JP4255759B2 - Polyphenylene ether resin composition, prepreg containing the same, laminate, copper-clad laminate and printed wiring board - Google Patents

Description

（式中、ｎは１〜１０の整数である。）で表される化合物が挙げられる。
【００１６】
この縮合リン酸エステル化合物は、樹脂組成物の難燃性を維持しつつ、樹脂組成物の架橋密度を適当に低下させることで弾性率を適度に低下させ、結果として樹脂硬度を低下させる応力緩和剤として機能することで高温での半田耐熱性を向上させるものである。
【００１７】
また、（Ａ）縮合リン酸エステル化合物の配合量としては、［（Ａ）成分＋（Ｂ）成分＋（Ｃ）成分］に対して１０〜５０重量％の範囲で含有することを特徴とするものである。
【００１８】
本発明に用いられる（Ｂ）酸変性ポリフェニレンエーテルは、ポリフェニレンエーテルが酸性化合物で変性されたものであり、例えば、ポリフェニレンエーテルと不飽和カルボン酸及び／又は酸無水物とを反応させることにより生成する反応生成物を挙げることができる。
【００１９】
このとき、原料となるポリフェニレンエーテルとしては、例えば、２，６−ジメチルフェノールの単独重合で得られるポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）のスチレングラフト共重合体、２，６−ジメチルフェノールと２−メチル−６−フェニルフェノールとの共重合体、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体、２，６−ジメチルフェノールと多官能フェノール化合物の存在下で重合して得られた多官能ポリフェニレンエーテル、２，６−ジメチルフェノールを置換アニリンや脂肪族第２アミンの存在下で重合して得られる含窒素ポリフェニレンエーテル等が挙げられる。
【００２０】
不飽和カルボン酸としては、二重結合を有し少なくともカルボキシル基を１個以上有するカルボン酸又はジカルボン酸無水物が挙げられ、無水マレイン酸、マレイン酸、フマル酸、イタコン酸であることが好ましい。これらは単独又は２種以上を混合して使用することができる。
【００２１】
これらを原料として、例えば溶媒や他樹脂の存在下、ポリフェニレンエーテルと不飽和カルボン酸とを反応させることにより酸変性ポリフェニレンエーテルを得ることができる。このときの変性方法については特に制限はなく、公知の方法、例えば、二軸押出機、ロールミル等を用いて１５０〜３５０℃の範囲の温度において溶融混練し、反応させる方法、ベンゼン、トルエン、キシレン等の溶媒中で加熱反応させる方法等により行うことができる。
【００２２】
さらに、これらの反応を容易にするために、反応系にベンゾイルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルパーオキシベンゾエート、アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、２，３−ジフェニル−２，３−ジメチルブタン等のラジカル発生剤を存在させることが好ましい。
【００２３】
ここで、（Ｂ）酸変性ポリフェニレンエーテルの配合量としては、［（Ａ）成分＋（Ｂ）成分＋（Ｃ）成分］に対して１０〜５０重量％の範囲で含有することが好ましい。
【００２４】
本発明で用いられる（Ｃ）トリアリルイソシアヌレート及び／又はトリアリルシアヌレートは、ポリフェニレンエーテル樹脂に対して架橋剤として働き、単独又は２種以上を混合して使用することができ、トリアリルイソシアヌレート及び／又はトリアリルシアヌレートを用いることで誘電特性及び耐熱性に優れた硬化物を得ることができる。
【００２５】
この（Ｃ）トリアリルイソシアヌレート及び／又はトリアリルシアヌレートの配合量としては、［（Ａ）成分＋（Ｂ）成分＋（Ｃ）成分］に対して、４０〜５０重量％の範囲で含有することが好ましい。
【００２６】
また、ポリフェニレンエーテルと不飽和カルボン酸との反応生成物にトリアリルイソシアヌレート又はトリアリルシアヌレートを架橋させる際には、ラジカル開始剤等の硬化促進剤を使用することが好ましい。このラジカル開始剤としては、例えば、パーヘキシン２５Ｂ（日本油脂株式会社製、商品名）等のラジカル開始剤として通常用いられている過酸化物等が挙げられる。
【００２７】
本発明で用いられる（Ｄ）成分としては、ホウ酸亜鉛と酸化亜鉛を用いることができるが、これらは単独又は混合して使用することができる。
【００２８】
この（Ｄ）成分により、本発明のポリフェニレンエーテル樹脂組成物が、ハロゲンフリーでも優れた誘電特性を有することができる。
【００２９】
この（Ｄ）無機充填剤の配合量としては、［（Ａ）成分＋（Ｂ）成分＋（Ｃ）成分］１００重量部に対して、５〜４０重量部の範囲で含有することが好ましい。配合量が５重量部未満の場合は、十分な難燃性、耐熱性、耐湿性が得られず、また、４０重量部を超えると、金属箔との密着性、組成物の溶媒流動性が低下してしまう。
【００３０】
さらに、これらの成分に加えて、（Ｂ）及び（Ｃ）の構成成分以外の熱可塑性樹脂又は熱硬化性樹脂を１種又は２種以上混合して用いることができる。
【００３１】
ここで用いることができる熱可塑性樹脂としては、例えば、ＧＰＰＳ（汎用ポリスチレン）、ＨＩＰＳ（耐衝撃性ポリスチレン）、ポリブタジエン、スチレンブタジエンブロックコポリマー等が挙げられ、熱硬化性樹脂としては、例えば、エポキシ樹脂等が挙げられる。これらの樹脂は、単独または２種以上を混合して使用することができる。
【００３２】
以上述べた本発明のポリフェニレンエーテル樹脂組成物は、これをトルエン等の好適な有機溶剤で希釈してワニスとし、これをガラス不織布、ガラス織布等の多孔質ガラス基材に塗布、含浸させ、加熱するという通常の方法によりプリプレグを製造することができる。
【００３３】
また、このプリプレグを複数枚重ね合わせ、その積層構造の片面又は両面に銅箔を重ね合わせた後、これを通常の条件で加熱、加圧してガラスエポキシ銅張積層板（内層板）に回路を形成し、ついで銅箔をエッチング処理した後、内層板の少なくとも片面にプリプレグ及び銅箔を重ね合わせ、これを例えば１７０℃、４ＭＰａの圧力で１００分間加熱・加圧するという通常の方法により製造することができる。
【００３４】
さらにプリント配線板は、銅張積層板又は多層板にスルーホールを形成し、スルーホールメッキを行った後、所定の回路を形成するという通常の方法により製造することができる。
【００３５】
本発明に用いるガラス織布及び銅箔は、通常、ガラスエポキシ銅張積層板に使用されるものであれば特に制限はなく使用することができる。
【００３６】
【実施例】
次に、本発明を参考例及び実施例を参照しながら説明する。
【００３７】
（参考例１）
ポリ（２，６−ジメチル−１，４−フェニレンエーテル） １ｋｇ、無水マレイン酸 ６０ｇ、ラジカル発生剤として２，３−ジメチル−２，３−ジフェニルブタン １０ｇをドライブレンドし、二軸押出機を用いて、３００℃で溶融混練を行った。このとき、樹脂温度は約３３０℃であった。ストランドを冷却後ペレット化し、無水マレイン酸変性ポリフェニレンエーテルを製造した。
【００３８】
（参考例２）
無水マレイン酸変性ポリフェニレンエーテル ５０重量部、トリアリルイソシアヌレート（日本化成株式会社製） ４６重量部、ＧＰＰＳ（汎用ポリスチレン、重量平均分子量 ２７万） ４重量部、ＰＸ−２００（大八化学工業株式会社製、商品名） １５重量部、ＦＵＳＥＬＥＸ Ｅ−２（株式会社龍森製、商品名、平均粒径 ７μｍ） １５重量部、パーヘキシン２５Ｂ（日本油脂株式会社製、商品名） ６重量部をトルエンに溶解させてワニスを作製した。
調整したワニスをガラス織布に連続的に含浸塗布し、１６０℃の温度で乾燥しプリプレグを製造した。製造したプリプレグ８枚を重ね合わせ、その両面に厚さ１８μｍの銅箔を重ね合わせて、１７０℃、圧力４０ｋｇ／ｃｍで９０分間、加熱加圧一体に成形して、板厚１．６ｍｍのガラスエポキシ銅張積層板を製造した。
【００３９】
（参考例３）
無水マレイン酸変性ポリフェニレンエーテル ５０重量部、トリアリルイソシアヌレート（日本化成株式会社製） ４６重量部、ＧＰＰＳ（汎用ポリスチレン、重量平均分子量 ２７万） ４重量部、ＰＸ−２０７（大八化学工業株式会社製、商品名） １５重量部、ＦＵＳＥＬＥＸ Ｅ−２（株式会社龍森製、商品名、平均粒径 ７μｍ） １５重量部、パーヘキシン２５Ｂ（日本油脂株式会社製、商品名） ６重量部をトルエンに溶解させてワニスを作製した。
調整したワニスを用いて参考例２と同様にしてガラスエポキシ銅張積層板を製造した。
【００４０】
（実施例１）
無水マレイン酸変性ポリフェニレンエーテル ５０重量部、トリアリルイソシアヌレート（日本化成株式会社製） ４６重量部、ＧＰＰＳ（汎用ポリスチレン、重量平均分子量 ２７万） ４重量部、ＰＸ−２００（大八化学工業株式会社製、商品名） １５重量部、ホウ酸亜鉛（ボラックス社製、商品名：Ｆｉｒｅｂｒａｋｅ ＺＢ、平均粒径２μｍ） １５重量部、パーヘキシン２５Ｂ（日本油脂株式会社製、商品名） ６重量部をトルエンに溶解させてワニスを作製した。調整したワニスを用いて参考例２と同様にしてガラスエポキシ銅張積層板を製造した。
【００４１】
（比較例１）
無水マレイン酸変性ポリフェニレンエーテル ５０重量部、トリアリルイソシアヌレート（日本化成株式会社製） ４６重量部、ＧＰＰＳ（汎用ポリスチレン、重量平均分子量 ２７万） ４重量部、ＦＵＳＥＬＥＸ Ｅ−２（株式会社龍森製、商品名、平均粒径 ７μｍ） １５重量部、パーヘキシン２５Ｂ（日本油脂株式会社製） ６重量部、三酸化アンチモン ４重量部、臭素難燃剤ＳＡＹＴＥＸ８０１０（アルベマール浅野製、商品名） ２０重量部をトルエンに溶解させてワニスを作製した。
調整したワニスを用いて参考例２と同様にしてガラスエポキシ銅張積層板を製造した。
【００４２】
（試験例１）
参考例２〜３、実施例１及び比較例１で製造したガラスエポキシ銅張積層板のそれぞれについて、引き剥がし強さ、難燃性、耐熱性、耐湿性等の試験を行い、その結果を表１に示した。
【００４３】
【表１】

＊１：ＪＩＳ−Ｃ−６４８１に準じて測定した。
＊２：ＵＬ９４難燃性試験に準じて測定した。
＊３：ＪＩＳ−Ｃ−６４８１に準じて２６０℃の半田に８分サンプルを浮かべ、膨れの有無を観察した。
＊４：ＪＩＳ−Ｃ−６４８１に準じ、ＴＭＡ法にて測定した。
＊５：ＪＩＳ−Ｃ−６４８１に準じて測定した。
【００４４】
【発明の効果】
本発明のポリフェニレンエーテル樹脂組成物やこの樹脂組成物を含有するプリプレグ並びに積層板、銅張積層板及びプリント配線板は、難燃化手法としてハロゲン等の有害物質を使用しないことを特徴としており、燃焼時有毒ガスである臭素化水素を発生させることなく、誘電特性、耐熱性、耐湿性、耐食性等に優れたものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyphenylene ether resin composition, and particularly to a halogen-free resin composition having high flame retardancy by containing a condensed phosphate ester compound. The present invention further relates to a prepreg impregnated with the polyphenylene ether resin composition, a laminate, a copper-clad laminate, and a printed wiring board.
[0002]
[Prior art]
In recent years, the development of electronic devices using integrated circuits such as IC and LSI has been remarkable, and a variety of copper-clad laminates have been used, and those having excellent characteristics according to their respective uses have been required. .
[0003]
For example, for laminates used in the ultra-high frequency region such as the X-band (8-70 GHz) region used for satellite communications and the like, a material having excellent dielectric properties is particularly required. Currently, polyphenylene ether is mainly used. Is used.
[0004]
The materials used for such applications are also required to have high flame retardance from the viewpoint of product safety, and 1,2-bis- (pentabromo) is used as a method for flame-retarding polyphenylene ether. Methods using brominated resins such as phenyl) ethane, antimony oxide and the like are known.
[0005]
However, with the growing concern about global environmental issues and human safety, electrical and electronic devices are required to have less harmfulness and higher safety in addition to good flame retardancy. It has been.
[0006]
Although brominated resin can give good flame retardancy to materials, it may generate harmful hydrogen halide gas, brominated dioxins, furans, and antimony oxide. Due to its toxicity, both are being controlled.
[0007]
In this way, flame retardant properties can be achieved without using harmful substances such as halogens so that polyphenylene ether resin compositions with little impact on the human body and the environment, prepregs and laminates containing them can be produced. For example, a curable resin composition using melamine polyphosphate has been proposed (see, for example, Patent Document 1).
[0008]
[Patent Document 1]
Japanese Patent Laid-Open No. 2002-129006
[Problems to be solved by the invention]
The present invention provides a resin composition which exhibits good flame retardancy and excellent dielectric properties even without containing harmful substances such as halogens and melamine polyphosphate, and also has excellent heat resistance, moisture resistance and corrosion resistance. The purpose is to provide.
[0010]
Furthermore, the present invention provides a prepreg containing such a resin composition, and a laminate, a copper-clad laminate, and a printed wiring board that are manufactured using these prepregs and are excellent in heat resistance and moisture resistance. Also aimed.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventor uses acid-modified polyphenylene ether as a material having excellent dielectric properties, and by adding a condensed phosphate ester compound thereto, it is excellent in containing no halogen. The inventors have found that a resin composition exhibiting flame retardancy and excellent heat resistance, moisture resistance, and corrosion resistance can be obtained, and the present invention has been completed.
[0012]
That is, the polyphenylene ether resin composition of the present invention comprises (A) a condensed phosphate ester compound, (B) an acid-modified polyphenylene ether compound, (C) triallyl isocyanurate and / or triallyl cyanurate, (D ) Zinc borate, zinc oxide or a mixture thereof as an essential component, and 10 to 50% by weight of (A) condensed phosphate ester compound with respect to [(A) component + (B) component + (C) component]. It is characterized by containing in the ratio.
[0013]
Hereinafter, the present invention will be described in detail.
[0014]
The (A) condensed phosphate ester compound used in the present invention may be a compound having a condensed phosphate ester skeleton, and those having a melting point of 80 ° C. or higher can be suitably used.
[0015]
The condensed phosphate ester compound has the following general formula:

(Wherein n is an integer of 1 to 10).
[0016]
This condensed phosphate ester compound moderately lowers the elastic modulus by appropriately reducing the crosslink density of the resin composition while maintaining the flame retardancy of the resin composition, resulting in stress relaxation that lowers the resin hardness. It functions as an agent to improve solder heat resistance at high temperatures.
[0017]
Further, the blending amount of the (A) condensed phosphate ester compound is characterized in that it is contained in a range of 10 to 50% by weight with respect to [(A) component + (B) component + (C) component]. Is.
[0018]
The acid-modified polyphenylene ether (B) used in the present invention is obtained by modifying polyphenylene ether with an acidic compound, for example, by reacting polyphenylene ether with an unsaturated carboxylic acid and / or acid anhydride. Mention may be made of reaction products.
[0019]
At this time, examples of the polyphenylene ether used as a raw material include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2,6-dimethyl-1) obtained by homopolymerization of 2,6-dimethylphenol. , 4-phenylene ether), styrene graft copolymer, 2,6-dimethylphenol and 2-methyl-6-phenylphenol copolymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol, Copolymer, polyfunctional polyphenylene ether obtained by polymerization in the presence of 2,6-dimethylphenol and a polyfunctional phenol compound, 2,6-dimethylphenol in the presence of a substituted aniline or an aliphatic secondary amine. Examples thereof include nitrogen-containing polyphenylene ether obtained by polymerization.
[0020]
Examples of the unsaturated carboxylic acid include a carboxylic acid or dicarboxylic anhydride having a double bond and at least one carboxyl group, and maleic anhydride, maleic acid, fumaric acid, and itaconic acid are preferable. These can be used individually or in mixture of 2 or more types.
[0021]
Using these as raw materials, for example, an acid-modified polyphenylene ether can be obtained by reacting polyphenylene ether with an unsaturated carboxylic acid in the presence of a solvent or other resin. There is no particular limitation on the modification method at this time, and a known method, for example, a method of melt kneading and reacting at a temperature in the range of 150 to 350 ° C. using a twin screw extruder, a roll mill, etc., benzene, toluene, xylene It can carry out by the method of making it heat-react in solvents, such as.
[0022]
Furthermore, in order to facilitate these reactions, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, azobisisovalero A radical generator such as nitrile or 2,3-diphenyl-2,3-dimethylbutane is preferably present.
[0023]
Here, the blending amount of the (B) acid-modified polyphenylene ether is preferably 10 to 50% by weight with respect to [(A) component + (B) component + (C) component].
[0024]
The (C) triallyl isocyanurate and / or triallyl cyanurate used in the present invention acts as a crosslinking agent for the polyphenylene ether resin, and can be used alone or in combination of two or more. By using nurate and / or triallyl cyanurate, a cured product having excellent dielectric properties and heat resistance can be obtained.
[0025]
The blending amount of (C) triallyl isocyanurate and / or triallyl cyanurate is in the range of 40 to 50% by weight with respect to [(A) component + (B) component + (C) component]. It is preferable to do.
[0026]
In addition, when cross-linking triallyl isocyanurate or triallyl cyanurate to the reaction product of polyphenylene ether and unsaturated carboxylic acid, it is preferable to use a curing accelerator such as a radical initiator. As this radical initiator, the peroxide etc. which are normally used as radical initiators, such as perhexine 25B (Nippon Yushi Co., Ltd. make, brand name), are mentioned, for example.
[0027]
As the component (D) used in the present invention, zinc borate and zinc oxide can be used, and these can be used alone or in combination.
[0028]
With this component (D), the polyphenylene ether resin composition of the present invention can have excellent dielectric properties even without halogen.
[0029]
The blending amount of the (D) inorganic filler is preferably in the range of 5 to 40 parts by weight with respect to 100 parts by weight of [(A) component + (B) component + (C) component]. When the blending amount is less than 5 parts by weight, sufficient flame retardancy, heat resistance, and moisture resistance cannot be obtained, and when it exceeds 40 parts by weight, the adhesion to the metal foil and the solvent fluidity of the composition are poor. It will decline.
[0030]
Furthermore, in addition to these components, thermoplastic resins or thermosetting resins other than the components (B) and (C) can be used alone or in combination.
[0031]
Examples of the thermoplastic resin that can be used here include GPPS (general purpose polystyrene), HIPS (impact polystyrene), polybutadiene, and styrene butadiene block copolymer. Examples of the thermosetting resin include epoxy resins. Etc. These resins can be used alone or in admixture of two or more.
[0032]
The polyphenylene ether resin composition of the present invention described above is diluted with a suitable organic solvent such as toluene to make a varnish, which is applied to a porous glass substrate such as a glass nonwoven fabric or a glass woven fabric, impregnated, A prepreg can be produced by the usual method of heating.
[0033]
Moreover, after superposing a plurality of the prepregs and superposing a copper foil on one or both sides of the laminated structure, the circuit is formed on the glass epoxy copper-clad laminate (inner layer board) by heating and pressing under normal conditions. After forming the copper foil and then etching the copper foil, the prepreg and the copper foil are superposed on at least one surface of the inner layer plate, and this is manufactured by the usual method of heating and pressurizing at 170 ° C. and 4 MPa for 100 minutes, for example. Can do.
[0034]
Furthermore, the printed wiring board can be manufactured by a normal method of forming a predetermined circuit after forming a through hole in a copper-clad laminate or multilayer board and performing through-hole plating.
[0035]
If the glass woven fabric and copper foil used for this invention are normally used for a glass epoxy copper clad laminated board, there will be no restriction | limiting in particular and it can be used.
[0036]
【Example】
Next, the present invention will be described with reference to reference examples and examples.
[0037]
(Reference Example 1)
1 kg of poly (2,6-dimethyl-1,4-phenylene ether), 60 g of maleic anhydride, 10 g of 2,3-dimethyl-2,3-diphenylbutane as a radical generator are dry blended, and a twin screw extruder is used. Then, melt kneading was performed at 300 ° C. At this time, the resin temperature was about 330 ° C. The strand was cooled and pelletized to produce maleic anhydride-modified polyphenylene ether.
[0038]
(Reference Example 2)
Maleic anhydride-modified polyphenylene ether 50 parts by weight, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) 46 parts by weight, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts by weight, PX-200 (Daihachi Chemical Industry Co., Ltd.) 15 parts by weight, FUSELEX E-2 (manufactured by Tatsumori Co., Ltd., trade name, average particle size 7 μm) 15 parts by weight, perhexine 25B (manufactured by NOF Corporation, trade name) 6 parts by weight in toluene A varnish was prepared by dissolving.
The prepared varnish was continuously impregnated onto a glass woven fabric and dried at a temperature of 160 ° C. to produce a prepreg. 8 manufactured prepregs are stacked, 18 μm thick copper foil is overlapped on both sides, and molded integrally at 170 ° C. and pressure 40 kg / cm for 90 minutes by heating and pressing, and glass with a thickness of 1.6 mm An epoxy copper clad laminate was produced.
[0039]
(Reference Example 3)
Maleic anhydride-modified polyphenylene ether 50 parts by weight, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) 46 parts by weight, GPPS (general purpose polystyrene, weight average molecular weight 270,000) 4 parts by weight, PX-207 (Dahachi Chemical Industry Co., Ltd.) 15 parts by weight, FUSELEX E-2 (manufactured by Tatsumori Co., Ltd., trade name, average particle size 7 μm) 15 parts by weight, perhexine 25B (manufactured by NOF Corporation, trade name) 6 parts by weight in toluene A varnish was prepared by dissolving.
A glass epoxy copper clad laminate was produced in the same manner as in Reference Example 2 using the adjusted varnish.
[0040]
Example 1
Maleic anhydride-modified polyphenylene ether 50 parts by weight, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) 46 parts by weight, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts by weight, PX-200 (Daihachi Chemical Industry Co., Ltd.) Product, trade name) 15 parts by weight, zinc borate (manufactured by Borax, trade name: Firebrake ZB, average particle size 2 μm) 15 parts by weight, perhexine 25B (manufactured by NOF Corporation, trade name) 6 parts by weight in toluene A varnish was prepared by dissolving. A glass epoxy copper clad laminate was produced in the same manner as in Reference Example 2 using the adjusted varnish.
[0041]
(Comparative Example 1)
Maleic anhydride-modified polyphenylene ether 50 parts by weight, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) 46 parts by weight, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts by weight, FUSELEX E-2 (manufactured by Tatsumori Co., Ltd.) , Trade name, average particle size 7 μm) 15 parts by weight, perhexine 25B (manufactured by NOF Corporation) 6 parts by weight, antimony trioxide 4 parts by weight, bromine flame retardant SAYTEX 8010 (manufactured by Albemarle Asano, trade name) 20 parts by weight of toluene A varnish was prepared by dissolving in the solution.
A glass epoxy copper clad laminate was produced in the same manner as in Reference Example 2 using the adjusted varnish.
[0042]
(Test Example 1)
For each of the glass epoxy copper clad laminates produced in Reference Examples 2 to 3, Example 1 and Comparative Example 1, tests such as peel strength, flame retardancy, heat resistance and moisture resistance were conducted, and the results are shown. It was shown in 1.
[0043]
[Table 1]

* 1: Measured according to JIS-C-6481.
* 2: Measured according to UL94 flame retardant test.
* 3: A sample was floated on a solder at 260 ° C. for 8 minutes in accordance with JIS-C-6481, and the presence or absence of swelling was observed.
* 4: Measured by the TMA method according to JIS-C-6481.
* 5: Measured according to JIS-C-6481.
[0044]
【The invention's effect】
The polyphenylene ether resin composition of the present invention and prepregs and laminates, copper-clad laminates and printed wiring boards containing this resin composition are characterized in that no harmful substances such as halogens are used as a flame retardant method, It has excellent dielectric properties, heat resistance, moisture resistance, corrosion resistance, etc. without generating hydrogen bromide which is a toxic gas during combustion.

Claims (5)

(A) a condensed phosphate ester compound;
(B) acid-modified polyphenylene ether;
(C) triallyl isocyanurate and / or triallyl cyanurate;
(D) zinc borate as an essential component,
10 to 50% by weight of the (A) condensed phosphate ester compound and 10 to 50% by weight of the (B) acid-modified polyphenylene ether with respect to [(A) component + (B) component + (C) component]. And (C) triallyl isocyanurate and / or triallyl cyanurate in a proportion of 40 to 50% by weight, and [(A) component + (B) component + (C) component] in 100 parts by weight On the other hand, the polyphenylene ether resin composition comprising (D) zinc borate in a range of 5 to 40 parts by weight . A prepreg comprising a glass substrate impregnated with the polyphenylene ether resin composition according to claim 1. A laminate comprising the prepreg according to claim 2, wherein the polyphenylene ether resin composition is cured. A copper-clad laminate comprising a substrate comprising the prepreg according to claim 2, wherein the polyphenylene ether resin composition is cured, and a copper foil bonded to at least one surface of the substrate. A printed wiring board comprising: a substrate comprising the prepreg according to claim 2 wherein the polyphenylene ether resin composition is cured; and a copper foil circuit formed on at least one surface of the substrate.