epoxy resin, (D) 17.0% by mass of a condensed phosphate ester flame retardant, and (E) 20.0% by mass of a phenoxy resin. A prepreg was prepared by impregnating, drying, and semi-curing a base plate with a thermosetting resin composition for laminates to which 50.0 parts by mass of (F) inorganic filler was added per 100 parts by mass of the composition. . Next, 5 sheets of this prepreg were laminated, and both sides were sandwiched between 18 μm copper foils, and heated and pressurized under predetermined conditions to obtain a laminated board for printed wiring board. Further, the obtained laminated plate was etched and punched in a state where the copper foil was removed, and the amount of powder falling after the punching was measured. In addition, Tg and combustion resistance were evaluated.
〔両面プリント配線板の打抜加工後の粉落ち量測定〕
実施例１〜３、比較例１〜２の全面エッチングされたプリント配線板用積層板を作製し、積層板専用の打抜きパワープレスで打抜いた後、金型上に残った打抜き粉および打抜きクズを採取し、その質量を測定することで、打抜粉落ち量の評価を実施した。打抜きの形状は、およそ縦１８ｃｍ、横２３ｃｍの長方形の形状を有している。
[Measurement of amount of powder fall after punching of double-sided printed wiring board]
After manufacturing the laminated board for printed wiring boards of Examples 1 to 3 and Comparative Examples 1 to 2 and punching with a punching power press dedicated to the laminated board, punching powder and punching scraps remaining on the mold Was collected and the mass was measured to evaluate the amount of punched-off powder. The punched shape has a rectangular shape of approximately 18 cm in length and 23 cm in width.
〔ガラス転移温度（Ｔｇ）の測定〕
全面エッチングされたプリント配線板用積層板を作製し、これを用いて５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置（デュポン社製、ＴＭＡ２９４０）を用い、評価基板の熱膨張特性を観察することにより測定した。
[Measurement of glass transition temperature (Tg)]
A laminated board for printed wiring board etched on the entire surface is prepared, and a 5 mm square evaluation board is prepared using the laminated board, and a thermal expansion characteristic of the evaluation board is observed using a TMA test apparatus (manufactured by DuPont, TMA2940). It was measured by.
〔難燃性の評価〕
全面エッチングされたプリント配線板用積層板を作製し、これを長さ１２７ｍｍ、幅１２．７ｍｍに切り出した試験片を作製し、ＵＬ９４の試験法（Ｖ法）に準じて評価した。
[Evaluation of flame retardancy]
A laminated board for printed wiring board etched on the entire surface was prepared, and a test piece cut out to a length of 127 mm and a width of 12.7 mm was prepared and evaluated according to the UL94 test method (Method V).
実施例１〜３及び比較例１〜２の打抜加工後の粉落ち量、Ｔｇ、難燃性の耐燃焼性（平均燃焼時間）、耐燃焼性の判定の測定結果を表１にそれぞれ示した。 Table 1 shows the measurement results of the amount of powder fall, Tg, flame resistance of flame resistance (average combustion time), and determination of flame resistance after punching in Examples 1 to 3 and Comparative Examples 1 and 2. It was.
表１の結果から、（Ａ）〜（Ｆ)成分を含有する積層板用熱硬化性樹脂組成物を用いて作製したプリント配線板用積層板は、例えば実施例１と（Ｅ）成分のフェノキシ樹脂を含有しない比較例１を比較した場合、打抜加工後の粉落ち量は約０．６５ｍｇ（＝2.05-1.40ｍｇ）低く、約３２％低減できることが分かった。
比較例２から、（Ｅ）フェノキシ樹脂の配合量が２０質量％になると、Ｔｇ、耐燃焼性が低下する。
実施例１〜３に示したように、（Ｅ）成分のフェノキシ樹脂を特定範囲で適用することにより、従来から用いられてきた比較例１に比べ、打抜加工後の粉落ち量が３２％低減されるプリント配線板用積層板の提供が可能となった。
From the result of Table 1, the laminated board for printed wiring boards produced using the thermosetting resin composition for laminated boards containing the components (A) to (F) is, for example, Example 1 and the phenoxy of the (E) ingredient. When the comparative example 1 which does not contain resin was compared, it turned out that the amount of powder fall | offset after a punching process is about 0.65 mg (= 2.05-1.40 mg) low, and can reduce about 32%.
From Comparative Example 2, when the blending amount of (E) phenoxy resin is 20% by mass, Tg and combustion resistance are lowered.
As shown in Examples 1 to 3, by applying the phenoxy resin of the component (E) in a specific range, the amount of powder falling after punching is 32% compared to Comparative Example 1 that has been conventionally used. It has become possible to provide a laminate for printed wiring boards that can be reduced.
Claims (6)
前記積層板用熱硬化性樹脂組成物の総量中に、（Ａ）２０〜４０質量％、（Ｂ）１０〜３０質量％、（Ｃ）２０〜４０質量％、（Ｄ）５〜３５質量％、（Ｅ）１〜１５質量％を含み、（Ａ）〜（Ｅ）の総量１００質量部に対して、（Ｆ）を１０〜１００質量部含む積層板用熱硬化性樹脂組成物。 (A) a thermosetting resin having a dihydrobenzoxazine ring, (B) a polycondensation product of a phenol and a compound having a triazine ring and an aldehyde, (C) a phenol novolac epoxy resin, and (D) a condensed phosphorus. An acid ester flame retardant, (E) a phenoxy resin, (F) an inorganic filler,
In the total amount of the thermosetting resin composition for laminates, (A) 20-40% by mass, (B) 10-30% by mass, (C) 20-40% by mass, (D) 5-35% by mass. The thermosetting resin composition for laminated boards which contains 1-15 mass% of (E), and contains 10-100 mass parts of (F) with respect to 100 mass parts of total amounts of (A)-(E).
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| CN112739771A (en) * | 2018-09-27 | 2021-04-30 | 松下知识产权经营株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board |
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