JP2000095938A - Production of flame-retardant resin composition for printed wiring board and such composition obtained thereby - Google Patents
Production of flame-retardant resin composition for printed wiring board and such composition obtained therebyInfo
- Publication number
- JP2000095938A JP2000095938A JP10269689A JP26968998A JP2000095938A JP 2000095938 A JP2000095938 A JP 2000095938A JP 10269689 A JP10269689 A JP 10269689A JP 26968998 A JP26968998 A JP 26968998A JP 2000095938 A JP2000095938 A JP 2000095938A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- cyanate
- resin composition
- flame retardant
- printed wiring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高周波帯域におい
て信号の低損失が要求される無線通信機器や動作周波数
が数百ＭＨｚを超えるような高速コンピュータ等に使用
される誘電特性と耐燃性に優れた印刷配線板用難燃性樹
脂組成物の製造方法及びその製造方法により得られた印
刷配線板用難燃性樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent dielectric properties and flame resistance for use in radio communication equipment requiring low signal loss in a high-frequency band and high-speed computers whose operating frequency exceeds several hundred MHz. The present invention relates to a method for producing a flame-retardant resin composition for printed wiring boards and a flame-retardant resin composition for printed wiring boards obtained by the method.
【０００２】[0002]
【従来の技術】近年、無線情報通信分野における各種電
子機器やコンピュータ等では、大容量の情報を高速で処
理することが要求され、ここで扱う電気信号は高周波数
化が進んでいる。しかし、信号の強度は高周波になれば
なるほど減衰しやすくなる性質を持つため、この分野の
印刷配線板には低損失の基板材料、すなわち比誘電率及
び誘電正接の低い樹脂材料が望まれている。従来、この
分野においては比誘電率や誘電正接の低いふっ素樹脂や
ポリフェニレンエーテル等の熱可塑性樹脂をベースとし
た樹脂材料が使用されてきたが、これらは溶融粘度が高
いため流動性が不足し、プレス成形時に高温高圧が必要
という問題や寸法安定性及び金属めっきとの接着性に劣
るという欠点を有している。一方、熱硬化性樹脂材料の
中で比誘電率や誘電正接が低い樹脂として知られるシア
ネートエステル樹脂及びこれを用いたＢＴ（ビスマレイ
ミドトリアジン）樹脂等の樹脂材料も提案されている。
しかし、これらの樹脂材料単独では耐燃性に乏しいとい
う欠点があった。2. Description of the Related Art In recent years, various electronic devices and computers in the field of wireless information communication have been required to process large-capacity information at high speed, and the electrical signals handled here have been increasing in frequency. However, since the signal strength has a property of being easily attenuated as the frequency becomes higher, a low-loss substrate material, that is, a resin material having a low relative dielectric constant and a low dielectric loss tangent is desired for a printed wiring board in this field. . Conventionally, in this field, resin materials based on thermoplastic resins such as fluororesins and polyphenylene ethers having low relative permittivity and dielectric loss tangent have been used, but these have a high melt viscosity and lack fluidity, It has a problem that high temperature and high pressure are required at the time of press molding, and a defect that dimensional stability and adhesion to metal plating are poor. On the other hand, among thermosetting resin materials, resin materials such as a cyanate ester resin known as a resin having a low relative dielectric constant and a low dielectric loss tangent, and a BT (bismaleimide triazine) resin using the same have been proposed.
However, these resin materials alone have a disadvantage of poor flame resistance.
【０００３】上記問題の改良を目的として、ＢＴ（ビス
マレイミドトリアジン）樹脂又はシアネートエステル樹
脂に特公平４−２４３７０号公報に示されている臭素化
ビスフェノールＡ及び臭素化ビスフェノールＡのヒドロ
キシルエーテル化物、特開平２−２８６７２３号公報に
示されている臭素化フェノールノボラックのグリシジル
エーテル化物、特開平５−３３９３４２号公報に示され
ている臭素化ビスフェノールＡのグリシジルエーテル化
物、特開平７−２０７０２２号公報に示されている臭素
化マレイミド類化合物等の難燃剤を併用させる方法等が
ある。[0003] In order to improve the above-mentioned problems, BT (bismaleimide triazine) resin or cyanate ester resin is disclosed in Japanese Patent Publication No. 4-24370, brominated bisphenol A and hydroxyl etherified product of brominated bisphenol A. Glycidyl etherified product of brominated phenol novolak shown in JP-A-2-286723, glycidyl etherified product of brominated bisphenol A shown in JP-A-5-339342, and JP-A-7-207022. And a flame retardant such as a brominated maleimide compound.
【０００４】[0004]
【発明が解決しようとする課題】しかし、特公平４−２
４３７０号公報、特開平２−２８６７２３号公報、特開
平５−３３９３４２号公報、特開平７−２０７０２２号
公報に示されているような難燃剤を併用させる方法で
は、耐燃性は付加できるものの誘電特性が悪化し、この
傾向はＧＨｚを超えるような周波数帯域では特に顕著と
なり高周波用途には対応できないという問題があった。
また、分子中にシアネート基を２個有するシアネート類
化合物のモノマは結晶性が高く、これらのモノマを溶剤
でワニス化する場合、固形分濃度にもよるがワニス中で
再結晶する場合があり、さらに、比較的低分子で低極性
構造の難燃剤は、結晶性が高く溶剤への溶解性が劣り溶
剤が限定されたり、必要量を溶解できないとかワニス中
で析出したりする問題があった。[Problems to be solved by the invention]
In the method using a flame retardant as disclosed in JP-A-4370, JP-A-2-286723, JP-A-5-339342, and JP-A-7-207022, flame resistance can be added, but dielectric properties are increased. This tendency is particularly remarkable in a frequency band exceeding GHz, and there is a problem that it cannot be used for high frequency applications.
Further, a monomer of a cyanate compound having two cyanate groups in the molecule has high crystallinity, and when these monomers are varnished with a solvent, they may be recrystallized in the varnish depending on the solid content concentration, Further, the flame retardant having a relatively low molecular weight and a low polarity structure has a problem that the crystallinity is high and the solubility in the solvent is inferior, the solvent is limited, the required amount cannot be dissolved, or the flame retardant precipitates in the varnish.
【０００５】本発明は、かかる状況に鑑みなされたもの
で、良好な誘電特性、特に高周波帯域で優れた誘電特性
と耐燃性を両立し、ワニス作製時の溶解性や保存安定性
が良好な印刷配線板用難燃性樹脂組成物の製造方法及び
その製造方法により得られた印刷配線板用難燃性樹脂組
成物を提供することを課題とした。The present invention has been made in view of the above circumstances, and has good dielectric properties, especially excellent dielectric properties and high flame resistance in a high frequency band, and has good solubility and storage stability during varnish production. An object of the present invention is to provide a method for producing a flame-retardant resin composition for wiring boards and a flame-retardant resin composition for printed wiring boards obtained by the method.
【０００６】[0006]
【課題を解決するための手段】すなわち本発明は、
（Ａ）式（１）で示される分子中にシアナト基を２つ以
上含有するシアネート類化合物を予め反応させて得られ
るシアネートエステルオリゴマー、（Ｂ）式（１）で示
されるシアネート類化合物との反応性を有しない難燃剤
を必須成分として配合する樹脂組成物において、（Ａ）
シアネートエステルオリゴマーと（Ｂ）シアネート類化
合物との反応性を有しない難燃剤とを５０〜１５０℃の
温度で混合又は溶融することを特徴とする印刷配線板用
樹脂組成物の製造方法である。That is, the present invention provides:
(A) a cyanate ester oligomer obtained by previously reacting a cyanate compound having two or more cyanato groups in a molecule represented by the formula (1); and (B) a cyanate ester oligomer represented by the formula (1). In a resin composition containing a flame retardant having no reactivity as an essential component, (A)
A method for producing a resin composition for a printed wiring board, comprising mixing or melting a cyanate ester oligomer and a flame retardant (B) having no reactivity with a cyanate compound at a temperature of 50 to 150 ° C.
【０００７】[0007]
【化３】 Embedded image
【０００８】また、本発明は、式（１）で示される分子
中にシアナト基を２つ以上含有するシアネート類化合物
が、２，２−ビス（４−シアナトフェニル）プロパン、
ビス（４−シアナトフェニル）エタン、ビス（３，５−
ジメチル−４−シアナトフェニル）メタン、２，２−ビ
ス（４−シアナトフェニル）−１，１，１，３，３，３
−ヘキサフルオロプロパン、α，α’−ビス（４−シア
ナトフェニル）−ｍ−ジイソプロピルベンゼンまたはフ
ェノール付加ジシクロペンタジエン重合体のシアネート
類化合物から選ばれる１種類又は２種類以上の混合物で
あると好ましい印刷配線板用難燃性樹脂組成物の製造方
法であり、（Ａ）式（１）で示される分子中にシアナト
基を２つ以上含有するシアネート類化合物を予め反応さ
せて得られるシアネートエステルオリゴマーにおいて、
シアナト基の反応率が１０〜７０％であると好ましい印
刷配線板用難燃性樹脂組成物の製造方法である。そし
て、本発明は、（Ｂ）シアネート類化合物との反応性を
有しない難燃剤が、１，２−ジブロモ−４−（１，２−
ジブロモエチル）シクロヘキサン、テトラブロモシクロ
オクタンまたはヘキサブロモシクロドデカンから選ばれ
る脂肪族環型難燃剤の少なくとも１種類以上であると好
ましい印刷配線板用難燃性樹脂組成物の製造方法であ
り、（Ｂ）式（１）で示される分子中にシアナト基を２
つ以上含有するシアネート類化合物との反応性を有しな
い難燃剤が、式（２）で示される複素環型難燃剤または
これらの少なくとも１種類以上とシアネート類化合物と
の反応性を有しない難燃剤との混合物であると好ましい
印刷配線板用難燃性樹脂組成物の製造方法である。Further, the present invention relates to a compound represented by the formula (1) wherein the cyanate compound having two or more cyanate groups is 2,2-bis (4-cyanatophenyl) propane,
Bis (4-cyanatophenyl) ethane, bis (3,5-
Dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3
It is preferably one or a mixture of two or more selected from hexafluoropropane, α, α'-bis (4-cyanatophenyl) -m-diisopropylbenzene, and a cyanate compound of a phenol-added dicyclopentadiene polymer. A method for producing a flame-retardant resin composition for a printed wiring board, comprising: (A) a cyanate ester oligomer obtained by previously reacting a cyanate compound containing two or more cyanato groups in a molecule represented by the formula (1): At
This is a method for producing a flame-retardant resin composition for a printed wiring board in which the reaction rate of a cyanate group is preferably 10 to 70%. The present invention relates to (B) a flame retardant having no reactivity with a cyanate compound, which comprises 1,2-dibromo-4- (1,2-
Dibromoethyl) cyclohexane, tetrabromocyclooctane or hexabromocyclododecane, a method for producing a flame-retardant resin composition for printed wiring boards, which is preferably at least one or more aliphatic cyclic flame retardants selected from the group consisting of (B ) A cyanato group is added to the molecule represented by the formula (1).
The flame retardant having no reactivity with at least one cyanate compound is a heterocyclic flame retardant represented by the formula (2) or a flame retardant having no reactivity between at least one or more of these and the cyanate compound. And a method for producing a flame-retardant resin composition for a printed wiring board.
【０００９】[0009]
【化４】 Embedded image
【００１０】さらに本発明は、上記の印刷配線板用難燃
性樹脂組成物の製造方法により得られた印刷配線板用難
燃性樹脂組成物である。この印刷配線板用難燃性樹脂組
成物をワニスとしガラス織布等の基材に含浸、乾燥させ
プリプレグとし、このプリプレグの１枚以上を用いて銅
箔等の金属箔、内層回路板に積層し、加熱加圧成形する
ことにより金属箔張積層板、多層配線板とし、外層回路
を形成し印刷配線板とする。Further, the present invention is a flame-retardant resin composition for a printed wiring board obtained by the method for producing a flame-retardant resin composition for a printed wiring board described above. The flame-retardant resin composition for a printed wiring board is used as a varnish, impregnated into a substrate such as a glass woven fabric, and dried to form a prepreg. Then, it is heated and pressed to form a metal foil-clad laminate and a multilayer wiring board, and an outer layer circuit is formed to obtain a printed wiring board.
【００１１】[0011]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明において用いられる（Ａ）シアネートエステルオ
リゴマーは、式（１）で示される分子中にシアナト基を
２つ以上含有するシアネート類化合物を予め反応させて
得られるオリゴマーであり、具体例としては、２，２−
ビス（４−シアナトフェニル）プロパン、ビス（４−シ
アナトフェニル）エタン、ビス（３，５−ジメチル−４
−シアナトフェニル）メタン、２，２−ビス（４−シア
ナトフェニル）−１，１，１，３，３，３−ヘキサフル
オロプロパン、α，α’−ビス（４−シアナトフェニ
ル）−ｍ−ジイソプロピルベンゼン、フェノール付加ジ
シクロペンタジエン重合体のシアネート類化合物のオリ
ゴマーが挙げられ、これらは一種類単独で用いてもよ
く、または二種類以上を混合して用いてもよい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The (A) cyanate ester oligomer used in the present invention is an oligomer obtained by previously reacting a cyanate compound having two or more cyanate groups in a molecule represented by the formula (1), and specific examples thereof include: 2,2-
Bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3,5-dimethyl-4)
-Cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl)- Oligomers of cyanate compounds of m-diisopropylbenzene and a phenol-added dicyclopentadiene polymer may be mentioned, and these may be used alone or in a combination of two or more.
【００１２】本発明において用いられる（Ｂ）難燃剤
は、式（１）で示される分子中にシアナト基を２つ以上
含有するシアネート類化合物との反応性を有しない難燃
剤であり、具体例としては、１，２−ジブロモ−４−
（１，２−ジブロモエチル）シクロヘキサン、テトラブ
ロモオクタンまたはヘキサブロモシクロドデカン等の脂
肪族環型難燃剤及び式（２）で示される複素環型難燃剤
が挙げられる。式（２）で表される複素環型難燃剤とし
ては、２，４，６−トリス（トリブロモフェノキシ）−
１，３，５−トリアジンが挙げられる。また、上記のシ
アネート類化合物との反応性を有しない難燃剤は１種類
単独で用いてもよく、２種類以上を混合して用いてもよ
い。The flame retardant (B) used in the present invention is a flame retardant having no reactivity with a cyanate compound having two or more cyanato groups in the molecule represented by the formula (1). Is 1,2-dibromo-4-
Aliphatic ring type flame retardants such as (1,2-dibromoethyl) cyclohexane, tetrabromooctane or hexabromocyclododecane, and heterocyclic type flame retardants represented by the formula (2) are exemplified. As the heterocyclic flame retardant represented by the formula (2), 2,4,6-tris (tribromophenoxy)-
1,3,5-triazine is mentioned. The flame retardant having no reactivity with the cyanate compound may be used alone or in combination of two or more.
【００１３】また、本発明においては、（Ａ）式（１）
で示される分子中にシアナト基を２つ以上含有するシア
ネート類化合物を予め反応させて得られるシアネートエ
ステルオリゴマーと（Ｂ）式（１）で示されるシアネー
ト類化合物との反応性を有しない難燃剤を５０〜１５０
℃の温度で混合又は溶融することが必須である。本発明
におけるこの手法は、５０℃以上で軟化した（Ａ）シア
ネートエステルオリゴマーと（Ｂ）式（１）で示される
シアネート類化合物との反応性を有しない難燃剤を投入
攪拌し混合又は溶融させることにより、この樹脂を溶剤
に溶解させて溶液とする際に、（Ａ）シアネートエステ
ルオリゴマーの溶解性が高い溶剤を用いて難燃化に必要
な配合量の難燃剤を溶解できる難燃性樹脂組成物の製造
方法である。すなわち本発明によれば、難燃剤の溶解性
が低い溶剤を用いた場合でも難燃剤を当該溶剤への溶解
度を超える配合量で用いることが可能となり、さらに、
ワニスを室温以下の状態で保管しても難燃剤が再結晶す
ることなく、あるいは析出することがあっても析出する
までの時間を長くすることができる。難燃剤の溶解度が
低い溶剤を用いてワニス化する場合は、（Ａ）シアネー
トエステルオリゴマーと（Ｂ）シアネート類化合物との
反応性を有しない難燃剤の混合又は溶融の５０〜１５０
℃の温度での加熱中に溶剤を加えても冷却後に投入して
もどちらでもよいが、加熱中に溶剤を加えた方が難燃剤
の析出を防ぐのにより効果的である。また、（Ａ）シア
ネートオリゴマーと（Ｂ）難燃剤を混合又は溶融する温
度範囲は、５０〜１５０℃とされ、６０〜１２０℃とす
ることがより好ましく、７０℃〜１１０℃とすることが
さらに好ましい。５０℃未満の場合は上記の効果が発揮
されにくく、１５０℃を超える温度ではシアネートオリ
ゴマーが熱反応することにより分子量が大きくなり、ゲ
ル化時間が短くなったりワニスとした時の粘度が増加す
る可能性があるため好ましくない。In the present invention, (A) Formula (1)
(B) a flame retardant having no reactivity between a cyanate ester oligomer obtained by previously reacting a cyanate compound containing two or more cyanato groups in a molecule and (B) a cyanate compound represented by the formula (1) 50 to 150
It is essential to mix or melt at a temperature of ° C. According to this method in the present invention, a flame retardant having no reactivity between (A) a cyanate ester oligomer softened at 50 ° C. or more and (B) a cyanate compound represented by the formula (1) is charged, stirred and mixed or melted. Thus, when this resin is dissolved in a solvent to form a solution, (A) a flame-retardant resin capable of dissolving a flame retardant in a necessary amount for flame retardation using a solvent having a high solubility of a cyanate ester oligomer. This is a method for producing a composition. That is, according to the present invention, even when a solvent having low solubility of the flame retardant is used, the flame retardant can be used in a compounding amount exceeding the solubility in the solvent, and further,
Even if the varnish is stored at room temperature or lower, the flame retardant does not recrystallize, or the time until the varnish precipitates can be increased even if it is. When varnishing is performed using a solvent having low solubility of the flame retardant, the mixing or melting of the flame retardant having no reactivity between (A) the cyanate ester oligomer and (B) the cyanate compound is performed at 50 to 150.
Either a solvent may be added during heating at a temperature of ° C. or a charge may be added after cooling, but adding a solvent during heating is more effective in preventing precipitation of the flame retardant. The temperature range in which (A) the cyanate oligomer and (B) the flame retardant are mixed or melted is 50 to 150 ° C, more preferably 60 to 120 ° C, and further preferably 70 to 110 ° C. preferable. When the temperature is lower than 50 ° C., the above effects are hardly exhibited, and when the temperature exceeds 150 ° C., the molecular weight increases due to the thermal reaction of the cyanate oligomer, thereby shortening the gelation time and increasing the viscosity of the varnish. It is not preferable because of its properties.
【００１４】本発明における（Ａ）式（１）で示される
分子中にシアナト基を２つ以上含有するシアネート類化
合物を予め反応させて得られるシアネートエステルオリ
ゴマーは、式（１）で示されるシアネート類化合物のシ
アナト基の反応率が１０〜７０％であることが好まし
く、好ましくは反応率２０〜６０％の転化物がより望ま
しい。１０％未満の場合、難燃剤のシアネートエステル
オリゴマーへの溶解性や分散性が低下するためワニス化
した際に難燃剤が析出しやすくなり、あるいはシアネー
ト類化合物は結晶性が高いため、ワニス化した際に溶剤
中にシアネート類化合物モノマーが再結晶する場合があ
る。７０％を超える場合は、ワニスとした時の粘度が高
くなりガラス基材等への含浸性が低下しプリプレグ表面
の平滑性が失われるおそれがあり、またゲル化時間が塗
工作業上問題となるまで短くなったりワニスの保存安定
性（ポットライフ）が失われるため望ましくない。In the present invention, (A) a cyanate ester oligomer obtained by previously reacting a cyanate compound having two or more cyanate groups in a molecule represented by the formula (1) is a cyanate ester oligomer represented by the formula (1): The conversion of the cyanato group of the compound is preferably 10 to 70%, and more preferably a converted product having a conversion of 20 to 60%. When the content is less than 10%, the solubility and dispersibility of the flame retardant in the cyanate ester oligomer are reduced, so that the flame retardant easily precipitates when varnished, or the varnish is formed because the cyanate compound has high crystallinity. At that time, the cyanate compound monomer may be recrystallized in the solvent. If it exceeds 70%, the viscosity as a varnish increases, impregnating the glass substrate or the like may decrease, and the smoothness of the prepreg surface may be lost. It is not desirable because the varnish becomes shorter or the storage stability (pot life) of the varnish is lost.
【００１５】本発明における（Ｂ）シアネート類化合物
との反応性を有しない難燃剤の配合量は、（Ａ）式
（１）で示される分子中にシアナト基を２つ以上含有す
るシアネート類化合物を予め反応させて得られるシアネ
ートエステルオリゴマーの配合量１００重量部に対して
５〜３０重量部とすることが好ましく、５〜２０重量部
とすることがより好ましく、１０〜２０重量部とするこ
とがさらに好ましい。（Ｂ）シアネート類化合物との反
応性を有しない難燃剤の配合量が５重量部未満では耐燃
性が不十分となる傾向があり、３０重量部を超えると樹
脂の耐熱性が低下する傾向がある。In the present invention, the compounding amount of the flame retardant (B) having no reactivity with the cyanate compound is (A) a cyanate compound containing two or more cyanate groups in a molecule represented by the formula (1). Is preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight, and more preferably 10 to 20 parts by weight based on 100 parts by weight of the cyanate ester oligomer obtained by previously reacting Is more preferred. If the blending amount of the flame retardant (B) having no reactivity with the cyanate compound is less than 5 parts by weight, the flame resistance tends to be insufficient, and if it exceeds 30 parts by weight, the heat resistance of the resin tends to decrease. is there.
【００１６】本発明においては、難燃性樹脂組成物の硬
化反応を促進するための硬化促進剤を用いることが好ま
しい。硬化促進剤の具体例としては、コバルト、マンガ
ン、スズ、ニッケル、亜鉛、銅等の有機金属塩化合物を
用いることができる。有機金属塩化合物は１種類単独で
用いてもよく、または２種類以上を併用して用いてもよ
い。In the present invention, it is preferable to use a curing accelerator for accelerating the curing reaction of the flame-retardant resin composition. Specific examples of the curing accelerator include organic metal salt compounds such as cobalt, manganese, tin, nickel, zinc, and copper. The organometallic salt compounds may be used alone or in combination of two or more.
【００１７】本発明においては、エポキシ樹脂、イミド
類、フェノール類、アルコール類等の各種樹脂や化合物
を印刷配線板とした時の誘電特性や耐熱性等の特性を悪
化させない範囲の配合量で併用して用いることができ
る。In the present invention, various resins and compounds, such as epoxy resins, imides, phenols, and alcohols, are used together in a compounding amount within a range that does not deteriorate the properties such as the dielectric properties and heat resistance of the printed wiring board. Can be used.
【００１８】また本発明においては、必要に応じて充填
剤及びその他添加剤を配合することができる。必要に応
じて配合される充填剤としては、通常、無機充填剤が好
適に用いられ、具体例としては溶融シリカ、ガラス、ア
ルミナ、チタニア、ジルコン、炭酸カルシウム、珪酸カ
ルシウム、珪酸マグネシウム、珪酸アルミニウム、窒化
珪素、窒化ホウ素、ベリリア、ジルコニア、チタン酸バ
リウム、チタン酸カリウム、チタン酸カルシウム等を用
いることができる。In the present invention, a filler and other additives can be added as required. As the filler to be blended as necessary, usually, an inorganic filler is suitably used, and specific examples thereof are fused silica, glass, alumina, titania, zircon, calcium carbonate, calcium silicate, magnesium silicate, aluminum silicate, Silicon nitride, boron nitride, beryllia, zirconia, barium titanate, potassium titanate, calcium titanate, or the like can be used.
【００１９】本発明の印刷配線板用難燃性樹脂組成物は
加熱硬化させることにより、誘電特性や耐熱性に優れた
印刷配線板の製造に供せられる。すなわち、本発明の印
刷配線板用難燃性樹脂組成物を溶剤に溶解していったん
ワニス化し、ガラス織布等の基材に含浸し乾燥すること
によってまずプリプレグを作製する。次いでこのプリプ
レグの任意枚数と上下に金属箔を重ねて加熱成形するこ
とによって印刷配線板又は金属張積層板とすることがで
きる。ここでの乾燥とは、溶剤を使用した場合には溶剤
を除去すること、溶剤を使用しない場合には室温での流
動性がなくなるようにすることをいう。The flame-retardant resin composition for a printed wiring board of the present invention can be subjected to heat curing to provide a printed wiring board having excellent dielectric properties and heat resistance. That is, the flame-retardant resin composition for a printed wiring board of the present invention is dissolved in a solvent to form a varnish once, impregnated into a base material such as a glass woven fabric, and dried to prepare a prepreg. Next, a printed wiring board or a metal-clad laminate can be obtained by laminating a metal foil on an arbitrary number of the prepregs and heating and forming the metal foils. Here, drying means removing the solvent when a solvent is used, or eliminating fluidity at room temperature when a solvent is not used.
【００２０】本発明の印刷配線板用難燃性樹脂組成物を
ワニス化する場合は、溶剤は特に限定するものではない
が、具体例としては、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のケトン
類、トルエン、キシレン、メシチレン等の芳香族炭化水
素類、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、酢酸エチル等のエ
ステル系、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のアミド類等の溶剤が
用いられる。その中でも（Ａ）式（１）で示される分子
中にシアナト基を２つ以上含有するシアネート類化合物
を予め反応させて得られるシアネートエステルオリゴマ
ーの溶解性やワニスとした時の粘度やワニスの保存安定
性が良好となる溶剤を用いることが好ましく、具体的に
はケトン類が好ましい。また、これら上記溶剤は１種類
単独で用いてもよく、または２種類以上を混合して用い
てもよい。When varnishing the flame-retardant resin composition for a printed wiring board of the present invention, the solvent is not particularly limited, but specific examples include acetone, methyl ethyl ketone, and the like.
Ketones such as methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ester systems such as ethyl acetate, N-methylpyrrolidone, formamide, N −
Methylformamide, N, N-dimethylformamide,
Solvents such as amides such as N, N-dimethylacetamide are used. Among them, (A) the solubility of a cyanate ester oligomer obtained by previously reacting a cyanate ester compound having two or more cyanato groups in a molecule represented by the formula (1), the viscosity of a varnish, and the storage of a varnish It is preferable to use a solvent having good stability, and specifically, ketones are preferable. These solvents may be used alone or in a combination of two or more.
【００２１】一般に、樹脂硬化物の誘電特性は、分子構
造、即ち分子内の極性基の量や強さ及び分子骨格の動き
やすさ等に影響を受ける。元来、シアネートエステル樹
脂硬化物は低極性、剛直かつ対称性構造のトリアジン骨
格を有するため低誘電率及び低誘電正接である。しか
し、耐燃性を付加するためシアネートエステルに臭素化
エポキシ樹脂、臭素化多価フェノール類、臭素化イミド
類等のシアナト基との反応性を有する反応型難燃剤の併
用といった従来の方法では、シアナト基との反応により
トリアジン環以外の極性基が生成したり、硬化反応の進
行に伴って反応系が流動性を失い反応しきれない未反応
の官能基（シアナト基、グリシジル基、フェノール性水
酸基、イミド基等）が残存しやすくなるため誘電特性が
悪化し、この傾向は高周波領域でさらに顕著となる。こ
れに対して、本発明において用いられる難燃剤は、低極
性構造でかつシアナト基に対して非反応型でありトリア
ジン環の生成を妨げないことから誘電特性を悪化させる
ことなく耐燃性を付加できる。ただし、このような難燃
剤は比較的低分子で低極性構造であることから結晶性が
高く、溶剤への溶解性に劣り溶剤が限定されることがあ
るため、シアネート類化合物と難燃剤を溶剤でワニス化
する場合に同一の溶剤では難燃化に必要な配合量の難燃
剤を溶解できないことがある。また、混合溶剤を使用し
た時でも難燃剤またはシアネート類化合物のどちらかが
溶解できなかったり溶解しても再結晶しやすくなる。あ
るいは難燃剤またはシアネート類化合物のどちらの溶解
性が低い溶剤を多量に使用して溶解させた場合は濃度が
低いワニスしか得ることができず、結果的にプリプレグ
の樹脂付着量が低くなりプレス成形後に積層板のカスレ
不良が発生したり、多層板を製造する際には内層回路の
溝を十分に埋め込むことができずボイドが発生する可能
性がある。しかし、本発明が提案するところの、５０〜
１５０℃の温度でシアネートエステルオリゴマーと難燃
剤とを混合又は溶融する印刷配線板用難燃性樹脂組成物
の製造方法を採用することにより、シアネートエステル
オリゴマーと難燃剤を相互に溶解させやすくかつオリゴ
マーの分子内に難燃剤の骨格を絡めやすくすることによ
り、シアネートエステルオリゴマーに対する良溶剤に溶
解性が劣る難燃剤であってもワニス中で難燃剤の再結晶
を抑制したり少なくできる。したがって、本発明の印刷
配線板用難燃性樹脂組成物の製造方法及びその製造方法
により得られる印刷配線板用難燃性樹脂組成物は、高周
波領域においてシアネート樹脂系硬化物の優れた誘電特
性を悪化させることなく耐燃性を付与できる。Generally, the dielectric properties of the cured resin are affected by the molecular structure, that is, the amount and strength of the polar group in the molecule, the mobility of the molecular skeleton, and the like. Originally, a cured product of a cyanate ester resin has a low dielectric constant and a low dielectric loss tangent because it has a triazine skeleton having a low polarity, rigid and symmetric structure. However, in order to add flame resistance, conventional methods such as the use of a cyanate ester with a reactive flame retardant having a reactivity with a cyanate group such as a brominated epoxy resin, a brominated polyphenol, and a brominated imide have been proposed. A polar group other than the triazine ring is generated by the reaction with the group, and the unreacted functional group (cyanato group, glycidyl group, phenolic hydroxyl group, (E.g., an imide group) is likely to remain, thereby deteriorating the dielectric properties, and this tendency becomes even more pronounced in the high frequency range. On the other hand, the flame retardant used in the present invention has a low polarity structure and is non-reactive with respect to the cyanato group, and does not hinder the formation of a triazine ring, so that the flame retardant can be added without deteriorating the dielectric properties. . However, since such a flame retardant has a relatively low molecular weight and a low polarity structure, it has high crystallinity, poor solubility in a solvent, and the solvent may be limited. In some cases, the same solvent may not be able to dissolve the flame retardant in the amount required for flame retardation. In addition, even when a mixed solvent is used, either the flame retardant or the cyanate compound cannot be dissolved, or recrystallization is likely to occur even if dissolved. Alternatively, when a large amount of a solvent having low solubility, either a flame retardant or a cyanate compound, is used for dissolution, only a varnish having a low concentration can be obtained, and as a result, the resin adhesion amount of the prepreg decreases and press molding is performed. There is a possibility that a defective lamination of the laminated board may occur later, or a groove of the inner circuit may not be sufficiently buried when a multilayer board is manufactured, so that a void may be generated. However, the present invention proposes that
By adopting a method for producing a flame-retardant resin composition for a printed wiring board in which a cyanate ester oligomer and a flame retardant are mixed or melted at a temperature of 150 ° C., the cyanate ester oligomer and the flame retardant are easily dissolved in each other and the oligomer By making the skeleton of the flame retardant easily entangled in the molecule, even if the flame retardant has poor solubility in a good solvent for the cyanate ester oligomer, recrystallization of the flame retardant in the varnish can be suppressed or reduced. Therefore, the method for producing a flame-retardant resin composition for a printed wiring board of the present invention and the flame-retardant resin composition for a printed wiring board obtained by the production method are excellent in the dielectric properties of the cyanate resin-based cured product in a high frequency region. Can be imparted without deteriorating the flame resistance.
【００２２】[0022]
【実施例】以下、具体例を挙げて本発明を具体的に説明
するが、本発明はこれらに限られるものではない。EXAMPLES The present invention will now be described specifically with reference to specific examples, but the present invention is not limited to these examples.
【００２３】（実施例１）温度計、冷却管、攪拌装置を
備えた２リットルの４つ口セパラブルフラスコに２，２
−ビス（４−シアナトフェニル）プロパン（Ａｒｏｃｙ
Ｂ−１０，旭チバ株式会社製商品名）を投入後、１８
０℃で５時間加熱反応させシアナト基の反応率が約４５
％のシアネートエステルオリゴマーを製造した。シアナ
ト基の反応率は、液体クロマトグラフィー（機種：ポン
プ；株式会社日立製作所製Ｌ−６２００，ＲＩ検出器；
Ｌ−３３００，カラム：東ソー株式会社製ＴＳＫｇｅｌ
−Ｇ４０００Ｈ，Ｇ２０００Ｈ，溶媒：ＴＨＦ，濃度：
１重量％）で確認した。このシアネートエステルオリゴ
マーを８０℃に冷却後、１，２−ジブロモ−４−（１，
２−ジブロモエチル）シクロヘキサン（ＳＡＹＴＥＸ
ＢＣＬ−４６２，アルベマール社製商品名）を配合し１
時間攪拌した。次いで、メチルエチルケトンを攪拌しな
がら投入し、更にｐ−ノニルフェノールと硬化促進剤と
してナフテン酸亜鉛を配合して、不揮発分６５重量％、
ゲル化時間（１６０℃）が約４００秒のワニスを作製し
た。各材料の配合量は表１に示した。Example 1 A 2-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer was charged with 2,2.
-Bis (4-cyanatophenyl) propane (Arocy
B-10, trade name of Asahi Ciba Co., Ltd.)
The mixture was heated at 0 ° C for 5 hours, and the reaction rate of cyanato group was about 45.
% Of cyanate ester oligomer was prepared. The reaction rate of the cyanate group was determined by liquid chromatography (model: pump; L-6200, manufactured by Hitachi, Ltd .; RI detector;
L-3300, column: TSKgel manufactured by Tosoh Corporation
-G4000H, G2000H, solvent: THF, concentration:
1% by weight). After cooling the cyanate ester oligomer to 80 ° C., 1,2-dibromo-4- (1,1
2-dibromoethyl) cyclohexane (SAYTEX
BCL-462, trade name of Albemarle)
Stirred for hours. Next, methyl ethyl ketone was added with stirring, and p-nonylphenol and zinc naphthenate were added as a curing accelerator to obtain a nonvolatile content of 65% by weight.
A varnish having a gel time (160 ° C.) of about 400 seconds was produced. The amount of each material is shown in Table 1.
【００２４】（実施例２）実施例１において、１，２−
ジブロモ−４−（１，２−ジブロモエチル）シクロヘキ
サンをテトラブロモシクロオクタン（ＳＡＹＴＥＸ Ｂ
Ｃ−４８，アルベマール社製商品名）に代えて表１に示
す配合量で配合した他は実施例１と同様にしてワニスを
製造した。(Example 2) In Example 1, 1,2-
Dibromo-4- (1,2-dibromoethyl) cyclohexane was converted to tetrabromocyclooctane (SAYTEX B
A varnish was produced in the same manner as in Example 1, except that C-48 was used in place of C-48 (trade name, manufactured by Albemarle Co., Ltd.).
【００２５】（実施例３）実施例１において、２，２−
ビス（４−シアナトフェニル）プロパンをビス（３，５
−ジメチル−４−シアネートフェニル）メタン（Ａｒｏ
ｃｙ Ｍ−１０，旭チバ株式会社製商品名）に代えて、
１８０℃で８時間加熱反応させ反応率が約４３％のシア
ネートエステルオリゴマーを製造し、１，２−ジブロモ
−４−（１，２−ジブロモエチル）シクロヘキサンをヘ
キサブロモシクロドデカン（ＣＤ−７５Ｐ，グレートレ
イクス社製商品名）に代えて、表１に示す配合量で配合
した他は実施例１と同様にしてワニスを作製した。(Example 3) In Example 1, 2,2-
Bis (4-cyanatophenyl) propane is replaced with bis (3,5
-Dimethyl-4-cyanatephenyl) methane (Aro
cy M-10, trade name of Asahi Ciba Co., Ltd.)
The reaction was carried out at 180 ° C. for 8 hours to produce a cyanate ester oligomer having a reaction rate of about 43%, and 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane was converted to hexabromocyclododecane (CD-75P, grade A varnish was prepared in the same manner as in Example 1 except that the blending amount was as shown in Table 1 in place of (trade name, manufactured by Lakes Inc.).
【００２６】（実施例４）実施例３において、ヘキサブ
ロモシクロドデカンを臭素化トリフェニルシアヌレート
（ピロガードＳＲ−２４５，第一工業製薬株式会社製商
品名）に代えて表１に示す配合量で配合した他は実施例
３と同様にしてワニスを作製した。(Example 4) In Example 3, hexabromocyclododecane was replaced with brominated triphenylcyanurate (Pyroguard SR-245, trade name of Daiichi Kogyo Seiyaku Co., Ltd.) at the compounding amount shown in Table 1. A varnish was prepared in the same manner as in Example 3 except for mixing.
【００２７】（実施例５）実施例４において、ビス
（３，５−ジメチル−４−シアネートフェニル）メタン
をα，α’−ビス（４−シアネートフェニル）−ｍ−ジ
イソプロピルベンゼン（ＲＴＸ−３６６，旭チバ株式会
社製商品名）に代えて、１８０℃で３時間加熱反応させ
シアナト基の反応率が約４７％のシアネートエステルオ
リゴマーを製造した他は実施例４と同様にして表１に示
す配合量でワニスを作製した。Example 5 In Example 4, bis (3,5-dimethyl-4-cyanatephenyl) methane was replaced with α, α′-bis (4-cyanatephenyl) -m-diisopropylbenzene (RTX-366, The formulation shown in Table 1 was carried out in the same manner as in Example 4 except that the reaction was carried out at 180 ° C. for 3 hours to produce a cyanate ester oligomer having a cyanate group reaction rate of about 47% in place of Asahi Ciba Corporation. Varnishes were made in quantities.
【００２８】（実施例６）実施例３において、ビス
（３，５−ジメチル−４−シアネートフェニル）メタン
を２，２−ビス（４−シアネートフェニル）−１，１，
１，３，３，３−ヘキサフルオロプロパン（Ａｒｏｃｙ
Ｆ−１０，旭チバ株式会社製商品名）に代えて、１８
０℃で５時間加熱反応させシアナト基の反応率が約４５
％のシアネートエステルオリゴマーを製造した他は実施
例３と同様にして表１に示す配合量でワニスを製造し
た。Example 6 In Example 3, bis (3,5-dimethyl-4-cyanatephenyl) methane was replaced with 2,2-bis (4-cyanatephenyl) -1,1,1.
1,3,3,3-hexafluoropropane (Arocy
F-10, trade name, manufactured by Asahi Ciba Co., Ltd.)
The mixture was heated at 0 ° C for 5 hours, and the reaction rate of cyanato group was about 45.
% Varnish was produced in the same manner as in Example 3 except that the cyanate ester oligomer was prepared in the same manner as in Example 3.
【００２９】（実施例７）実施例４において、メチルエ
チルケトンをトルエンに代えて表１に示す配合量で配合
した他は実施例４と同様にしてワニスを作製した。Example 7 A varnish was prepared in the same manner as in Example 4, except that methyl ethyl ketone was used in place of toluene in the amount shown in Table 1.
【００３０】（比較例１）実施例１において、１，２−
ジブロモ−４−（１，２−ジブロモエチル）シクロヘキ
サンを臭素化ビスフェノールＡ型エポキシ樹脂（ＥＳＢ
４００Ｔ，住友化学工業株式会社製商品名）に代えて表
１に示す配合量で室温（約１５℃）において配合した他
は実施例１と同様にしてワニスを作製した。Comparative Example 1 In Example 1, 1,2-
Dibromo-4- (1,2-dibromoethyl) cyclohexane is converted to a brominated bisphenol A type epoxy resin (ESB
A varnish was prepared in the same manner as in Example 1 except that the mixture was blended at room temperature (about 15 ° C.) in the amounts shown in Table 1 in place of 400T (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
【００３１】（比較例２）実施例３において、ヘキサブ
ロモシクロドデカンを臭素化フェノールノボラック型エ
ポキシ樹脂（ＢＲＥＮ−Ｓ，日本化薬株式会社製商品
名）に代えて表１に示す配合量で室温（約１５℃）にお
いて配合した他は実施例３と同様にしてワニスを作製し
た。Comparative Example 2 The same procedure as in Example 3 was repeated, except that hexabromocyclododecane was replaced with a brominated phenol novolak type epoxy resin (BREN-S, trade name of Nippon Kayaku Co., Ltd.) at the compounding amount shown in Table 1 and at room temperature. A varnish was prepared in the same manner as in Example 3 except that the varnish was blended at (about 15 ° C.).
【００３２】（比較例３）比較例１において、臭素化ビ
スフェノールＡ型エポキシ樹脂を臭素化ビスフェノール
Ａ（ＦＧ−２０００，帝人化成株式会社製商品名）に代
えて表１に示す配合量で配合した他は比較例１と同様に
してワニスを作製した。(Comparative Example 3) In Comparative Example 1, the brominated bisphenol A type epoxy resin was blended in the amount shown in Table 1 in place of brominated bisphenol A (FG-2000, trade name, manufactured by Teijin Chemicals Ltd.). Otherwise, a varnish was produced in the same manner as in Comparative Example 1.
【００３３】（比較例４）実施例３において、ヘキサブ
ロモシクロドデカン、メチルエチルケトン、ｐ−ノニル
フェノール及び硬化促進剤を室温（約１５℃）において
配合した他は実施例３と同様にして表１に示す配合量で
ワニスを作製した。(Comparative Example 4) Table 1 is shown in the same manner as in Example 3 except that hexabromocyclododecane, methyl ethyl ketone, p-nonylphenol and a curing accelerator were blended at room temperature (about 15 ° C). A varnish was prepared with the compounding amount.
【００３４】（比較例５）実施例４において、臭素化ト
リフェニルシアヌレート、メチルエチルケトン、ｐ−ノ
ニルフェノール及び硬化促進剤を室温（約１５℃）にお
いて配合した他は実施例４と同様にして表１に示す配合
量でワニスを作製した。Comparative Example 5 Table 1 was prepared in the same manner as in Example 4 except that brominated triphenyl cyanurate, methyl ethyl ketone, p-nonylphenol and a curing accelerator were blended at room temperature (about 15 ° C.). A varnish was prepared in the amounts shown in Table 1.
【００３５】（比較例６）比較例５において、メチルエ
チルケトンをトルエンに代えて表１に示す配合量で配合
した他は比較例５と同様にしてワニスを作製した。Comparative Example 6 A varnish was prepared in the same manner as in Comparative Example 5, except that methyl ethyl ketone was used instead of toluene in the amount shown in Table 1.
【００３６】（参考例）実施例３において、ビス（３，
５−ジメチル−４−シアネートフェニル）メタンを１８
０℃で３０分間加熱反応させシアナト基の反応率が約８
％のシアネートエステルオリゴマーを製造した他は実施
例３と同様にして表１に示す配合量でワニスを作製し
た。Reference Example In Example 3, the screw (3,
5-dimethyl-4-cyanatephenyl) methane is 18
The mixture was heated at 0 ° C for 30 minutes, and the reaction rate of cyanato group was about 8
%, And a varnish was prepared in the same manner as in Example 3 except that the cyanate ester oligomer was prepared in the same manner as in Example 3.
【００３７】[0037]
【表１】 [Table 1]
【００３８】実施例１〜７及び比較例１〜６、参考例で
製造したワニスについて、配合直後及び温度２０℃で７
日放置後の粘度（２５℃，Ｅ型粘度計）を測定した。ま
た、配合直後及び配合後１０℃で１〜１０日間保管した
ワニスの外観を観察した。その結果を表１に示す。表中
のワニス外観について不良(1)〜(3)は、(1)シアネート
類化合物又は難燃剤が不溶、(2)シアネート類化合物が
再結晶、(3)難燃剤が再結晶をそれぞれ意味する。表中
の良好とは、不良(1)〜(3)がないことを意味する。The varnishes prepared in Examples 1 to 7 and Comparative Examples 1 to 6 and Reference Example were mixed immediately after compounding and at a temperature of 20 ° C.
The viscosity (25 ° C., E-type viscometer) after standing for a day was measured. In addition, the appearance of the varnish stored immediately after and after mixing at 10 ° C. for 1 to 10 days was observed. Table 1 shows the results. Poor (1) to (3) for varnish appearance in the table means (1) cyanate compound or flame retardant is insoluble, (2) cyanate compound recrystallized, (3) flame retardant means recrystallized, respectively. . Good in the table means that there are no defects (1) to (3).
【００３９】得られた配合直後のワニスを、厚み０．２
ｍｍのガラス織布（Ｅガラス、坪量２１０ｇ／ｍ2）に
樹脂分約４１重量％となるように含浸、乾燥してプリプ
レグを得た。得られたプリプレグについて、表面の外観
を目視で、内部を顕微鏡で観察した。その結果を表１に
示す。プリプレグ表面の外観について表中の良好とは、
ゆずはだ、はじきの発生又は難燃剤の析出がないことを
意味する。また、プリプレグ内部について表中の良好と
はボイドの発生がないことを意味する。The obtained varnish immediately after compounding was coated with a thickness of 0.2
mm woven glass (E glass, basis weight 210 g / m 2 ) was impregnated with a resin content of about 41% by weight and dried to obtain a prepreg. About the obtained prepreg, the external appearance of the surface was visually observed, and the inside was observed with a microscope. Table 1 shows the results. With regard to the appearance of the prepreg surface in the table is good,
It means that there is no occurrence of citron, repelling or deposition of flame retardant. In addition, “good” in the table for the inside of the prepreg means that no void is generated.
【００４０】次いで、得られたプリプレグ４枚を重ね、
その両最外層に厚み１８μｍの銅箔を配置し、１７０
℃、６０分間、２．５ＭＰａの条件で加熱加圧成形した
後、２３０℃で１２０分加熱処理し、厚み約０．８ｍｍ
の銅張積層板を作製した。得られた銅張積層板につい
て、誘電特性、はんだ耐熱性及び耐燃性を測定した。そ
の結果を表１に示す。Next, the four prepregs thus obtained were stacked,
An 18 μm thick copper foil was placed on both outermost layers,
After heating and pressing under the condition of 2.5 MPa at 60 ° C. for 60 minutes, heat treatment was performed at 230 ° C. for 120 minutes to obtain a thickness of about 0.8 mm.
Was produced. With respect to the obtained copper-clad laminate, dielectric properties, solder heat resistance and flame resistance were measured. Table 1 shows the results.
【００４１】銅張積層板の特性評価方法は以下の通りで
ある。 １ＭＨｚ比誘電率（εｒ）及び誘電正接（ｔａｎδ）：
ＪＩＳ−Ｃ−６４８１に準拠して測定した。 １ＧＨｚ比誘電率（εｒ）及び誘電正接（ｔａｎδ）：
トリプレート構造直線線路共振器法により測定した。 はんだ耐熱性：銅箔をエッチングし、ＰＣＴ（１２１
℃，０．２２ＭＰａ）中に保持した後、２６０℃の溶融
はんだに２０秒浸漬して、外観を調べた。表中の異常無
しとは、ミーズリング及びふくれの発生が無いことを意
味し、試験数を分母に、そして試験数の内異常の無い個
数を分子に示した。 耐燃性：ＵＬ−９４垂直試験法に準拠して測定した。The method for evaluating the characteristics of the copper-clad laminate is as follows. 1 MHz dielectric constant (εr) and dielectric loss tangent (tan δ):
It measured according to JIS-C-6481. 1 GHz relative dielectric constant (εr) and dielectric loss tangent (tan δ):
It was measured by the triplate structure straight line resonator method. Solder heat resistance: PCT (121
(0.2 ° C., 0.22 MPa), immersed in molten solder at 260 ° C. for 20 seconds, and examined for appearance. "No abnormality" in the table means that no measling and blistering occurred, and the number of tests was shown in the denominator, and the number of tests without abnormality was shown in the numerator. Flame resistance: measured in accordance with the UL-94 vertical test method.
【００４２】表１から明らかなように、本発明の実施例
１〜７のワニスは何れもシアネート類化合物や難燃剤の
析出がなく、これら実施例の銅張積層板は、吸湿時のは
んだ耐熱性が良好でかつ誘電特性に優れ、特に高周波帯
（１ＧＨｚ）での比誘電率、誘電正接の値が低く良好で
ある。これに対して、比較例１〜３のシアネート類化合
物と反応性を有する難燃剤を用いた銅張積層板は、各実
施例の銅張積層板と比較して比誘電率、誘電正接が共に
高く、特に１ＧＨｚでの誘電正接が更に高くなってい
る。また、これらの銅張積層板は吸湿時のはんだ耐熱性
が各実施例に比べて低い。一方、実施例同様シアネート
類化合物との反応性を有しない難燃剤を用いた比較例
４、５、６及び参考例の銅張積層板は誘電特性は良好で
あったが、室温で配合した比較例４についてはワニス保
存３日後に難燃剤が析出し、シアナト基の反応率が８％
と低い参考例については２日後にシアネート類化合物の
モノマ及び難燃剤が析出した。メチルエチルケトンから
トルエンに代え、室温で配合した比較例６については、
配合直後のワニス粘度が高くポットライフも著しく低下
し（保存７日後にはゲル化した）、このワニスを用いた
プリプレグの内部にはボイドが生じ、表面にはゆずはだ
及びはじきが発生した。またこのワニスは保存５日後に
難燃剤が析出した。また、室温で配合した比較例５につ
いては難燃剤が溶解できなかった。この難燃剤の溶解し
ていないワニスを用いて作製したプリプレグは表面に難
燃剤が不均一に散らばっているのが観察され、さらにこ
のプリプレグを用いた積層板は吸湿後のはんだ耐熱性が
劣り、耐燃性試験では全焼した。As is clear from Table 1, the varnishes of Examples 1 to 7 of the present invention did not have any precipitation of cyanate compounds or flame retardants. It has good properties and excellent dielectric properties, and particularly low values of relative permittivity and dielectric loss tangent in a high frequency band (1 GHz). On the other hand, the copper clad laminates using the flame retardant having reactivity with the cyanate compounds of Comparative Examples 1 to 3 have both a relative dielectric constant and a dielectric loss tangent as compared with the copper clad laminates of the respective examples. The dielectric loss tangent at 1 GHz is particularly high. Further, these copper-clad laminates have lower solder heat resistance at the time of moisture absorption than the respective examples. On the other hand, the copper-clad laminates of Comparative Examples 4, 5, 6 and the reference example using flame retardants having no reactivity with cyanate compounds as in the example had good dielectric properties, but were compared at room temperature. In Example 4, the flame retardant was precipitated 3 days after the varnish storage, and the reaction rate of the cyanato group was 8%.
In the case of the low reference example, the monomer of the cyanate compound and the flame retardant were precipitated after 2 days. For Comparative Example 6 in which methyl ethyl ketone was replaced with toluene and blended at room temperature,
The varnish viscosity immediately after blending was high, and the pot life was remarkably reduced (gelled after 7 days of storage). Voids were formed inside the prepreg using this varnish, and tingling and repelling occurred on the surface. In addition, in this varnish, a flame retardant was deposited after 5 days of storage. In Comparative Example 5 blended at room temperature, the flame retardant could not be dissolved. In the prepreg prepared using the varnish in which the flame retardant is not dissolved, it is observed that the flame retardant is scattered unevenly on the surface, and the laminate using the prepreg has poor solder heat resistance after absorbing moisture, In the fire resistance test, it was completely burned.
【００４３】[0043]
【発明の効果】本発明の印刷配線板用難燃性樹脂組成物
の製造方法によって得られるワニスは、樹脂組成物の溶
解性や保存安定性が良好で、かつ印刷配線板にした場
合、耐燃性や吸湿時の耐熱性に優れ、高周波領域での比
誘電率及び誘電正接が低く誘電特性に優れ高周波信号を
扱う機器に用いる印刷配線板として好適である。The varnish obtained by the method for producing a flame-retardant resin composition for a printed wiring board of the present invention has good solubility and storage stability of the resin composition and, when formed into a printed wiring board, has a high flammability resistance. It is excellent in heat resistance and heat resistance at the time of moisture absorption, has a low relative dielectric constant and dielectric loss tangent in a high frequency range, has excellent dielectric properties, and is suitable as a printed wiring board used in a device that handles a high frequency signal.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐瀬 茂雄 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館研究所内 Ｆターム(参考） 4F070 AA56 AC33 AE07 4J002 CM021 EB096 EB137 EU187 FD136 FD137 GQ00 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Shigeo Sase 1500 Oji Ogawa, Shimodate City, Ibaraki Prefecture F-term in Shimodate Research Laboratory, Hitachi Chemical Co., Ltd. 4F070 AA56 AC33 AE07 4J002 CM021 EB096 EB137 EU187 FD136 FD137 GQ00
Claims (6)
ナト基を２つ以上含有するシアネート類化合物を予め反
応させて得られるシアネートエステルオリゴマー、
（Ｂ）式（１）で示されるシアネート類化合物との反応
性を有しない難燃剤を必須成分として配合する樹脂組成
物において、（Ａ）シアネートエステルオリゴマーと
（Ｂ）シアネート類化合物との反応性を有しない難燃剤
とを５０〜１５０℃の温度で混合又は溶融することを特
徴とする印刷配線板用難燃性樹脂組成物の製造方法。 【化１】 (A) a cyanate ester oligomer obtained by previously reacting a cyanate compound having two or more cyanate groups in a molecule represented by the formula (1),
(B) In a resin composition containing a flame retardant having no reactivity with the cyanate compound represented by the formula (1) as an essential component, the reactivity between (A) the cyanate ester oligomer and (B) the cyanate compound A method for producing a flame-retardant resin composition for printed wiring boards, comprising mixing or melting a flame retardant having no resin at a temperature of 50 to 150 ° C. Embedded image
を２つ以上含有するシアネート類化合物が、２，２−ビ
ス（４−シアナトフェニル）プロパン、ビス（４−シア
ナトフェニル）エタン、ビス（３，５−ジメチル−４−
シアナトフェニル）メタン、２，２−ビス（４−シアナ
トフェニル）−１，１，１，３，３，３−ヘキサフルオ
ロプロパン、α，α’−ビス（４−シアナトフェニル）
−ｍ−ジイソプロピルベンゼンまたはフェノール付加ジ
シクロペンタジエン重合体のシアネート類化合物から選
ばれる１種類又は２種類以上の混合物である請求項１に
記載の印刷配線板用難燃性樹脂組成物の製造方法。2. A cyanate compound having two or more cyanato groups in a molecule represented by the formula (1) is 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) Ethane, bis (3,5-dimethyl-4-
Cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl)
The method for producing a flame-retardant resin composition for a printed wiring board according to claim 1, wherein the composition is one kind or a mixture of two or more kinds of cyanate compounds of m-diisopropylbenzene or a phenol-added dicyclopentadiene polymer.
ナト基を２つ以上含有するシアネート類化合物を予め反
応させて得られるシアネートエステルオリゴマーにおい
て、シアナト基の反応率が１０〜７０％であることを特
徴とする請求項１または請求項２に記載の印刷配線板用
難燃性樹脂組成物の製造方法。3. (A) In a cyanate ester oligomer obtained by previously reacting a cyanate compound having two or more cyanate groups in a molecule represented by the formula (1), the reaction rate of the cyanate group is 10 to 70. %. The method for producing a flame-retardant resin composition for a printed wiring board according to claim 1, wherein
有しない難燃剤が、１，２−ジブロモ−４−（１，２−
ジブロモエチル）シクロヘキサン、テトラブロモシクロ
オクタンまたはヘキサブロモシクロドデカンから選ばれ
る脂肪族環型難燃剤の少なくとも１種類以上である請求
項１ないし請求項３のいずれかに記載の印刷配線板用難
燃性樹脂組成物の製造方法。4. The flame retardant having no reactivity with the cyanate compound (B) is 1,2-dibromo-4- (1,2-
The flame retardancy for a printed wiring board according to any one of claims 1 to 3, which is at least one kind of an aliphatic cyclic flame retardant selected from dibromoethyl) cyclohexane, tetrabromocyclooctane, and hexabromocyclododecane. A method for producing a resin composition.
ナト基を２つ以上含有するシアネート類化合物との反応
性を有しない難燃剤が、式（２）で示される複素環型難
燃剤またはこれらの少なくとも１種類以上とシアネート
類化合物との反応性を有しない難燃剤との混合物である
請求項１ないし請求項３のいずれかに記載の印刷配線板
用難燃性樹脂組成物の製造方法。 【化２】 5. A flame retardant which does not react with a cyanate compound having two or more cyanato groups in a molecule represented by the formula (1): (B) a heterocyclic type represented by the formula (2): The flame-retardant resin composition for a printed wiring board according to any one of claims 1 to 3, which is a mixture of a flame retardant or a flame retardant having no reactivity with at least one or more of these compounds and a cyanate compound. Manufacturing method. Embedded image
載の印刷配線板用難燃性樹脂組成物の製造方法により得
られた印刷配線板用難燃性樹脂組成物。6. A flame-retardant resin composition for a printed wiring board obtained by the method for producing a flame-retardant resin composition for a printed wiring board according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10269689A JP2000095938A (en) | 1998-09-24 | 1998-09-24 | Production of flame-retardant resin composition for printed wiring board and such composition obtained thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10269689A JP2000095938A (en) | 1998-09-24 | 1998-09-24 | Production of flame-retardant resin composition for printed wiring board and such composition obtained thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000095938A true JP2000095938A (en) | 2000-04-04 |
Family
ID=17475827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10269689A Pending JP2000095938A (en) | 1998-09-24 | 1998-09-24 | Production of flame-retardant resin composition for printed wiring board and such composition obtained thereby |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000095938A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007049422A1 (en) | 2005-10-25 | 2007-05-03 | Mitsubishi Gas Chemical Company, Inc. | Cyanate ester polymer |
| WO2013021869A1 (en) | 2011-08-09 | 2013-02-14 | 三菱瓦斯化学株式会社 | Novel cyanic acid ester compound, method for producing same, curable resin composition containing novel cyanic acid ester compound, and cured product of curable resin composition |
| US9706651B2 (en) | 2011-12-07 | 2017-07-11 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, and laminate |
-
1998
- 1998-09-24 JP JP10269689A patent/JP2000095938A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007049422A1 (en) | 2005-10-25 | 2007-05-03 | Mitsubishi Gas Chemical Company, Inc. | Cyanate ester polymer |
| US9169356B2 (en) | 2005-10-25 | 2015-10-27 | Mitsubishi Gas Chemical Company, Inc. | Cyanate ester polymer |
| WO2013021869A1 (en) | 2011-08-09 | 2013-02-14 | 三菱瓦斯化学株式会社 | Novel cyanic acid ester compound, method for producing same, curable resin composition containing novel cyanic acid ester compound, and cured product of curable resin composition |
| KR20140046007A (en) | 2011-08-09 | 2014-04-17 | 미츠비시 가스 가가쿠 가부시키가이샤 | Novel cyanic acid ester compound, method for producing same, curable resin composition containing novel cyanic acid ester compound, and cured product of curable resin composition |
| US10155835B2 (en) | 2011-08-09 | 2018-12-18 | Mitsubishi Gas Chemical Company, Inc. | Cyanate ester compound and method for producing the same, and curable resin composition comprising the compound, and cured product thereof composition |
| US9706651B2 (en) | 2011-12-07 | 2017-07-11 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, and laminate |
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