JP5370735B2 - Resin composition and prepreg, laminate and wiring board using the same - Google Patents
Resin composition and prepreg, laminate and wiring board using the same Download PDFInfo
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本発明は、電子機器に用いられる樹脂組成物及びそれを用いたプリプレグ、積層板、配線板に関する。 The present invention relates to a resin composition used for an electronic device, and a prepreg, a laminate, and a wiring board using the same.
通常の積層板は、エポキシ樹脂を主剤とした樹脂組成物とガラス織布とを硬化・一体成形したものが一般的である。エポキシ樹脂は絶縁性や耐熱性、コストなどのバランスが優れるが、燃焼し易いという欠点を有する。このため、積層板の難燃化は必須であり、従来ブロム系難燃剤が用いられていた（特許文献１参照）。しかし、環境意識の高まりから燃焼時に環境に好ましくない物質を発生する可能性がある材料は電子部品も含めて規制する動きが活発になっている。このため、水酸化アルミニウムや水酸化マグネシウム等の水酸化物（特許文献２参照）、リン酸エステル等のリン化合物（特許文献３参照）、メラミン等の窒素化合物が難燃剤（特許文献４参照）として使用されている。しかしながら、水酸化物は多量に配合しないと難燃機能が発現しない、リン化合物は腐食性を有する、窒素化合物は難燃効果が低いなどの問題も知られている。また、ケイ酸塩、炭酸塩、金属酸化物等も難燃効果を発現することが知られている（特許文献５参照）。 A typical laminate is generally obtained by curing and integrally molding a resin composition mainly composed of an epoxy resin and a glass woven fabric. Epoxy resins have an excellent balance of insulation, heat resistance, cost, etc., but have the disadvantage of being easy to burn. For this reason, the flame retarding of a laminated board is indispensable, and the brominated flame retardant was conventionally used (refer patent document 1). However, due to increasing environmental awareness, there is an active movement to regulate materials including electronic components that may generate undesirable substances for the environment during combustion. For this reason, hydroxides such as aluminum hydroxide and magnesium hydroxide (see Patent Document 2), phosphorus compounds such as phosphate esters (see Patent Document 3), and nitrogen compounds such as melamine are flame retardants (see Patent Document 4). It is used as However, there are also known problems that the flame retardant function does not appear unless a large amount of hydroxide is blended, the phosphorus compound is corrosive, and the nitrogen compound has a low flame retardant effect. Silicates, carbonates, metal oxides, and the like are also known to exhibit a flame retardant effect (see Patent Document 5).
水酸化アルミニウム等の水酸化物は難燃効果を発現するが、十分な難燃性を発現するには多量の配合を必要とする。しかし、多量の配合による界面増加に伴う絶縁性の低下や多量の水酸化物の分解に伴う耐熱性の低下など多くの課題がある。このため、水酸化物の配合量を低減できる手法が求められていた。
本発明の目的は、上記課題を解決し、難燃性の高い樹脂組成物及びそれを用いたプリプレグ、積層板、配線板を提供することである。
A hydroxide such as aluminum hydroxide exhibits a flame retardant effect, but a large amount of blending is required to exhibit sufficient flame retardancy. However, there are many problems such as a decrease in insulation due to an increase in interface due to a large amount of blending and a decrease in heat resistance due to decomposition of a large amount of hydroxide. For this reason, the technique which can reduce the compounding quantity of a hydroxide was calculated | required.
The object of the present invention is to solve the above-mentioned problems and to provide a highly flame-retardant resin composition and a prepreg, laminate and wiring board using the same.
本発明者らは上記の課題を解決するために鋭意研究した結果、芳香環を有する樹脂と発泡剤を併用することで難燃性を向上できることがわかった。
本発明は、以下に関する。
（１） 芳香環を有するエポキシ樹脂、水酸化アルミニウム、及び発泡剤を含有する樹脂組成物であって、発泡剤の配合量が、芳香環を有するエポキシ樹脂を含む芳香環を有する樹脂１００質量部に対し、０．４から１０質量部である樹脂組成物を基材に塗布して含浸させ、次いで乾燥させて成るプリプレグ。
（２） 前記発泡剤のガス発生量が５０ｍｌ／ｇ以上であることを特徴とする（１）記載のプリプレグ。
（３） 前記発泡剤から発生するガスが不燃性ガスであることを特徴とする（１）または（２）に記載のプリプレグ。
（４） 前記発泡剤から発生するガスが窒素、二酸化炭素、水蒸気のいずれか１つ以上を含むことを特徴とする（１）〜（３）いずれかに記載のプリプレグ。
（５） 前記発泡剤がアミノ基を有する化合物であることを特徴とする（１）〜（４）いずれかに記載のプリプレグ。
（６） 基材がガラス織布、ガラス不織布、アラミド不織布のいずれかであることを特徴とする（１）〜（５）のいずれかに記載のプリプレグ。
（７） 所定枚数の（１）〜（６）のいずれかに記載のプリプレグを積層形成して成る積層板。
（８） （７）に記載の積層板に回路加工して成る配線板。
As a result of intensive studies to solve the above problems, the present inventors have found that flame retardancy can be improved by using a resin having an aromatic ring and a foaming agent in combination.
The present invention relates to the following.
(1) A resin composition containing an epoxy resin having an aromatic ring, aluminum hydroxide, and a foaming agent, the blending amount of the foaming agent being 100 parts by mass having an aromatic ring containing an epoxy resin having an aromatic ring to, impregnated by applying a 0.4 to 10 parts by der Ru tree fat composition to a substrate and then dried prepreg comprising.
(2) The prepreg according to (1), wherein a gas generation amount of the foaming agent is 50 ml / g or more.
(3) The prepreg according to (1) or (2), wherein the gas generated from the foaming agent is a nonflammable gas.
(4) The prepreg according to any one of (1) to (3), wherein the gas generated from the foaming agent contains one or more of nitrogen, carbon dioxide, and water vapor.
(5) The prepreg according to any one of (1) to (4), wherein the foaming agent is a compound having an amino group .
( 6 ) The prepreg according to any one of (1) to (5), wherein the substrate is any one of a glass woven fabric, a glass nonwoven fabric, and an aramid nonwoven fabric.
( 7 ) A laminate obtained by laminating a predetermined number of prepregs according to any one of (1) to (6) .
( 8 ) A wiring board obtained by processing a circuit on the laminated board according to (7) .
本発明によれば、芳香環を有する樹脂に発泡剤を配合することで、難燃性の高い樹脂組成物を得ることができる。 According to the present invention, a resin composition having high flame retardancy can be obtained by blending a foaming agent with a resin having an aromatic ring.
本発明は、芳香環を有する樹脂中に発泡剤を均一分散する、あるいは芳香環を有する樹脂と反応させることで難燃性を大きく向上させた樹脂組成物に関する。そして、本発明の樹脂組成物は、芳香環を有する樹脂及び発泡剤を含有する樹脂組成物であって、発泡剤の配合量が、芳香環を有する樹脂１００質量部に対し、０．４から１０質量部であることを特徴としている。 The present invention relates to a resin composition in which flame retardancy is greatly improved by uniformly dispersing a foaming agent in a resin having an aromatic ring or reacting with a resin having an aromatic ring. And the resin composition of this invention is a resin composition containing the resin which has an aromatic ring, and a foaming agent, Comprising: The compounding quantity of a foaming agent is from 0.4 with respect to 100 mass parts of resin which has an aromatic ring. It is characterized by 10 parts by mass.
本発明で用いる芳香環を有する樹脂は、芳香環を有していれば特に限定するものではないが、多層配線板用途では絶縁性や吸湿性の面で優れているエポキシ樹脂が好適に用いられる。用いるエポキシ樹脂は、分子内に２個以上のエポキシ基をもつ化合物であればどのようなものでもよく、例えば、ナフタレン型エポキシ樹脂、ナフタレンノボラック型エポキシ樹脂、アントラセン型エポキシ樹脂、ジヒドロアントラセン型エポキシ樹脂、ビフェニル型エポキシ樹脂、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、ビフェニルノボラック型エポキシ樹脂、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などがあり、特にナフタレン型エポキシ樹脂、ナフタレンノボラック型エポキシ樹脂、アントラセン型エポキシ樹脂、ジヒドロアントラセン型エポキシ樹脂などの芳香環の多いエポキシ樹脂が好ましい。これらの化合物の分子量はどのようなものでもよく、何種類かを併用することもできる。 The resin having an aromatic ring used in the present invention is not particularly limited as long as it has an aromatic ring, but an epoxy resin excellent in insulation and hygroscopicity is suitably used for multilayer wiring board applications. . The epoxy resin to be used may be any compound as long as it has two or more epoxy groups in the molecule, for example, naphthalene type epoxy resin, naphthalene novolac type epoxy resin, anthracene type epoxy resin, dihydroanthracene type epoxy resin. , Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc., especially naphthalene type epoxy resin Epoxy resins having many aromatic rings such as naphthalene novolac type epoxy resin, anthracene type epoxy resin, dihydroanthracene type epoxy resin are preferable. These compounds may have any molecular weight, and several types may be used in combination.
本発明で用いる発泡剤は、加熱分解して発生するガスで芳香環を有する樹脂から発生する燃焼ガスを希釈して難燃効果を発現すると考えられる。したがって、芳香環を有する樹脂から発生する燃焼ガスより燃焼性の低いガスを発生すればどのような発泡剤を用いても良いが、不燃性ガスであるとより好ましく、窒素、二酸化炭素、水蒸気のいずれか１つ以上を含有するガスを発生する発泡剤が特に好ましい。また、発泡剤の形状はどのような形状でもよいが、樹脂の流動性に対する影響を低減するために、球状であることが好ましく、溶剤に溶解できる発泡剤がさらに好ましい。また、アミノ基を有する発泡剤は、アンモニウム化することで熱分解温度を高くすることができる、樹脂と反応しても熱分解温度を高くできるため好ましい。なお、アミノ基を有する発泡剤としては、例えば、化合物（材料）として、ヒドラゾカルボンアミド、アゾジカルボンアミドなどが挙げられる。 The foaming agent used in the present invention is considered to exhibit a flame retardant effect by diluting a combustion gas generated from a resin having an aromatic ring with a gas generated by thermal decomposition. Therefore, any blowing agent may be used as long as it generates a gas that is less flammable than a combustion gas generated from a resin having an aromatic ring, but is preferably a non-flammable gas, such as nitrogen, carbon dioxide, water vapor. A foaming agent that generates a gas containing any one or more is particularly preferable. The foaming agent may have any shape, but in order to reduce the influence on the fluidity of the resin, the foaming agent is preferably spherical, and more preferably a foaming agent that can be dissolved in a solvent. Moreover, the foaming agent which has an amino group can raise a thermal decomposition temperature by ammonium-izing, Since it can raise a thermal decomposition temperature even if it reacts with resin, it is preferable. Examples of the foaming agent having an amino group include hydrazocarbonamide and azodicarbonamide as compounds (materials).
発泡剤のガス発生量は５０ｍｌ／ｇ以上であれば好ましく、７０ｍｌ／ｇ以上であればより好ましく、９０ｍｌ／ｇ以上であれば特に好ましい。発泡剤のガス発生量が５０ｍｌ／ｇ未満の場合、難燃効果が不十分のため、好ましくない。また、発泡剤のガス発生量は４００ｍｌ／ｇ以下であれば好ましく、３５０ｍｌ／ｇ以下であればより好ましく、３００ｍｌ／ｇ以下であれば特に好ましい。発泡剤のガス発生量が４００ｍｌ／ｇを超える場合、耐熱性が低下するため、好ましくない。 The gas generation amount of the blowing agent is preferably 50 ml / g or more, more preferably 70 ml / g or more, and particularly preferably 90 ml / g or more. When the amount of gas generated by the foaming agent is less than 50 ml / g, the flame retardant effect is insufficient, which is not preferable. Further, the gas generation amount of the foaming agent is preferably 400 ml / g or less, more preferably 350 ml / g or less, and particularly preferably 300 ml / g or less. When the amount of gas generated by the foaming agent exceeds 400 ml / g, the heat resistance is lowered, which is not preferable.
使用できる発泡剤の市販品としては、例えば、セルマイク１４２（ガス発生量９０ｍｌ／ｇ）、セルマイクＣ−２（ガス発生量２７０ｍｌ／ｇ）、セルマイク２６６（ガス発生量１２０ｍｌ／ｇ）、セルマイク３０６（ガス発生量１００ｍｌ／ｇ）、セルマイク４１７（ガス発生量９０ｍｌ／ｇ）、セルマイク４９４（ガス発生量１２０ｍｌ／ｇ）、セルマイク４９６（ガス発生量１１０ｍｌ／ｇ）（すべて三協化成株式会社製、商品名）などが挙げられる。 Examples of commercially available foaming agents that can be used include cell microphone 142 (gas generation amount 90 ml / g), cell microphone C-2 (gas generation amount 270 ml / g), cell microphone 266 (gas generation amount 120 ml / g), cell microphone 306 ( Gas generation amount 100 ml / g), cell microphone 417 (gas generation amount 90 ml / g), cell microphone 494 (gas generation amount 120 ml / g), cell microphone 496 (gas generation amount 110 ml / g) (all manufactured by Sankyo Kasei Co., Ltd., products) Name).
本発明で芳香環を有する樹脂と発泡剤の配合比率は、芳香環を有する樹脂１００質量部に対し、発泡剤が０．４から１０質量部であり、０．５から８質量部の範囲が好ましく、０．７から５質量部がより好ましく、１から４質量部が特に好ましい。芳香環を有する樹脂１００質量部に対して発泡剤が０．４質量部未満では難燃効果が乏しく、１０質量部を超えた場合では芳香環を有する樹脂の特性が低下するおそれがある。発泡剤を均一に分散させるため、らいかい機、ホモジナイザー、ビーズミル、ナノマイザー等の分散装置、粉砕装置を用いることが有効である。 In the present invention, the blending ratio of the resin having an aromatic ring and the foaming agent is such that the foaming agent is 0.4 to 10 parts by mass and the range of 0.5 to 8 parts by mass is 100 parts by mass of the resin having an aromatic ring. Preferably, 0.7 to 5 parts by mass is more preferable, and 1 to 4 parts by mass is particularly preferable. When the foaming agent is less than 0.4 parts by mass with respect to 100 parts by mass of the resin having an aromatic ring, the flame-retardant effect is poor, and when it exceeds 10 parts by mass, the properties of the resin having an aromatic ring may be deteriorated. In order to uniformly disperse the foaming agent, it is effective to use a dispersing device such as a raking machine, a homogenizer, a bead mill, or a nanomizer, or a pulverizing device.
本発明の芳香環を有する樹脂の溶解と発泡剤を混合（分散）、溶解するため、溶剤を加えることが好ましい。溶剤は、芳香環を有する樹脂の溶解と発泡剤を分散、溶解できればどのようなものでもよいが、特にアセトン、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、酢酸エチル、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジメチルアセトアミド、エタノール、エチ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メチルエーテルアセテート等が溶解性に優れ、好ましい。これらの溶剤の配合量は、芳香環を有する樹脂の溶解と発泡剤の溶解、分散ができればどのような量でもよいが、芳香環を有する樹脂と発泡剤の総量１００質量部に対して、３０〜３００質量部の範囲が好ましく、５０〜２００質量部の範囲がさらに好ましい。また、上記の溶剤は、組み合わせて用いても構わない。 In order to mix (disperse) and dissolve the blowing agent and the resin having an aromatic ring of the present invention, it is preferable to add a solvent. The solvent may be any solvent as long as it can dissolve and dissolve the foaming agent, and particularly acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, N, N-dimethylformamide, N N-dimethylacetamide, ethanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable because of excellent solubility. The amount of these solvents may be any amount as long as the resin having an aromatic ring can be dissolved and the foaming agent can be dissolved and dispersed. The range of -300 mass parts is preferable, and the range of 50-200 mass parts is more preferable. Moreover, you may use said solvent in combination.
無機充填剤を配合しても構わないし、添加剤を添加してもかまわない。無機充填剤としては、シリカ、アルミナ、水酸化アルミニウム、炭酸カルシウム、クレイ、タルク、窒化珪素、窒化ホウ素、酸化チタン、チタン酸バリウム、チタン酸鉛、チタン酸ストロンチウム等を使用することができる。無機充填剤の配合量としては、芳香環を有する樹脂と発泡剤の総量１００質量部に対して、３００質量部以下とすることが好ましく、２００質量部以下にすることが本発明の樹脂組成物（多層配線板用材料）が均一でかつ良好な取扱性を得るためにより好ましい。また、０．５質量部以上とすることが好ましく、１質量部以上とすることがより好ましい。無機充填剤を均一に分散させるため、らいかい機、ホモジナイザー、ビーズミル、ナノマイザー等を用いることが有効である。 An inorganic filler may be blended or an additive may be added. As the inorganic filler, silica, alumina, aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride, boron nitride, titanium oxide, barium titanate, lead titanate, strontium titanate and the like can be used. As a compounding quantity of an inorganic filler, it is preferable to set it as 300 mass parts or less with respect to 100 mass parts of total of resin which has an aromatic ring, and a foaming agent, and it is 200 mass parts or less. (Multilayer wiring board material) is more preferable in order to obtain uniform and good handleability. Moreover, it is preferable to set it as 0.5 mass part or more, and it is more preferable to set it as 1 mass part or more. In order to disperse the inorganic filler uniformly, it is effective to use a raking machine, a homogenizer, a bead mill, a nanomizer or the like.
添加剤としては、各種シランカップリング剤、硬化促進剤、消泡剤等を使用できる。この配合量としては芳香環を有する樹脂と発泡剤の総量１００質量部に対して、５質量部以下が好ましく、３質量部以下にすることが樹脂組成物の特性を維持する上でより好ましい。また、０．１質量部以上とすることが好ましく、１質量部以上とすることがより好ましい。 As the additive, various silane coupling agents, curing accelerators, antifoaming agents and the like can be used. The blending amount is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, with respect to 100 parts by mass of the total amount of the resin having an aromatic ring and the foaming agent, in order to maintain the characteristics of the resin composition. Moreover, it is preferable to set it as 0.1 mass part or more, and it is more preferable to set it as 1 mass part or more.
本発明のプリプレグは、上述の樹脂組成物を基材に塗布乾燥させて得られる。ここで使用する基材の種類には特に指定はなく、厚さ０．０２〜０．４ｍｍまでのものを、目的のプリプレグまたは積層板の厚さに合わせて使用することができる。また、基材としては、ガラス織布、ガラス不織布、アラミド不織布が好適に用いられる。プリプレグの含浸量は樹脂分として示されるが、樹脂分とはプリプレグの全質量に対する有機樹脂固形分と無機充填剤類の合計質量の割合のことであり、３０〜９０質量％であると好ましく、４０〜８０質量％であるとより好ましい。樹脂分は目的のプリプレグの性能、および積層後の絶縁層の厚さに合せて適宜決定される。プリプレグを製造する時の乾燥条件は乾燥温度６０〜２００℃、乾燥時間１〜３０分間の間で目的のプリプレグ特性に合わせて自由に選択することができる The prepreg of the present invention is obtained by applying and drying the above resin composition on a substrate. The type of the substrate used here is not particularly specified, and those having a thickness of 0.02 to 0.4 mm can be used according to the thickness of the target prepreg or laminate. Moreover, as a base material, a glass woven fabric, a glass nonwoven fabric, and an aramid nonwoven fabric are used suitably. The impregnation amount of the prepreg is shown as a resin content, and the resin content is a ratio of the total mass of the organic resin solid content and the inorganic fillers to the total mass of the prepreg, and is preferably 30 to 90% by mass, More preferably, it is 40-80 mass%. The resin content is appropriately determined according to the performance of the target prepreg and the thickness of the insulating layer after lamination. The drying conditions for producing the prepreg can be freely selected according to the desired prepreg characteristics within a drying temperature of 60 to 200 ° C. and a drying time of 1 to 30 minutes.
また、本発明の積層板は、所定枚数の前記のプリプレグを積層成形して得られる。積層成形条件は特に限定されず、また、積層成形の際、金属箔を配し、金属張積層板としても良い。通常、目的とする積層板の厚みに合わせて得られたプリプレグを積層し、その片側または両側に金属箔を重ね、加熱加圧して積層板を製造する。金属箔としては主に銅箔やアルミ箔を用いるが、他の金属箔を用いてもよい。金属箔の厚みは通常３〜２００μｍである。積層板製造時の加熱温度は１３０〜２５０℃、より好ましくは１６０〜２００℃で、圧力は０．５〜１０ＭＰａ、より好ましくは１〜４ＭＰａであり、プリプレグ特性や、プレス機の能力、目的の積層板の厚み等により適宜決定する。 The laminate of the present invention is obtained by laminating a predetermined number of the prepregs. Lamination molding conditions are not particularly limited, and a metal foil may be provided at the time of lamination molding to form a metal-clad laminate. Usually, the prepreg obtained according to the thickness of the target laminated board is laminated | stacked, metal foil is piled up on the one side or both sides, and it heat-presses and manufactures a laminated board. As the metal foil, copper foil or aluminum foil is mainly used, but other metal foil may be used. The thickness of the metal foil is usually 3 to 200 μm. The heating temperature during the production of the laminate is 130 to 250 ° C., more preferably 160 to 200 ° C., and the pressure is 0.5 to 10 MPa, more preferably 1 to 4 MPa. It determines suitably by the thickness etc. of a laminated board.
また本発明の配線板は上述の積層板に一般的な回路加工を施して得られる。一般的な回路加工として、エッチング法、アディテッブ法、セミアディテッブ法などで、回路形成が可能である。 The wiring board of the present invention can be obtained by subjecting the above laminated board to general circuit processing. As general circuit processing, a circuit can be formed by an etching method, an additive method, a semi-additive method, or the like.
以下に、本発明を実施例に基づいて詳細に説明するが、本発明はこれに限定されるものではない。
実施例１
ビーカーに、芳香環を有する樹脂としてフェノールノボラック型エポキシ樹脂（Ｎ−７７０、大日本インキ化学工業株式会社製商品名）１００ｇ、エポキシ樹脂の硬化剤としてクレゾールノボラック樹脂（ＫＡ−１１６５、大日本インキ化学工業株式会社製商品名）６３．０ｇ、シリカ（ＳＯ−Ｇ１、株式会社アドマテックス製商品名）１２２．２ｇ、水酸化アルミニウム（ＨＰ−３５０、昭和電工株式会社製商品名）１３４．４ｇ、発泡剤（セルマイク１４２、三協化成株式会社製商品名、ガス発生量９０ｍｌ／ｇ）を１．６ｇ、硬化促進剤２ＰＺ−ＣＮ（四国化成工業株式会社商品名）：０．５ｇ、メチルエチルケトン（関東化学株式会社製）３００ｇを投入し、１時間撹拌して目的の樹脂組成物ワニスを得た。
Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.
Example 1
In a beaker, 100 g of a phenol novolac type epoxy resin (N-770, trade name, manufactured by Dainippon Ink and Chemicals, Inc.) as a resin having an aromatic ring, and a cresol novolak resin (KA-1165, Dainippon Ink Chemical) as a curing agent for the epoxy resin. Kogyo Co., Ltd. trade name) 63.0 g, Silica (SO-G1, Admatex Co., Ltd. trade name) 122.2 g, Aluminum hydroxide (HP-350, Showa Denko KK trade name) 134.4 g, Foam 1.6 g of agent (Cermic 142, trade name, Sankyo Kasei Co., Ltd., gas generation amount 90 ml / g), curing accelerator 2PZ-CN (trade name of Shikoku Kasei Co., Ltd.): 0.5 g, methyl ethyl ketone (Kanto Chemical) 300 g) was added and stirred for 1 hour to obtain the desired resin composition varnish.
作製した樹脂組成物ワニスを厚みが０．１ｍｍのガラス織布（坪量１０５ｇ／ｍ２）に含浸し、１６０℃で３分間加熱して半硬化（Ｂステージ状態）のプリプレグを得た。このプリプレグを８枚重ね、その両側に１８μｍの商品名Ｆ２−ＷＳ銅はく（Ｒｚ：２．０μｍ、Ｒａ：０．３μｍ）を重ね、１８５℃、９０分、３．０ＭＰａのプレス条件で両面銅張積層板を作製した。この銅張積層板を過硫酸アンモニウム１５０ｇ／ｌの水溶液に４０℃−２０分間浸漬して銅はくをエッチング除去した。その後、１３ｍｍ×１３０ｍｍにサンプルを切り出し、ＵＬ−９４垂直法に準拠して難燃性を評価した。 The produced resin composition varnish was impregnated into a 0.1 mm thick glass woven fabric (basis weight 105 g / m 2 ) and heated at 160 ° C. for 3 minutes to obtain a semi-cured (B stage state) prepreg. Eight prepregs are stacked, and 18 μm product name F2-WS copper foil (Rz: 2.0 μm, Ra: 0.3 μm) is stacked on both sides of the prepreg, and both sides are pressed at 185 ° C., 90 minutes, 3.0 MPa. A copper clad laminate was prepared. The copper clad laminate was immersed in an aqueous solution of 150 g / l ammonium persulfate at 40 ° C. for 20 minutes to remove the copper foil by etching. Then, the sample was cut out to 13 mm x 130 mm, and the flame retardance was evaluated based on the UL-94 vertical method.
実施例２
発泡剤（セルマイク１４２、三協化成株式会社製商品名、ガス発生量９０ｍｌ／ｇ）の配合量を４．９ｇに変えた以外は全て実施例１と同様にして行った。
Example 2
The same procedure as in Example 1 was performed except that the blending amount of the foaming agent (CELLMIC 142, trade name, manufactured by Sankyo Kasei Co., Ltd., gas generation amount 90 ml / g) was changed to 4.9 g.
実施例３
発泡剤をセルマイク１４２からセルマイクＣ−２（三協化成株式会社製商品名、ガス発生量２７０ｍｌ／ｇ）１．６ｇに変えた以外は全て実施例１と同様にして行った。
Example 3
The same procedure as in Example 1 was performed except that the foaming agent was changed from Cell Microphone 142 to Cell Microphone C-2 (trade name, Sankyo Kasei Co., Ltd., gas generation amount 270 ml / g) 1.6 g.
比較例１
ビーカーにフェノールノボラック型エポキシ樹脂（Ｎ−７７０、大日本インキ化学工業株式会社製商品名）１００ｇ、エポキシ樹脂の硬化剤としてクレゾールノボラック樹脂（ＫＡ−１１６５、大日本インキ化学工業株式会社製商品名）６３．０ｇ、シリカ（ＳＯ−Ｇ１、株式会社アドマテックス製商品名）１２２．２ｇ、水酸化アルミニウム（ＨＰ−３５０、昭和電工株式会社製商品名）１３４．４ｇ、硬化促進剤２ＰＺ−ＣＮ（四国化成工業株式会社商品名）：０．５ｇ、メチルエチルケトン（関東化学株式会社製）３００ｇを投入し、１時間撹拌して樹脂組成物ワニスを得た。
Comparative Example 1
In a beaker, phenol novolac type epoxy resin (N-770, Dainippon Ink Chemical Co., Ltd. product name) 100 g, cresol novolak resin (KA-1165, Dainippon Ink Chemical Co., Ltd. product name) as a curing agent for epoxy resin. 63.0 g, silica (SO-G1, trade name manufactured by Admatechs Corporation) 122.2 g, aluminum hydroxide (HP-350, trade name manufactured by Showa Denko KK) 134.4 g, curing accelerator 2PZ-CN (Shikoku) Kasei Kogyo Co., Ltd. trade name): 0.5 g, 300 g of methyl ethyl ketone (manufactured by Kanto Chemical Co., Inc.) were added and stirred for 1 hour to obtain a resin composition varnish.
作製した樹脂組成物ワニスを厚みが０．１ｍｍのガラス織布（坪量１０５ｇ／ｍ２）に含浸し、１６０℃で３分間加熱して半硬化（Ｂステージ状態）のプリプレグを得た。このプリプレグを８枚重ね、その両側に１８μｍの商品名Ｆ２−ＷＳ銅はく（Ｒｚ：２．０μｍ、Ｒａ：０．３μｍ）を重ね、１８５℃、９０分、３．０ＭＰａのプレス条件で両面銅張積層板を作製した。この銅張積層板を過硫酸アンモニウム１５０ｇ／ｌの水溶液に４０℃−２０分間浸漬して銅はくをエッチング除去した。その後、１３ｍｍ×１３０ｍｍにサンプルを切り出し、ＵＬ−９４垂直法に準拠して難燃性を評価した。 The produced resin composition varnish was impregnated into a 0.1 mm thick glass woven fabric (basis weight 105 g / m 2 ) and heated at 160 ° C. for 3 minutes to obtain a semi-cured (B stage state) prepreg. Eight prepregs are stacked, and 18 μm product name F2-WS copper foil (Rz: 2.0 μm, Ra: 0.3 μm) is stacked on both sides of the prepreg, and both sides are pressed at 185 ° C., 90 minutes, 3.0 MPa. A copper clad laminate was prepared. The copper clad laminate was immersed in an aqueous solution of 150 g / l ammonium persulfate at 40 ° C. for 20 minutes to remove the copper foil by etching. Then, the sample was cut out to 13 mm x 130 mm, and the flame retardance was evaluated based on the UL-94 vertical method.
比較例２
発泡剤（セルマイク１４２、三協化成株式会社製商品名、ガス発生量９０ｍｌ／ｇ）を０．５ｇ配合した以外は全て比較例１と同様にして行った。
Comparative Example 2
All were carried out in the same manner as Comparative Example 1 except that 0.5 g of a foaming agent (Cermic 142, trade name, manufactured by Sankyo Kasei Co., Ltd., gas generation amount 90 ml / g) was added.
実施例で作製したサンプルの燃焼性試験結果を表１に示した。一方、比較例で作製したサンプルの燃焼性試験結果を表２に示した。 Table 1 shows the flammability test results of the samples produced in the examples. On the other hand, Table 2 shows the flammability test results of the samples produced in the comparative examples.
表１の実施例１、２の比較から、発泡剤配合量が増えるに従って、平均燃焼時間が短くなっていくことがわかる。また、表１の実施例１，３の比較から、ガス発生量が多い発泡剤を使用した場合ほど燃焼時間が短くなっていくことがわかる。実施例の平均燃焼時間が６．６〜７．３ｓ（秒）であるのに対し、表２の比較例１、２の平均燃焼時間が９．２〜９．３ｓ（秒）であり、実施例に比較して長かった（悪かった）。すなわち、比較例２に示したように、芳香環を有する樹脂（Ｎ−７７０及びＫＡ−１１６５）１００質量部に対し、発泡剤配合量（セルマイク１４２）が０．３質量部程度である場合は、発泡剤配合による難燃効果が乏しいことが判る。したがって、芳香環を有する樹脂の難燃性向上には、一定量以上の発泡剤の配合が有効であることがわかる。
本発明によれば、芳香環を有する樹脂に発泡剤を一定量以上配合することで、難燃性の高い樹脂組成物を得ることができる。
From the comparison of Examples 1 and 2 in Table 1, it can be seen that the average combustion time decreases as the blending amount of the blowing agent increases. Moreover, it can be seen from the comparison between Examples 1 and 3 in Table 1 that the combustion time becomes shorter as the foaming agent having a larger gas generation amount is used. While the average burning time of the examples is 6.6 to 7.3 s (seconds), the average burning time of Comparative Examples 1 and 2 in Table 2 is 9.2 to 9.3 s (seconds). It was longer (bad) than the example. That is, as shown in Comparative Example 2, when 100 parts by mass of the aromatic ring-containing resin (N-770 and KA-1165) is 100 parts by mass of the foaming agent (Cermic 142), about 0.3 parts by mass It can be seen that the flame retardant effect by blending the foaming agent is poor. Therefore, it can be seen that blending a certain amount or more of the foaming agent is effective for improving the flame retardancy of the resin having an aromatic ring.
According to the present invention, a resin composition having high flame retardancy can be obtained by blending a certain amount or more of a foaming agent with a resin having an aromatic ring.
Claims (8)
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