JP4122320B2 - Halogen-free flame-retardant resin composition, prepreg using the same, and use thereof. - Google Patents
Halogen-free flame-retardant resin composition, prepreg using the same, and use thereof. Download PDFInfo
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Description
本発明は、ハロゲンフリー難燃性樹脂組成物、それを用いたプリプレグ及びその用途に関する。さらに詳しくは、本発明は、難燃化手法としてハロゲン系難燃剤を用いておらず、燃焼時に有毒ガスである臭化水素などを発生させることなく、優れた誘電特性を有すると共に、耐燃性、耐熱性、密着性、耐湿性などに優れるハロゲンフリー難燃性樹脂組成物、及び該難燃性樹脂組成物を用いてなるプリプレグ、フィルム、樹脂付きの金属箔やポリイミドフィルムや液晶ポリマーフィルム、並びにこれらを使用した積層板、銅張積層板、プリント配線板に関するものである。 The present invention relates to a halogen-free flame-retardant resin composition, a prepreg using the same, and its use. More specifically, the present invention does not use a halogen-based flame retardant as a flame retardant method, has excellent dielectric properties without generating hydrogen bromide, which is a toxic gas during combustion, and has flame resistance, Halogen-free flame-retardant resin composition having excellent heat resistance, adhesion, moisture resistance, and the like, and prepregs, films, metal foils with resin, polyimide films, liquid crystal polymer films, and the like, and The present invention relates to a laminated board, a copper clad laminated board, and a printed wiring board using these.
近年、ＬＳＩの高速、高集積化とメモリーの大容量化が進み、それに伴って各種電子部品の小型化、軽量化、薄型化が急速に進んでいる。これに伴い、材料の面でもより優れた耐熱性、寸法安定性、電気特性が要求されている。プリント配線板用には、従来からフェノール樹脂、エポキシ樹脂、ポリイミド樹脂等の熱硬化性樹脂が用いられてきた。これらの樹脂は、各種の性能をバランスよく有しているが、高周波領域での誘電特性が十分でないという欠点をもっていた。この問題を解決する新しい材料として、ポリフェニレンエーテルが注目を浴び、銅張積層板への応用が試みられてる。このような用途に用いられるポリフェニレンエーテルとして、例えば硬化性ポリフェニレンエーテルが開示されている（例えば、特許文献１参照）。
一方、近年、衛星通信などに用いられるＸバンド（８〜１２ＧＨｚ）領域などの超高周波領域で使用される積層板には優れた誘電特性をもつ材料が要求されることから、その材料として主にポリフェニレンエーテルが使用されている。そして難燃化手法として、１，２−ビス（ペンタブロモフェニル）エタンなどの芳香族臭素系難燃剤の単独系と酸化アンチモンとの併用系が採用されてきた。
しかしながら、このような臭素系難燃剤は、主な難燃機構として、ポリマーの熱分解により生成し、気相に拡散したラジカル化合物をトラップして燃焼サイクルを中断し、難燃化を発揮する。このため、臭化水素、一酸化炭素等の有毒ガスが発生する可能性が高い。またダイオキシン、フラン類の発生も懸念される。さらに酸化アンチモンは劇物に指定されており、また発ガン性も懸念されている。そのため使用が抑制されつつある。
In recent years, LSIs have increased in speed, integration, and memory capacity, and accordingly, various electronic components have been rapidly reduced in size, weight, and thickness. Accordingly, more excellent heat resistance, dimensional stability, and electrical characteristics are required in terms of materials. For printed wiring boards, thermosetting resins such as phenol resins, epoxy resins, and polyimide resins have been conventionally used. These resins have various performances in a well-balanced manner, but have the disadvantage that the dielectric properties in the high frequency region are not sufficient. As a new material for solving this problem, polyphenylene ether has attracted attention, and its application to copper-clad laminates has been attempted. For example, curable polyphenylene ether is disclosed as a polyphenylene ether used for such applications (see, for example, Patent Document 1).
On the other hand, in recent years, materials having excellent dielectric properties are required for laminates used in the ultra-high frequency region such as the X band (8 to 12 GHz) region used for satellite communications and the like. Polyphenylene ether is used. As a flame retardant technique, a single system of an aromatic bromine-based flame retardant such as 1,2-bis (pentabromophenyl) ethane and a combined system of antimony oxide have been adopted.
However, such a brominated flame retardant exhibits flame retardancy as a main flame retardant mechanism by trapping a radical compound produced by thermal decomposition of a polymer and diffusing into the gas phase to interrupt the combustion cycle. For this reason, there is a high possibility that toxic gases such as hydrogen bromide and carbon monoxide are generated. There are also concerns about the generation of dioxins and furans. Furthermore, antimony oxide has been designated as a deleterious substance, and carcinogenicity is a concern. Therefore, use is being suppressed.
本発明は、このような状況下で、難燃化手法として、燃焼時に有毒ガスである臭化水素などを発生させる難燃剤を用いることなく、優れた誘電特性を有すると共に、耐燃性、耐熱性、密着性、耐湿性などに優れるハロゲンフリー難燃性樹脂組成物、及び該難燃性樹脂組成物を用いてなるプリプレグ、フィルム、樹脂付きの金属箔やポリイミドフィルムや液晶ポリマーフィルム、並びにこれらを使用した積層板、銅張積層板、プリント配線板を提供することを目的とするものである。 Under such circumstances, the present invention has excellent dielectric properties, flame resistance, and heat resistance without using a flame retardant that generates toxic gas such as hydrogen bromide as a flame retardant method. , Halogen-free flame retardant resin composition having excellent adhesion, moisture resistance, and the like, and prepregs, films, metal foils with resin, polyimide films, liquid crystal polymer films, and the like using these flame retardant resin compositions, and An object of the present invention is to provide a used laminated board, a copper clad laminated board, and a printed wiring board.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、架橋性官能基を有する変性ポリフェニレンエーテル系樹脂と架橋剤を含むと共に、難燃剤として、ある種のリン系化合物とホウ酸亜鉛をそれぞれ特定の割合で含むハロゲンフリー難燃性樹脂組成物により、その目的を達成し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。
すなわち、本発明は、
（１）（Ａ）ポリフェニレンエーテルと不飽和カルボン酸及び／又は酸無水物との反応生成物、並びにアリル化ポリフェニレンエーテルの中から選ばれる少なくとも一種の架橋性官能基を有する変性ポリフェニレンエーテル系樹脂、及び（Ｂ）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である架橋剤を含むと共に、前記（Ａ）成分と（Ｂ）成分との合計量１００質量部に対し、（Ｃ）下記一般式（Ｉ）
（２）（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｄ）成分それぞれのハロゲン含有量が、ハロゲン原子として０．１質量％以下である上記（１）項に記載のハロゲンフリー難燃性樹脂組成物、
As a result of intensive studies to achieve the above object, the inventors of the present invention include a modified polyphenylene ether resin having a crosslinkable functional group and a crosslinking agent, and as a flame retardant, a certain phosphorus compound and boron. It has been found that the object can be achieved by a halogen-free flame retardant resin composition containing zinc acid in a specific ratio. The present invention has been completed based on such findings.
That is, the present invention
(1) (A) a modified polyphenylene ether resin having at least one crosslinkable functional group selected from the reaction product of polyphenylene ether and unsaturated carboxylic acid and / or acid anhydride, and allylated polyphenylene ether ; And (B) a cross-linking agent that is triallyl isocyanurate and / or triallyl cyanurate, and (C) the following general formula (100) with respect to 100 parts by mass of the total amount of component (A) and component (B): I)
(2) Halogen-free as described in the above item (1), wherein the halogen content of each of the components (A), (B), (C) and (D) is 0.1% by mass or less as a halogen atom Flame retardant resin composition,
（３）（Ｄ）成分のホウ酸亜鉛が、ＺｎＯとＢ2Ｏ3を含有する上記（１）または（２）項のいずれかに記載のハロゲンフリー難燃性樹脂組成物、
（４）上記（１）ないし（３）項のいずれかに記載のハロゲンフリー難燃性樹脂組成物をガラス繊維基材に含浸させてなるプリプレグ、
( 3 ) The halogen-free flame retardant resin composition according to any one of (1) or ( 2 ) above, wherein the zinc borate of component (D) contains ZnO and B 2 O 3 ,
( 4 ) A prepreg obtained by impregnating a glass fiber substrate with the halogen-free flame-retardant resin composition according to any one of (1) to ( 3 ) above,
（５）上記（１）ないし（３）項のいずれかに記載のハロゲンフリー難燃性樹脂組成物を有機繊維基材に含浸させてなるプリプレグ、 ( 5 ) A prepreg obtained by impregnating an organic fiber base material with the halogen-free flame-retardant resin composition according to any one of (1) to ( 3 ) above,
（６）上記（４）又は（５）項に記載のプリプレグを加熱処理し、ハロゲンフリー難燃性樹脂組成物を硬化させてなる基板、
（７）上記（４）又は（５）項に記載のプリプレグを複数枚重ね合わせて加圧加熱処理し、ハロゲンフリー難燃性樹脂組成物を硬化させて一体化してなる積層板、
（８）上記（６）項に記載の基板又は上記（７）項に記載の積層板の少なくとも片面に銅箔を接合してなる銅張積層板、
（９）上記（１）ないし（３）項のいずれかに記載のハロゲンフリー難燃性樹脂組成物からなるフィルム、
（１０）上記（１）ないし（３）項のいずれかに記載のハロゲンフリー難燃性樹脂組成物からなる未硬化膜が金属箔の片面に形成されてなる樹脂付き金属箔、
（１１）上記（１）ないし（３）項のいずれかに記載のハロゲンフリー難燃性樹脂組成物からなる未硬化膜がポリイミドフィルムの片面に形成されてなる樹脂付きポリイミドフィルム、
（１２）上記（１）ないし（３）項のいずれかに記載のハロゲンフリー難燃性樹脂組成物からなる未硬化膜が液晶ポリマーフィルムの片面に形成されてなる樹脂付き液晶ポリマーフィルム、及び
（１３）上記（８）項に記載の銅張積層板を用いて得られたことを特徴とするプリント配線板、
を提供するものである。
( 6 ) A substrate obtained by heat-treating the prepreg according to ( 4 ) or ( 5 ) above and curing the halogen-free flame-retardant resin composition,
( 7 ) A laminate comprising a plurality of the prepregs according to the above ( 4 ) or ( 5 ) which are laminated and subjected to pressure and heat treatment, and the halogen-free flame retardant resin composition is cured and integrated,
( 8 ) A copper-clad laminate obtained by bonding a copper foil to at least one surface of the substrate described in ( 6 ) or the laminate described in ( 7 ),
( 9 ) A film comprising the halogen-free flame-retardant resin composition according to any one of (1) to ( 3 ) above,
( 10 ) A resin-coated metal foil in which an uncured film made of the halogen-free flame-retardant resin composition according to any one of (1) to ( 3 ) is formed on one side of a metal foil,
( 11 ) A polyimide film with a resin, wherein an uncured film made of the halogen-free flame-retardant resin composition according to any one of (1) to ( 3 ) above is formed on one side of a polyimide film,
( 12 ) A resin-attached liquid crystal polymer film in which an uncured film comprising the halogen-free flame-retardant resin composition according to any one of (1) to ( 3 ) above is formed on one side of a liquid crystal polymer film, and ( 13 ) A printed wiring board obtained by using the copper-clad laminate as described in ( 8 ) above,
Is to provide.
本発明によれば、難燃化手法としてハロゲン系難燃剤を用いておらず、燃焼時に有毒ガスである臭化水素などを発生させることなく、優れた誘電特性を有すると共に、耐燃性、耐熱性、密着性、耐湿性などに優れるハロゲンフリー難燃性樹脂組成物を提供することができる。さらに前記難燃性樹脂組成物を用いてなるプリプレグ、フィルム、樹脂付きの金属箔やポリイミドフィルムや液晶ポリマーフィルム、並びにこれらを使用した積層板、銅張積層板、プリント配線板を提供することができる。 According to the present invention, a halogen-based flame retardant is not used as a flame retardant method, and it has excellent dielectric properties without generating hydrogen bromide, which is a toxic gas during combustion, and has flame resistance and heat resistance. In addition, it is possible to provide a halogen-free flame retardant resin composition having excellent adhesion, moisture resistance, and the like. Furthermore, it is possible to provide a prepreg, a film, a resin-attached metal foil, a polyimide film, a liquid crystal polymer film, a laminate using the same, a copper-clad laminate, and a printed wiring board using the flame retardant resin composition. it can.
本発明のハロゲンフリー難燃性樹脂組成物（以下、単に樹脂組成物と称すことがある。）は、（Ａ）変性ポリフェニレンエーテル系樹脂、（Ｂ）架橋剤、（Ｃ）９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体及び（Ｄ）ホウ酸亜鉛を含む樹脂組成物である。
本発明の樹脂組成物における（Ａ）成分の変性ポリフェニレンエーテル系樹脂は、架橋性官能基を有しており、このような変性ポリフェニレンエーテル系樹脂としては、（１）ポリフェニレンエーテルと不飽和カルボン酸及び／又は酸無水物との反応生成物、あるいは（２）アリル化ポリフェニレンエーテルを好ましく用いることができる。
前記（１）のポリフェニレンエーテルと不飽和カルボン酸及び／又は酸無水物との反応生成物において、原料として用いられ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−フェニルフェニレンエーテルの共重合体、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などが挙げられる。
また、もう一つの原料である不飽和カルボン酸や酸無水物は、二重結合と少なくとも１個のカルボン酸もしくはジカルボン酸無水物基とを分子構造内にもつ化合物であり、このようなものとしては、例えば無水マレイン酸、マレイン酸、フマル酸、イタコン酸などが挙げられる。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
前記のポリフェニレンエーテルの不飽和カルボン酸及び／又は酸無水物による変性反応方法については特に制限はなく、従来公知の方法を用いることができる。
The halogen-free flame-retardant resin composition of the present invention (hereinafter sometimes simply referred to as a resin composition) includes (A) a modified polyphenylene ether resin, (B) a crosslinking agent, and (C) 9,10-dihydro. A resin composition comprising a -9-oxa-10-phosphaphenanthrene-10-oxide derivative and (D) zinc borate.
The modified polyphenylene ether resin of component (A) in the resin composition of the present invention has a crosslinkable functional group. Examples of such modified polyphenylene ether resin include (1) polyphenylene ether and unsaturated carboxylic acid. And / or a reaction product with an acid anhydride, or (2) allylated polyphenylene ether can be preferably used.
In the reaction product of the polyphenylene ether (1) and the unsaturated carboxylic acid and / or acid anhydride, the polyphenylene ether used as a raw material may be, for example, poly (6) obtained by homopolymerization of 2,6-dimethylphenol. 2,6-dimethyl-1,4-phenylene ether), poly (2,6-dimethyl-1,4-phenylene ether) styrene graft copolymer, 2,6-dimethylphenol and 2-methyl-6-phenyl Phenylene ether copolymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol copolymer, polyfunctionality obtained by polymerization in the presence of 2,6-dimethylphenol and polyfunctional phenol compound Polymerization of polyphenylene ether and 2,6-dimethylphenol in the presence of substituted anilines and aliphatic secondary amines And nitrogen-containing polyphenylene ethers obtained Te are exemplified.
Another raw material, unsaturated carboxylic acid or acid anhydride, is a compound having a double bond and at least one carboxylic acid or dicarboxylic acid anhydride group in its molecular structure. Examples include maleic anhydride, maleic acid, fumaric acid, and itaconic acid. These may be used individually by 1 type, and may be used in combination of 2 or more types.
There is no restriction | limiting in particular about the modification reaction method by the unsaturated carboxylic acid and / or acid anhydride of the said polyphenylene ether, A conventionally well-known method can be used.
一方、前記（２）のアリル化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と２−アリル−６−メチルフェノールの共重合体、特公平５−８９３１号公報記載のｎ−ブチルリチウムと臭化アリルを用いた方法などにより合成したもの等が挙げられる。
本発明においては、（Ａ）成分として、前記（１）のポリフェニレンエーテルと不飽和カルボン酸及び／又は酸無水物との反応生成物を一種用いてもよいし、二種以上組み合わせて用いてもよく、また、前記（２）のアリル化ポリフェニレンエーテルを一種用いてもよいし、二種以上組み合わせて用いてもよい。あるいは前記（１）のポリフェニレンエーテルと不飽和カルボン酸及び／又は酸無水物との反応生成物一種以上と、前記（２）のアリル化ポリフェニレンエーテル一種以上とを組み合わせて用いてもよい。
On the other hand, as the allylated polyphenylene ether of (2), for example, a copolymer of 2,6-dimethylphenol and 2-allyl-6-methylphenol, n-butyllithium described in JP-B-5-8931 and odor And those synthesized by a method using allyl chloride.
In the present invention, as the component (A), the reaction product of the polyphenylene ether of the above (1) and an unsaturated carboxylic acid and / or acid anhydride may be used singly or in combination of two or more. Moreover, one kind of the allylated polyphenylene ether of the above (2) may be used, or two or more kinds may be used in combination. Alternatively, one or more reaction products of the polyphenylene ether (1) and unsaturated carboxylic acid and / or acid anhydride may be used in combination with one or more allylated polyphenylene ethers (2).
本発明の樹脂組成物における（Ｂ）成分の架橋剤としては、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が好ましく用いられる。このトリアリルイソシアヌレートやトリアリルシアヌレートを用いることにより、誘電特性並びに耐燃性、耐熱性、密着性、耐湿性、耐薬品性、信頼性等に優れた硬化物を得ることができる。
当該（Ｂ）成分の配合量は、前記（Ａ）成分と（Ｂ）成分との合計量に対し、通常１０〜７０質量％の範囲で選定される。この（Ｂ）成分の配合量が上記の範囲にあれば、前記の特性を有する硬化物を得ることができる。好ましい配合量は２５〜６０質量％であり、特に３５〜５５質量％が好ましい。
As the crosslinking agent of the component (B) in the resin composition of the present invention, triallyl isocyanurate and / or triallyl cyanurate are preferably used. By using this triallyl isocyanurate or triallyl cyanurate, a cured product having excellent dielectric properties and flame resistance, heat resistance, adhesion, moisture resistance, chemical resistance, reliability and the like can be obtained.
The blending amount of the component (B) is usually selected in the range of 10 to 70% by mass with respect to the total amount of the component (A) and the component (B). If the blending amount of the component (B) is in the above range, a cured product having the above characteristics can be obtained. A preferable compounding amount is 25 to 60% by mass, and particularly preferably 35 to 55% by mass.
本発明の樹脂組成物における（Ｃ）成分の９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体としては、一般式（Ｉ） As the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative of the component (C) in the resin composition of the present invention, the general formula (I)
（式中、Ｒ1及びＲ2は、それぞれ独立にハロゲン原子を含まない有機基、Ｒ3は水素原子又はハロゲン原子を含まない有機基、ａ及びｂは、それぞれ０〜４の整数を示す。）
で表される化合物を用いることができる。
前記一般式（Ｉ）において、Ｒ1、Ｒ2で示されるハロゲン原子を含まない有機基としては、例えば炭素数１〜４のアルキル基やアルコキシル基などを挙げることができる。また、Ｒ3のうちのハロゲン原子を含まない有機基としては特に制限はないが、例えば（メタ）アクリロイルオキシ基、アリル基、スチリル基などを好ましく挙げることができる。
前記一般式（Ｉ）で表される９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体の具体例としては、特に、得られる硬化物の誘電特性及び耐燃性、耐熱性、密着性、耐湿性などの観点から、以下に示す式（ａ）、（ｂ）、（ｃ）、（ｄ）及び（ｅ）で表される化合物を挙げることができる。
(In the formula, R 1 and R 2 are each independently an organic group not containing a halogen atom, R 3 is an organic group not containing a hydrogen atom or a halogen atom, and a and b each represent an integer of 0 to 4. )
The compound represented by these can be used.
In the said general formula (I), as an organic group which does not contain the halogen atom shown by R < 1 >, R < 2 >, a C1-C4 alkyl group, an alkoxyl group, etc. can be mentioned, for example. Although there is no particular restriction on the organic group containing no halogen atom of R 3, for example, (meth) acryloyloxy group, an allyl group, and preferably a styryl group.
Specific examples of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative represented by the general formula (I) include, in particular, dielectric properties, flame resistance, and heat resistance of the obtained cured product. From the viewpoints of properties, adhesion, moisture resistance, etc., compounds represented by the following formulas (a), (b), (c), (d) and (e) can be mentioned.
（式中、Ｒ1、Ｒ2、ａ及びｂは、前記と同じである。）
本発明においては、この（Ｃ）成分の９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、その配合量は、前記（Ａ）成分と（Ｂ）成分との合計量１００質量部に対し、３〜６５質量部の範囲で選定される。この配合量が上記範囲にあれば、得られる硬化物は、良好な誘電特性、耐燃性、耐熱性、密着性、耐湿性などを発揮することができる。好ましい配合量は５〜４０質量部であり、特に１０〜３５質量部が好適である。
(In the formula, R 1 , R 2 , a and b are the same as described above.)
In the present invention, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative of the component (C) may be used alone or in combination of two or more. Also good. Moreover, the compounding quantity is selected in the range of 3-65 mass parts with respect to 100 mass parts of total amounts of the said (A) component and (B) component. If this blending amount is in the above range, the resulting cured product can exhibit good dielectric properties, flame resistance, heat resistance, adhesion, moisture resistance, and the like. A preferable compounding amount is 5 to 40 parts by mass, and 10 to 35 parts by mass is particularly preferable.
本発明の樹脂組成物における（Ｄ）成分のホウ酸亜鉛としては、特に組成物における分散性、安定性、及び得られる硬化物の誘電特性、耐燃性、耐熱性、密着性、耐湿性などの観点から、ＺｎＯ、Ｂ2Ｏ3及びＨ2Ｏを含有し、平均粒径が０．１〜１０μｍであって、最大粒径が３０μｍ以下の形状のものが好適である。この（Ｄ）成分の配合量は、前記（Ａ）成分と（Ｂ）成分との合計量１００質量部に対し、５〜３００質量部の範囲で選定される。この配合量が上記の範囲にあれば、得られる硬化物は、良好な誘電特性、耐燃性、耐熱性、密着性、耐湿性などを発揮することができる。好ましい配合量は５〜１００質量部であり、特に５〜５０質量部が好適である。
本発明の樹脂組成物には、硬化させる際に、前記（Ａ）成分と（Ｂ）成分の架橋反応を促進させるために、反応促進剤を含有させることができる。この反応促進剤としては、例えば有機過酸化物などのラジカル開始剤を用いることができる。
本発明の樹脂組成物においては、前記の（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）の各成分として、ノンハロゲン化合物であって、ハロゲン含有量が、ハロゲン原子として０．１質量％以下のものが用いられる。
As the zinc borate as the component (D) in the resin composition of the present invention, dispersibility and stability in the composition, and dielectric properties, flame resistance, heat resistance, adhesion, moisture resistance, and the like of the resulting cured product are particularly high. From the viewpoint, a material containing ZnO, B 2 O 3 and H 2 O, having an average particle size of 0.1 to 10 μm and a maximum particle size of 30 μm or less is preferable. The blending amount of the component (D) is selected in the range of 5 to 300 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). If this blending amount is within the above range, the resulting cured product can exhibit good dielectric properties, flame resistance, heat resistance, adhesion, moisture resistance, and the like. A preferable compounding amount is 5 to 100 parts by mass, and 5 to 50 parts by mass is particularly preferable.
The resin composition of the present invention can contain a reaction accelerator in order to accelerate the crosslinking reaction between the component (A) and the component (B) when cured. As the reaction accelerator, for example, a radical initiator such as an organic peroxide can be used.
In the resin composition of the present invention, the components (A), (B), (C) and (D) are non-halogen compounds, and the halogen content is 0.1% by mass as a halogen atom. The following are used.
本発明の樹脂組成物には、本発明の目的が損なわれない範囲で、必要に応じ、他のハロゲンを含有しない難燃剤、充填剤、前記（Ａ）成分及び（Ｂ）成分以外の熱可塑性樹脂又は熱硬化性樹脂などを含有させることができる。
前記ハロゲンを含有しない難燃剤としては特に制限はなく、例えばリン酸メラミン、ポリリン酸メラム、ポリリン酸メレム、ピロリン酸メラミン、ポリリン酸アンモニウム、赤燐、芳香族リン酸エステル、ホスホン酸エステル、ホスフィン酸エステル、ホスフィンオキサイド、ホスファゼン、メラミンシアノレート等が挙げられる。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。これらの中で、特に誘電特性、耐燃性、耐熱性、密着性、耐湿性、耐薬品性、信頼性等の観点からピロリン酸メラミン、ポリリン酸メラミン、ポリリン酸メラム、ポリリン酸アンモニウムを好ましく使用できる。これらの難燃剤の配合量は、前記（Ａ）成分と（Ｂ）成分との合計量１００質量部に対し、２０質量部以下が好ましい。２０質量部を超えると、誘電特性、耐熱性、密着性、耐湿性などが低下する傾向がみられる。
前記充填剤としては特に制限はなく、例えばタルク、溶融シリカ、合成シリカ、アルミナ、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、酸化亜鉛、低融点ガラス、酸化チタン、カーボンブラック等が挙げられる。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、その配合量は、前記（Ａ）成分と（Ｂ）成分との合計量１００質量部に対し、８０質量部以下が好ましい。８０質量部を超えると、金属箔との密着性や、組成物の溶融流動性が低下する原因となる。
前記熱可塑性樹脂の例としては、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などがあり、熱硬化性樹脂の例としてはエポキシ樹脂などがある。これらの樹脂は単独もしくは二種以上混合して用いることができる。
In the resin composition of the present invention, as long as the object of the present invention is not impaired, if necessary, other flame retardants not containing halogen, fillers, thermoplastics other than the components (A) and (B) Resin or thermosetting resin can be contained.
The halogen-free flame retardant is not particularly limited. For example, melamine phosphate, melam polyphosphate, melem polyphosphate, melamine pyrophosphate, ammonium polyphosphate, red phosphorus, aromatic phosphate ester, phosphonate ester, phosphinic acid Examples thereof include esters, phosphine oxides, phosphazenes, and melamine cyanolates. These may be used individually by 1 type, and may be used in combination of 2 or more types. Of these, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, and ammonium polyphosphate can be preferably used from the viewpoints of dielectric properties, flame resistance, heat resistance, adhesion, moisture resistance, chemical resistance, reliability, etc. . As for the compounding quantity of these flame retardants, 20 mass parts or less are preferable with respect to 100 mass parts of total amounts of the said (A) component and (B) component. If it exceeds 20 parts by mass, the dielectric properties, heat resistance, adhesion, moisture resistance and the like tend to be reduced.
The filler is not particularly limited, and examples thereof include talc, fused silica, synthetic silica, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, zinc oxide, low-melting glass, titanium oxide, and carbon black. These may be used individually by 1 type, and may be used in combination of 2 or more types. Moreover, the compounding quantity has preferable 80 mass parts or less with respect to 100 mass parts of total amounts of the said (A) component and (B) component. When it exceeds 80 mass parts, it will cause the adhesiveness with metal foil, and the melt fluidity of a composition to fall.
Examples of the thermoplastic resin include GPPS (general purpose polystyrene), HIPS (impact polystyrene), polybutadiene, and styrene butadiene block copolymer. Examples of the thermosetting resin include an epoxy resin. These resins can be used alone or in combination of two or more.
本発明のハロゲンフリー難燃性樹脂組成物は、以下のようにして本発明のプリプレグを作製することができる。当該樹脂組成物を、トルエンなどの適当な有機溶剤で希釈してワニスとなし、これをガラス不織布、ガラス織布等のガラス繊維基材や、有機不織布、有機織布等の有機繊維基材に塗布、含浸させ、加熱するという通常の方法により、本発明のプリプレグを製造することができる。
このようにして得られたプリプレグを加熱処理して、当該樹脂組成物を硬化させることにより、本発明の基板を作製することができ、また、前記プリプレグを複数枚重ね合わせて、通常の条件で加圧加熱処理し、当該樹脂組成物を硬化させて一体化することにより、本発明の積層板を作製することができる。この際、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のち、通常の条件で加圧加熱処理することにより、本発明の銅張積層板を作製することができる。
多層板は、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１９５℃、４ＭＰａの圧力で１２０分間加圧加熱処理するという通常の方法により製造することができる。さらに本発明のプリント配線板は、銅張積層板もしく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。
The halogen-free flame-retardant resin composition of the present invention can produce the prepreg of the present invention as follows. The resin composition is diluted with a suitable organic solvent such as toluene to form a varnish, which is used as a glass fiber substrate such as a glass nonwoven fabric or glass woven fabric, or an organic fiber substrate such as organic nonwoven fabric or organic woven fabric. The prepreg of the present invention can be produced by a usual method of coating, impregnating and heating.
The substrate of the present invention can be produced by heat-treating the prepreg thus obtained and curing the resin composition, and a plurality of the prepregs can be overlaid under normal conditions. The laminated board of this invention can be produced by carrying out a pressurization heat process, hardening the said resin composition, and integrating. At this time, a plurality of prepregs are overlaid, and copper foil is overlaid on one or both sides of the laminated structure, followed by pressure and heat treatment under normal conditions to produce the copper-clad laminate of the present invention. it can.
A multilayer board forms a circuit on a copper clad laminate (inner layer board), and then etches the copper foil, and then superimposes a prepreg and a copper foil on at least one side of the inner layer board, for example, at a pressure of 195 ° C. and 4 MPa. Can be produced by the usual method of pressurizing and heating for 120 minutes. Furthermore, the printed wiring board of the present invention can be produced by a usual method of forming a predetermined circuit after forming a through hole in a copper-clad laminate or multilayer board and performing through-hole plating.
本発明はまた、前記のハロゲンフリー難燃性樹脂組成物からなるフィルム、並びに当該樹脂組成物からなる未硬化膜が、金属箔の片面に形成されてなる樹脂付き金属箔、前記未硬化膜がポリイミドフィルムの片面に形成されてなる樹脂付きポリイミドフィルム及び前記未硬化膜が液晶ポリマーフィルムの片面に形成されてなる樹脂付き液晶ポリマーフィルムをも提供する。これらのフィルム、樹脂付き金属箔、樹脂付きポリイミドフィルム及び樹脂付き液晶ポリマーフィルムは、通常の方法により作製することができる。
前記のガラス不織布、ガラス織布、有機不織布、有機織布、銅箔は、通常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。また、前記ポリイミドフィルム、液晶ポリマーフィルムについても特に制限はなく、使用することができる。
The present invention also provides a film made of the halogen-free flame retardant resin composition, a metal foil with a resin in which an uncured film made of the resin composition is formed on one side of the metal foil, and the uncured film A polyimide film with resin formed on one side of a polyimide film and a liquid crystal polymer film with resin formed by forming the uncured film on one side of a liquid crystal polymer film are also provided. These films, metal foils with resin, polyimide films with resin, and liquid crystal polymer films with resin can be produced by ordinary methods.
The glass nonwoven fabric, glass woven fabric, organic nonwoven fabric, organic woven fabric, and copper foil are not particularly limited as long as they are usually used for epoxy copper clad laminates. Moreover, there is no restriction | limiting in particular also about the said polyimide film and a liquid crystal polymer film, It can use.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例で得られた銅張積層板の諸特性を以下に示す要領に従って求めた。
（１）耐燃性
ＵＬ−９４難燃性試験に準じて測定する。
（２）ガラス転移温度
ＴＭＡ法により測定する。
（３）誘電率、誘電正接
インピーダンスアナライザー法により測定する。
（４）耐熱性
２８８℃のハンダに３分間浸漬した後の膨れの発生の有無により評価する。
○：膨れなし
×：膨れあり
（５）耐ミーズリング性
１２１℃、０.２ＭＰａ、５時間のプレッシャークッカーテスト後、２６０℃のハンダ浴に３０秒間浸漬した後のミーズリングの発生の有無により評価する。
○：ミーズリングの発生なし
×：ミーズリングの発生あり
（６）ハロゲン含有量
ハロゲンフリー規格のＪＰＣＡ−ＥＳ−０１に準じて測定する。
○：合格
×：不合格
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the various characteristics of the copper clad laminated board obtained in each example were calculated | required according to the point shown below.
(1) Flame resistance Measured according to UL-94 flame resistance test.
(2) Glass transition temperature It is measured by the TMA method.
(3) Dielectric constant, dielectric loss tangent Measured by impedance analyzer method.
(4) Heat resistance Evaluation is based on the presence or absence of blistering after being immersed in 288 ° C solder for 3 minutes.
○: No blistering ×: Blistering (5) Mesling resistance 121 ° C., 0.2 MPa, after 5 hours pressure cooker test, evaluated by presence / absence of measling after immersion in a solder bath at 260 ° C. for 30 seconds To do.
○: No occurrence of measling ×: Occurrence of measling (6) Halogen content Measured according to halogen-free standard JPCA-ES-01.
○: Pass ×: Fail
実施例１
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体［式（ａ）］（ａ＝０、ｂ＝０）２０質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）４０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Example 1
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (Nihon Kasei Co., Ltd.), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative [formula (a)] (a = 0, b = 0) 20 parts by mass, 40 parts by mass of zinc borate "ZB-XF" (manufactured by BORAX) and 6 parts by mass of organic peroxide "Perhex 25B" (manufactured by NOF Corporation) in toluene or A varnish was prepared by dispersing.
実施例２
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体［式（ｂ）］（ａ＝０、ｂ＝０）２０質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）４０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Example 2
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (Nihon Kasei Co., Ltd.), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative [formula (b)] (a = 0, b = 0) 20 parts by mass, 40 parts by mass of zinc borate "ZB-XF" (manufactured by BORAX) and 6 parts by mass of organic peroxide "Perhex 25B" (manufactured by NOF Corporation) in toluene or A varnish was prepared by dispersing.
実施例３
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体［式（ｃ）］（ａ＝０、ｂ＝０）２０質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）４０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Example 3
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative [formula (c)] (a = 0, b = 0) 20 parts by mass, 40 parts by mass of zinc borate "ZB-XF" (manufactured by BORAX) and 6 parts by mass of organic peroxide "Perhex 25B" (manufactured by NOF Corporation) in toluene or A varnish was prepared by dispersing.
実施例４
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体［式（ｄ）］（ａ＝０、ｂ＝０）２０質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）４０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Example 4
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (Nihon Kasei Co., Ltd.), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative [formula (d)] (a = 0, b = 0) 20 parts by mass, 40 parts by mass of zinc borate "ZB-XF" (manufactured by BORAX) and 6 parts by mass of organic peroxide "Perhex 25B" (manufactured by NOF Corporation) in toluene or A varnish was prepared by dispersing.
実施例５
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体［式（ｄ）］（ａ＝０、ｂ＝０）２２質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）４０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Example 5
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (Nihon Kasei Co., Ltd.), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative [formula (d)] (a = 0, b = 0) 22 parts by mass, 40 parts by mass of zinc borate “ZB-XF” (manufactured by BORAX) and 6 parts by mass of organic peroxide “Perhex 25B” (manufactured by NOF Corporation) in toluene or A varnish was prepared by dispersing.
実施例６
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体［式（ｅ）］（ａ＝０、ｂ＝０）１５質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）３８質量部、ポリリン酸アンモニウム「ＥｘｏｌｉｔＡＰ４２２」（Ｃｌａｒｉａｎｔ社製）７質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Example 6
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative [formula (e)] (a = 0, b = 0) 15 parts by mass, 38 parts by mass of zinc borate “ZB-XF” (manufactured by BORAX), 7 parts by mass of ammonium polyphosphate “ExolitAP422” (manufactured by Clariant) and organic peroxide “Perhex 25B A varnish was prepared by dissolving or dispersing 6 parts by mass (manufactured by NOF Corporation) in toluene.
実施例７
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体［式（ｄ）］（ａ＝０、ｂ＝０）１９質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）２５質量部、水酸化マグネシウム「ＳＮ−Ｅ」（ティーエムジー社製）２０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Example 7
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (Nihon Kasei Co., Ltd.), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative [formula (d)] (a = 0, b = 0) 19 parts by mass, zinc borate “ZB-XF” (manufactured by BORAX), 20 parts by mass of magnesium hydroxide “SN-E” (manufactured by TMG) and organic peroxide A varnish was prepared by dissolving or dispersing 6 parts by mass of “Perhex 25B” (manufactured by NOF Corporation) in toluene.
実施例８
アリル化ポリフェニレンエーテル５２質量部、ＧＰＰＳ（汎用ポリスチレン、旭化成社製、重量平均分子量２７万）６質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体［式（ｄ）］（ａ＝０、ｂ＝０）２２質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）４０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Example 8
52 parts by mass of allylated polyphenylene ether, 6 parts by mass of GPPS (general-purpose polystyrene, manufactured by Asahi Kasei Co., Ltd., weight average molecular weight 270,000), 48 parts by mass of triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.), 9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide derivative [formula (d)] (a = 0, b = 0) 22 parts by mass, zinc borate “ZB-XF” (manufactured by BORAX), 40 parts by mass and organic peroxide A varnish was prepared by dissolving or dispersing 6 parts by mass of “Perhex 25B” (manufactured by NOF Corporation) in toluene.
比較例１
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド誘導体［式（ａ）］（ａ＝０、ｂ＝０）３０質量部、及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Comparative Example 1
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (Nihon Kasei Co., Ltd.), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative [formula (a)] (a = 0, b = 0) 30 parts by mass and 6 parts by mass of an organic peroxide “Perhex 25B” (manufactured by NOF Corporation) were dissolved or dispersed in toluene to prepare a varnish.
比較例２
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）６０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Comparative Example 2
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (Nippon Kasei Co., Ltd.), 60 parts by mass of zinc borate “ZB-XF” (manufactured by BORAX) and organic peroxide “Perhex 25B” (Nippon Yushi) A varnish was prepared by dissolving or dispersing 6 parts by mass in toluene.
比較例３
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、芳香族縮合リン酸エステル「ＰＸ−２００」（大八化学社製）３０質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）４０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Comparative Example 3
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (made by Nippon Kasei Co., Ltd.), 30 parts by mass of aromatic condensed phosphate “PX-200” (made by Daihachi Chemical Co., Ltd.), zinc borate “ZB-” A varnish was prepared by dissolving or dispersing 40 parts by mass of “XF” (manufactured by BORAX) and 6 parts by mass of an organic peroxide “Perhexi 25B” (manufactured by NOF Corporation) in toluene.
比較例４
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、ホスファゼン系難燃剤「ＳＰ−１００」（大塚化学社製）３０質量部、ホウ酸亜鉛「ＺＢ−ＸＦ」（ＢＯＲＡＸ社製）４０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Comparative Example 4
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.), 30 parts by mass of phosphazene flame retardant “SP-100” (manufactured by Otsuka Chemical), zinc borate “ZB-XF” ( A varnish was prepared by dissolving or dispersing 40 parts by mass of BORAX) and 6 parts by mass of an organic peroxide “Perhexi 25B” (manufactured by NOF Corporation) in toluene.
比較例５
アリル化ポリフェニレンエーテル５２質量部、トリアリルイソシアヌレート（日本化成社製）４８質量部、破砕シリカ「ＦＵＳＥＬＥＸ Ｅ−２」（龍森社製、平均粒径７μｍ）１５質量部、三酸化アンチモン４質量部、臭素系難燃剤「ＳＡＹＴＥＸ８０１０」（アルベマール浅野社製）２０質量部及び有機過酸化物「パーヘキシ２５Ｂ」（日本油脂社製）６質量部をトルエンに溶解又は分散させてワニスを調製した。
Comparative Example 5
52 parts by mass of allylated polyphenylene ether, 48 parts by mass of triallyl isocyanurate (Nihon Kasei Co., Ltd.), 15 parts by mass of crushed silica “FUSELEX E-2” (manufactured by Tatsumori Co., Ltd., average particle size 7 μm), 4 parts by mass of antimony trioxide A varnish was prepared by dissolving or dispersing 20 parts by mass of a bromine-based flame retardant “SAYTEX 8010” (manufactured by Albemarle Asano) and 6 parts by mass of an organic peroxide “Perhex 25B” (manufactured by NOF Corporation) in toluene.
試験例１
実施例１〜８、比較例１〜５で得られたポリフェニレンエーテル樹脂ワニスのそれぞれを１００μｍガラス織布に含浸・塗布・乾燥することにより樹脂含有量５０質量％のプリプレグを得た。
こうして得られた１００μｍプリプレグ８枚を重ね合わせたものを準備し、この積層体の両面に厚さ１８μｍの銅箔を重ね合わせて１９５℃の温度、４ＭＰａの圧力で１２０分間加熱・加圧し、厚さ０．８０ｍｍの銅張積層板を得た。各銅張積層板の評価結果を第１表及び第２表に示す。
Test example 1
Each of the polyphenylene ether resin varnishes obtained in Examples 1 to 8 and Comparative Examples 1 to 5 was impregnated, coated and dried on a 100 μm glass woven fabric to obtain a prepreg having a resin content of 50% by mass.
A stack of eight 100 μm prepregs thus obtained was prepared, and a 18 μm thick copper foil was stacked on both sides of this laminate, and heated and pressurized at a temperature of 195 ° C. and a pressure of 4 MPa for 120 minutes, A copper clad laminate having a thickness of 0.80 mm was obtained. The evaluation results of each copper-clad laminate are shown in Tables 1 and 2.
本発明のハロゲンフリー難燃性樹脂組成物は、難燃化手法としてハロゲン系難燃剤を用いておらず、燃焼時に有毒ガスである臭化水素などを発生させることなく、優れた誘電特性を有すると共に、耐燃性、耐熱性、密着性、耐湿性などに優れており、例えばプリプレグ、フィルム、樹脂付きの金属箔やポリイミドフィルムや液晶ポリマーフィルム、積層板、銅張積層板、プリント配線板などを作製することができる。
The halogen-free flame retardant resin composition of the present invention does not use a halogen-based flame retardant as a flame retardant method, and has excellent dielectric characteristics without generating hydrogen bromide which is a toxic gas at the time of combustion. In addition, it is excellent in flame resistance, heat resistance, adhesion, moisture resistance, etc., for example, prepreg, film, metal foil with resin, polyimide film, liquid crystal polymer film, laminate, copper-clad laminate, printed wiring board, etc. Can be produced.
Claims (13)
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| JP2007273648A (en) * | 2006-03-30 | 2007-10-18 | Furukawa Electric Co Ltd:The | Printed wiring board and its manufacturing method |
| KR100948811B1 (en) | 2007-04-05 | 2010-03-24 | 주식회사 잉크테크 | Phosphaphenanthrene-based organic light emitting compound and organic electroluminescent device using the same |
| CN102482500B (en) * | 2009-08-24 | 2014-09-03 | 株式会社钟化 | Flame retardant, production method therefor, and flame retardant thermoplastic resin composition comprising the same |
| KR101659081B1 (en) | 2010-03-26 | 2016-09-23 | 삼성전기주식회사 | Liquid crystalline thermoset oligomer or polymer and thermosetting composition and subratrate inclduing same |
| TWI519634B (en) * | 2011-01-25 | 2016-02-01 | Kaneka Corp | Flame retardant resin composition |
| JP6219112B2 (en) * | 2013-09-27 | 2017-10-25 | 旭化成株式会社 | PPE-containing resin composition |
| EP3055354B1 (en) * | 2013-10-11 | 2018-12-05 | Isola USA Corp. | Varnishes and prepregs and laminates made therefrom |
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| JPH07316383A (en) * | 1994-05-24 | 1995-12-05 | Asahi Chem Ind Co Ltd | Good-flowability flame-retardant resin composition excellent in shock resistance and stiffness |
| JP3716496B2 (en) * | 1996-05-21 | 2005-11-16 | 日本ジーイープラスチックス株式会社 | Flame retardant resin composition |
| JP2000336261A (en) * | 1999-03-24 | 2000-12-05 | Asahi Chem Ind Co Ltd | Curable resin composition |
| JP2003128909A (en) * | 2001-10-23 | 2003-05-08 | Asahi Kasei Corp | Flame-retardant thermosetting resin composition |
| JP2003231762A (en) * | 2002-02-13 | 2003-08-19 | Mitsubishi Gas Chem Co Inc | Prepreg and laminated sheet |
| JP2004210882A (en) * | 2002-12-27 | 2004-07-29 | Polyplastics Co | Fire-retardant resin composition |
| WO2004061008A1 (en) * | 2002-12-27 | 2004-07-22 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
| JP4255759B2 (en) * | 2003-06-20 | 2009-04-15 | 京セラケミカル株式会社 | Polyphenylene ether resin composition, prepreg containing the same, laminate, copper-clad laminate and printed wiring board |
| JP2005225913A (en) * | 2004-02-10 | 2005-08-25 | Kyocera Chemical Corp | Flame-retardant resin composition, and resin part and composite part using the same |
| JP2006063243A (en) * | 2004-08-30 | 2006-03-09 | Kyocera Chemical Corp | Halogen-free flame-retardant resin composition, prepreg using the same and application of the prepreg |
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