JPH11189718A - Modified cyanate ester-based curable resin composition for laminated plate, and prepreg and metal-lined laminated plate using the same - Google Patents
Modified cyanate ester-based curable resin composition for laminated plate, and prepreg and metal-lined laminated plate using the sameInfo
- Publication number
- JPH11189718A JPH11189718A JP36022597A JP36022597A JPH11189718A JP H11189718 A JPH11189718 A JP H11189718A JP 36022597 A JP36022597 A JP 36022597A JP 36022597 A JP36022597 A JP 36022597A JP H11189718 A JPH11189718 A JP H11189718A
- Authority
- JP
- Japan
- Prior art keywords
- cyanate ester
- resin composition
- weight
- compound
- curable resin
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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
て低損失性が求められる無線通信関連の端末機器やアン
テナ、マイクロプロセッサの動作周波数が数百ＭＨｚを
超えるような高速コンピュータなどに用いられる印刷配
線板用の基板を製造するのに適した積層板用変性シアネ
ートエステル系硬化性樹脂組成物並びにこれを用いたプ
リプレグ及び金属張り積層板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed wiring used in terminal equipment and antennas for wireless communication requiring low loss in a high frequency band, and high-speed computers in which the operating frequency of a microprocessor exceeds several hundred MHz. TECHNICAL FIELD The present invention relates to a modified cyanate ester-based curable resin composition for a laminate suitable for producing a board for a board, and a prepreg and a metal-clad laminate using the same.
【０００２】[0002]
【従来の技術】高度情報化社会では大量のデータを高速
で処理する必要があり、コンピュータや情報機器端末な
どでは信号の高周波化が進んでいる。しかしながら、電
気信号は周波数が高くなる程伝送損失が大きくなるとい
う性質があり、高周波化に対応した低損失性の印刷配線
板の開発が強く求められている。2. Description of the Related Art In an advanced information society, it is necessary to process a large amount of data at a high speed, and the frequency of signals in computers and information equipment terminals is increasing. However, the electrical signal has a property that the transmission loss increases as the frequency increases, and there is a strong demand for the development of a low-loss printed wiring board corresponding to a higher frequency.
【０００３】印刷配線板での伝送損失は、配線（導体）
の形状、表皮抵抗、特性インピーダンス等で決まる導体
損と配線周りの絶縁層（誘電体）の誘電特性で決まる誘
電体損とからなり、高周波回路では誘電体損による電力
ロスの影響が大きい。したがって、高周波回路の伝送損
失を低減するためにはプリント配線板用基板（特に絶縁
樹脂）の低誘電率及び低誘電正接（ｔａｎδ）化が必要
と考えられる。例えば、高周波信号を扱う移動体通信関
連の機器では、信号の高周波化に伴い準マイクロ波帯
（１〜３ＧＨｚ）での伝送損失を少なくするため誘電正
接の低い基板が強く望まれるようになっている。[0003] The transmission loss in a printed wiring board is determined by the wiring (conductor).
And the dielectric loss determined by the dielectric properties of the insulating layer (dielectric) around the wiring, and the power loss due to the dielectric loss is large in a high-frequency circuit. Therefore, it is considered necessary to reduce the dielectric constant and the dielectric loss tangent (tan δ) of the printed wiring board substrate (especially insulating resin) in order to reduce the transmission loss of the high-frequency circuit. For example, in a mobile communication related device that handles a high-frequency signal, a substrate having a low dielectric loss tangent is strongly desired in order to reduce a transmission loss in a quasi-microwave band (1 to 3 GHz) as the signal becomes higher in frequency. I have.
【０００４】またコンピュータなどの電子情報機器で
は、大量の情報を短時間で処理するために動作周波数が
２００ＭＨｚを超える高速マイクロプロセッサの開発や
信号の高周波化が進んでいる。このような高速パルス信
号を扱う機器では印刷配線板上での遅延が問題になって
きた。印刷配線板での信号遅延時間は配線まわりの絶縁
物の比誘電率εｒの平方根に比例して長くなるため、コ
ンピュータなどに用いられる配線板では誘電率の低い基
板用樹脂が要求されている。In electronic information devices such as computers, the development of high-speed microprocessors whose operating frequency exceeds 200 MHz and the use of high-frequency signals are progressing in order to process a large amount of information in a short time. In a device handling such a high-speed pulse signal, a delay on a printed wiring board has become a problem. Since the signal delay time in a printed wiring board becomes longer in proportion to the square root of the relative permittivity εr of the insulator around the wiring, a resin for a substrate having a low dielectric constant is required for a wiring board used in a computer or the like.
【０００５】以上のような信号の高周波化に対応し印刷
配線板の高周波特性を改善する樹脂組成物として、熱硬
化性樹脂の中で最も誘電率が低いシアネートエステル樹
脂による組成物として、特公昭４６−４１１１２号公報
に示されているシアネートエステル／エポキシ樹脂組成
物、特公昭５２−３１２７９号公報に示されているビス
マレイミド／シアネートエステル／エポキシ樹脂組成物
を用いる方法がある。As a resin composition for improving the high-frequency characteristics of a printed wiring board in response to the increase in the signal frequency as described above, a composition made of a cyanate ester resin having the lowest dielectric constant among thermosetting resins has been proposed. There is a method using a cyanate ester / epoxy resin composition disclosed in JP-A-46-41112 and a bismaleimide / cyanate ester / epoxy resin composition disclosed in JP-B-52-31279.
【０００６】また熱可塑性樹脂を用いて高周波特性を改
善するものとして、特公平５−７７７０５号公報に示さ
れているポリフェニレンエーテル樹脂（ＰＰＯ又はＰＰ
Ｅ）と架橋性ポリマ／モノマとの樹脂組成物及び特公平
６−９２５３３号公報に示されている特定の硬化性官能
基を持つポリフェニレンエーテル樹脂と架橋性モノマと
の樹脂組成物等のように耐熱性熱可塑性樹脂の中では誘
電特性が良好なポリフェニレンエーテル系樹脂組成物を
用いる方法がある。[0006] In order to improve high-frequency characteristics using a thermoplastic resin, a polyphenylene ether resin (PPO or PP) disclosed in Japanese Patent Publication No. 5-77705 has been proposed.
E) and a resin composition of a crosslinkable polymer / monomer and a resin composition of a polyphenylene ether resin having a specific curable functional group and a crosslinkable monomer as disclosed in JP-B-6-92533. Among the heat-resistant thermoplastic resins, there is a method using a polyphenylene ether-based resin composition having good dielectric properties.
【０００７】また誘電率が低いシアネートエステル樹脂
と誘電特性が良好なポリフェニレンエーテル樹脂からな
る樹脂組成物を用いて高周波特性を改善するものとし
て、特公昭６３−３３５０６号公報に示されているシア
ネートエステル／ビスマレイミドとポリフェニレンエー
テル樹脂との樹脂組成物、特開平５−３１１０７１号公
報に示されているフェノール変性樹脂／シアネートエス
テル反応物とポリフェニレンエーテル樹脂との樹脂組成
物を用いる方法がある。更に高周波特性の良い耐熱性成
形材料として、特公昭６１−１８９３７号公報に示され
ているようにポリフェニレンエーテル樹脂にシアネート
エステル樹脂を混練した樹脂組成物がある。Japanese Patent Publication No. 63-33506 discloses a cyanate ester disclosed in Japanese Patent Publication No. 33506/1988 for improving high frequency characteristics by using a resin composition comprising a cyanate ester resin having a low dielectric constant and a polyphenylene ether resin having a good dielectric property. / A resin composition of bismaleimide and a polyphenylene ether resin, and a method using a resin composition of a phenol-modified resin / cyanate ester reactant and a polyphenylene ether resin described in JP-A-5-311071. Further, as a heat-resistant molding material having better high-frequency characteristics, there is a resin composition obtained by kneading a cyanate ester resin with a polyphenylene ether resin as disclosed in JP-B-61-18937.
【０００８】[0008]
【発明が解決しようとする課題】特公昭４６−４１１１
２号公報や特公昭５２−３１２７９号公報に示される方
法は、誘電率が若干低くなるもののシアネートエステル
樹脂以外の他の熱硬化性樹脂を含有しているため高周波
特性が不十分という問題点があった。[Problems to be Solved by the Invention] JP-B-46-4111
The method disclosed in Japanese Patent Publication No. 2 and JP-B-52-31279 has a problem that the high-frequency characteristics are insufficient because it contains a thermosetting resin other than the cyanate ester resin, although the dielectric constant is slightly lowered. there were.
【０００９】特公平５−７７７０５号公報や特公平６−
９２５３３号公報に示される方法は、誘電特性は改善さ
れるものの、本来熱可塑性ポリマであるポリフェニレン
エーテル樹脂を主体としているために樹脂組成物の溶融
粘度が高く流動性が不足するという問題点があった。し
たがって、積層板をプレス成形する時に高温高圧が必要
となったり、微細な回路パターン間の溝を埋める必要の
有る多層印刷配線板を製造するには成形性が悪くて不適
であった。[0009] Japanese Patent Publication No. Hei 5-77705 and Japanese Patent Publication No.
The method disclosed in Japanese Patent No. 92533 has a problem that although the dielectric properties are improved, the melt viscosity of the resin composition is high and the fluidity is insufficient because the resin composition is mainly composed of a polyphenylene ether resin which is originally a thermoplastic polymer. Was. Therefore, the moldability is poor and unsuitable for manufacturing a multilayer printed wiring board that requires high temperature and high pressure when press-forming a laminated board or that needs to fill in the grooves between fine circuit patterns.
【００１０】特公昭６３−３３５０６号公報や特開平５
−３１１０７１号公報に示される方法は、ポリフェニレ
ンエーテル樹脂と併用する熱硬化性樹脂がビスマレイミ
ド／シアネートエステル樹脂やフェノール変性樹脂／シ
アネートエステル反応物であるため、誘電特性が若干改
善されるものの高周波特性は依然として不十分であると
いう問題点があった。なお、高周波特性を良くするため
にポリフェニレンエーテル樹脂の配合量を増加すると前
述のポリフェニレンエーテル系樹脂組成物と同様に樹脂
組成物の溶融粘度が高くなって流動性が不足するため成
形性が悪いという問題点があった。[0010] Japanese Patent Publication No. 63-33506 and Japanese Patent Laid-Open No.
In the method disclosed in JP-A-311071, since the thermosetting resin used in combination with the polyphenylene ether resin is a bismaleimide / cyanate ester resin or a phenol-modified resin / cyanate ester reactant, the dielectric properties are slightly improved but the high-frequency properties are improved. Was still insufficient. In addition, when the compounding amount of the polyphenylene ether resin is increased in order to improve the high frequency characteristics, the melt viscosity of the resin composition becomes high similarly to the above-mentioned polyphenylene ether-based resin composition, and the fluidity is insufficient, so that the moldability is poor. There was a problem.
【００１１】また特公昭６１−１８９３７号公報に示さ
れるポリフェニレンエーテル樹脂にシアネートエステル
樹脂を混練した樹脂組成物は、誘電特性が良好であり、
かつシアネートエステル樹脂で変性すると溶融粘度が低
くなるために樹脂組成物の成形性も比較的良好であるも
のの、硬化性成分としてシアネートエステルを単独で用
いるとその樹脂硬化物の誘電特性は誘電正接が誘電率の
値の割に高いという傾向にあり、高周波帯域の伝送損失
を十分に低減できないという問題点があった。さらに、
誘電正接を低くするためシアネートエステルの配合量を
少なく（ポリフェニレンエーテルの配合量を増加）する
と前述のポリフェニレンエーテル系樹脂組成物と同様に
樹脂組成物の溶融粘度が高なって流動性が不足するため
成形性が悪いという問題点があった。A resin composition obtained by kneading a cyanate ester resin with a polyphenylene ether resin disclosed in JP-B-61-18937 has good dielectric properties,
And when modified with a cyanate ester resin, the melt viscosity becomes low, so that the moldability of the resin composition is relatively good.However, when cyanate ester is used alone as a curable component, the dielectric properties of the resin cured product have a dielectric loss tangent. It tends to be higher than the value of the dielectric constant, and there is a problem that transmission loss in a high frequency band cannot be sufficiently reduced. further,
When the compounding amount of the cyanate ester is reduced (the compounding amount of the polyphenylene ether is increased) in order to lower the dielectric loss tangent, the melt viscosity of the resin composition becomes high and the fluidity becomes insufficient similarly to the aforementioned polyphenylene ether-based resin composition. There was a problem that the moldability was poor.
【００１２】このような状況に鑑みて本発明者らは、先
に特定のシアネートエステル樹脂を１価フェノール類化
合物で変性した組成物をマトリックス樹脂の一部または
全部に用いる方法（特願平９−８００３３号）を提案し
た。しかしながら、特定のシアネートエステル樹脂を１
価フェノール類化合物で変性することによって高周波特
性が良好な樹脂組成物を得ることができたが、使用して
いる特定のシアネートエステル樹脂が特殊かつ高価であ
るという問題点があった。In view of such circumstances, the present inventors have proposed a method in which a composition obtained by modifying a specific cyanate ester resin with a monohydric phenol compound is used for a part or all of a matrix resin (Japanese Patent Application No. Hei 9 (1994) -207,197). No. -80033). However, a particular cyanate ester resin is
Although a resin composition having good high-frequency characteristics could be obtained by modification with a polyhydric phenol compound, there was a problem that the specific cyanate ester resin used was special and expensive.
【００１３】本発明は、耐熱性が良好で、従来のエポキ
シ樹脂などの熱硬化性樹脂積層板と同様な成形性及び加
工性を具備し、かつ誘電特性、高周波帯域での誘電正接
が低く低損失性に優れた高密度多層配線板製造が可能な
積層板用変性シアネートエステル系硬化性樹脂組成物並
びにこれを用いたプリプレグ及び金属張り積層板を提供
するものである。The present invention has good heat resistance, has moldability and workability similar to those of conventional thermosetting resin laminates such as epoxy resin, and has low dielectric properties and low dielectric loss tangent in a high frequency band. An object of the present invention is to provide a modified cyanate ester-based curable resin composition for a laminate capable of producing a high-density multilayer wiring board excellent in loss property, and a prepreg and a metal-clad laminate using the same.
【００１４】[0014]
【課題を解決するための手段】本発明は、（Ａ）式
（１）で示されるシアネートエステル類化合物、（Ｂ）
式（２）で示される１価フェノール類化合物、（Ｃ）ジ
シクロペンタジエン樹脂、（Ｄ）シアネートエステル類
化合物と反応性を有しない難燃剤及び（Ｅ）金属系反応
触媒を必須成分として含有する高周波特性に優れた積層
板用変性シアネートエステル系硬化性樹脂組成物並びに
これを用いたプリプレグ及び金属張り積層板である。The present invention relates to (A) a cyanate ester compound represented by the formula (1), (B)
It contains, as essential components, a monohydric phenol compound represented by the formula (2), (C) a dicyclopentadiene resin, (D) a flame retardant having no reactivity with a cyanate ester compound, and (E) a metal-based reaction catalyst. A modified cyanate ester-based curable resin composition for a laminate excellent in high frequency characteristics, and a prepreg and a metal-clad laminate using the same.
【００１５】[0015]
【化４】 Embedded image
【００１６】[0016]
【化５】 Embedded image
【００１７】また更に加えて本発明は、（Ａ）式（１）
で示されるシアネートエステル類化合物の１００重量部
に対して（Ｂ）式（２）で示される１価フェノール類化
合物を４〜３０重量部配合して反応させて得られる変性
シアネートエステル系樹脂を用いることを特徴とする、
高周波帯域での誘電正接が低く低損失性に優れる積層板
用変性シアネートエステル系硬化性樹脂組成物並びにこ
れを用いたプリプレグ及び金属張り積層板である。Still further, the present invention provides a method of formula (A), wherein
(B) A modified cyanate ester-based resin obtained by mixing and reacting 4 to 30 parts by weight of a monohydric phenol compound represented by formula (2) with 100 parts by weight of the cyanate ester compound represented by formula (2) Characterized by the fact that
A modified cyanate ester-based curable resin composition for a laminate having a low dielectric loss tangent in a high frequency band and excellent in low loss property, and a prepreg and a metal-clad laminate using the same.
【００１８】[0018]
【発明の実施の形態】高分子材料など誘電特性は双極子
の配向分極による影響が大きく、したがって分子内の極
性基を少なくすることにより低誘電率化が図れ、また極
性基の運動性を抑えることにより誘電正接を低くするこ
とが可能である。シアネートエステル樹脂は、極性の強
いシアナト基を有していながら硬化時には対称性かつ剛
直なトリアジン構造を生成するので、熱硬化性樹脂とし
ては最も低い誘電率及び誘電正接の硬化物が得られると
いう特徴がある。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Dielectric properties such as polymer materials are greatly affected by the orientation polarization of dipoles. Therefore, by reducing the number of polar groups in the molecule, the dielectric constant can be reduced, and the mobility of polar groups can be suppressed. Thereby, the dielectric loss tangent can be reduced. The cyanate ester resin has a strong polar cyanato group, but generates a symmetric and rigid triazine structure during curing, so that a cured product having the lowest dielectric constant and dielectric loss tangent as a thermosetting resin can be obtained. There is.
【００１９】しかしながら、実際の硬化反応において
は、シアネートエステル樹脂中のすべてのシアナト基が
反応してトリアジン構造を生成するということは不可能
であり、硬化反応の進行に伴って反応系が流動性を失い
未反応のシアナト基として系内に残存することになる。
その結果、これまでは本来の硬化物より誘電率や誘電正
接の高い硬化物しか得られなかった。However, in the actual curing reaction, it is impossible that all the cyanato groups in the cyanate ester resin react to form a triazine structure, and as the curing reaction proceeds, the reaction system becomes more fluid. And remains in the system as an unreacted cyanato group.
As a result, hitherto, only a cured product having a higher dielectric constant and a higher dielectric tangent than the original cured product has been obtained.
【００２０】これに対して本発明の積層板用変性シアネ
ートエステル系硬化性樹脂組成物では、（Ｂ）１価フェ
ノール類化合物を適正量配合することで未反応として残
るシアナト基をイミドカーボネート化してその極性を減
じることにより硬化物の誘電率と誘電正接を低下させ、
更にジシクロペンタジエン樹脂の併用により一段と誘電
特性に優れた樹脂組成物を得たものである。この目的で
用いる材料としては、シアナト基との反応性が高く、ま
た単官能で比較的低分子量でありかつシアネートエステ
ル樹脂との相溶性が良い（分子構造に類似性があり）化
合物が適していると考えられる。本発明の積層板用変性
シアネートエステル系硬化性樹脂組成物で用いている一
価のフェノール類化合物は、このような理由によって特
定された化合物である。On the other hand, in the modified cyanate ester-based curable resin composition for laminates of the present invention, by mixing an appropriate amount of the (B) monohydric phenol compound, the cyanate group remaining as unreacted is converted to imide carbonate. Decreasing the polarity reduces the dielectric constant and dielectric loss tangent of the cured product,
Further, a resin composition having more excellent dielectric properties was obtained by using a dicyclopentadiene resin in combination. As a material used for this purpose, a compound having high reactivity with a cyanato group, a monofunctional compound having a relatively low molecular weight, and having good compatibility with a cyanate ester resin (having similarity in molecular structure) is suitable. It is thought that there is. The monovalent phenol compound used in the modified cyanate ester-based curable resin composition for a laminate of the present invention is a compound specified for such a reason.
【００２１】従来、シアネートエステルの三量化反応
（トリアジン環の生成）の助触媒として、ノニルフェノ
ール等のフェノール化合物はシアネートエステル１００
重量部に対して１〜２重量部程度用いられていた。しか
し、配合量が触媒量であったため上記のような、未反応
のシアナト基と反応し低極性化するという効果は認めら
れなかった。しかるに本発明者らがフェノール化合物の
配合量について検討した結果、フェノール化合物を従来
よりも多量に配合することにより硬化物の誘電率と誘電
正接が低下することを認め、かつ特定の一価フェノール
類化合物を用いれば、配合量が増える事による耐熱性の
低下も抑制できることを見出した。そのため本発明の方
法によれば、これまでのシアネートエステル樹脂単独の
硬化物や、従来のエポキシ樹脂や多価フェノール類（片
方の水酸基が未反応基として残り易いため誘電特性をか
えって悪化させる）及びビスマレイミド等を配合した樹
脂の硬化物よりも誘電率と誘電正接の低い硬化物が得ら
れるようになった。Conventionally, phenol compounds such as nonylphenol have been used as co-catalysts for the trimerization reaction of cyanate ester (formation of a triazine ring).
About 1 to 2 parts by weight based on parts by weight was used. However, since the compounding amount was a catalytic amount, the effect of lowering the polarity by reacting with the unreacted cyanato group as described above was not recognized. However, the present inventors examined the amount of the phenolic compound, and found that the incorporation of a larger amount of the phenolic compound lowers the dielectric constant and the dielectric loss tangent of the cured product. It has been found that if a compound is used, a decrease in heat resistance due to an increase in the compounding amount can be suppressed. Therefore, according to the method of the present invention, a cured product of a conventional cyanate ester resin alone, a conventional epoxy resin or a polyhydric phenol (one of the hydroxyl groups is likely to remain as an unreacted group, so that the dielectric properties are rather deteriorated) and A cured product having a lower dielectric constant and a lower dielectric loss tangent than a cured product of a resin containing bismaleimide or the like can be obtained.
【００２２】したがって本発明の積層板用変性シアネー
トエステル系硬化性樹脂組成物では、１価フェノール類
化合物の配合量が重要である。すなわち、配合量が少な
い場合は未反応として残存する全てのシアナト基と反応
し低極性化することができず、配合量が必要量より多い
場合はかえって自分自身が未反応として残存し、自身の
水酸基の極性によって硬化物の誘電特性を悪化させてし
まうことになるからである。Therefore, in the modified cyanate ester-based curable resin composition for a laminate of the present invention, the amount of the monohydric phenol compound is important. In other words, if the amount is small, it is not possible to react with all the cyanato groups remaining as unreacted to lower the polarity, and if the amount is more than the required amount, it itself remains unreacted and its own remains. This is because the polarity of the hydroxyl group deteriorates the dielectric properties of the cured product.
【００２３】さらに本発明の積層板用変性シアネートエ
ステル系硬化性樹脂組成物では、誘電特性が良好な
（Ｃ）ジシクロペンタジエン樹脂を上記の変性シアネー
トエステル樹脂に配合することにより誘電特性の向上を
図っている。シアネートエステル樹脂とジシクロペンタ
ジエン樹脂とは、本来非相容系であり均一な樹脂を得る
ことが困難であるが、本発明者らが見出した手法によれ
ば、（Ａ）シアネートエステル類化合物と（Ｂ）１価フ
ェノール類化合物の反応を、ジシクロペンタジエン樹脂
の溶媒溶液中で反応を行うと、いわゆる“セミＩＰＮ
（interpenetrating polymer network）化樹脂”が生成
し均一な樹脂溶液が得られることがわかった。Further, in the modified cyanate ester-based curable resin composition for a laminate according to the present invention, the dielectric properties are improved by blending (C) dicyclopentadiene resin having good dielectric properties with the above-mentioned modified cyanate ester resin. I'm trying. The cyanate ester resin and the dicyclopentadiene resin are originally incompatible with each other and it is difficult to obtain a uniform resin. However, according to the method discovered by the present inventors, (A) the cyanate ester compound and (B) When the reaction of the monohydric phenol compound is carried out in a solvent solution of dicyclopentadiene resin, a so-called “semi-IPN”
(Interpenetrating polymer network), and a uniform resin solution was obtained.
【００２４】また本発明の積層板用変性シアネートエス
テル系硬化性樹脂組成物において用いられる難燃剤は、
（Ａ）シアネートエステル類化合物と（Ｂ）１価フェノ
ール類化合物の反応を阻害しないようにシアネートエス
テル類化合物と反応性を有しないことが必須であり、炭
化水素系の低極性化合物であるため硬化物の誘電特性を
悪化させることが少ない。また、もう一種類の特定した
難燃剤は炭化水素系以外の化合物であってもシアネート
エステルの硬化物と同様なトリアジン構造をもっている
ためシアネートエステル樹脂硬化物に相容し易く、耐熱
性や誘電特性を悪化させることなく耐燃性を付与するこ
とができる。The flame retardant used in the modified cyanate ester-based curable resin composition for a laminate of the present invention includes:
It is essential that the cyanate ester compound has no reactivity with the cyanate ester compound so as not to inhibit the reaction between the cyanate ester compound and the (B) monohydric phenol compound. Deterioration of the dielectric properties of the product is small. Another type of flame retardant, even if it is a compound other than a hydrocarbon compound, has a triazine structure similar to that of a cured product of a cyanate ester, so it is easily compatible with a cured product of a cyanate ester resin, and has heat resistance and dielectric properties. Can be imparted without deteriorating the flame resistance.
【００２５】本発明の積層板用変性シアネートエステル
系硬化性樹脂組成物は、（Ａ）式（１）で示されるシア
ネートエステル類化合物、（Ｂ）式（２）で示される１
価フェノール類化合物、（Ｃ）ジシクロペンタジエン樹
脂、（Ｄ）シアネートエステル類化合物と反応性を有し
ない難燃剤及び（Ｅ）金属系反応触媒を必須成分とす
る。本発明における（Ａ）シアネートエステル類化合物
は，式（１）で示されように１分子中にシアナト基を２
個有するシアネートエステル類化合物である。式（１）
で示される化合物としては、例えば、ビス（４−シアナ
トフェニル）エタン、２，２−ビス（４−シアナトフェ
ニル）プロパン、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エステル化物等が挙げられ
る。その中でも、２，２−ビス（４−シアナトフェニ
ル）プロパン及びビス（３，５−ジメチル−４−シアナ
トフェニル）メタン等がより好ましい。また（Ａ）シア
ネートエステル類化合物は、一種類を単独で用いてもよ
く、又は二種類以上を混合して用いてもよい。The modified cyanate ester-based curable resin composition for a laminate of the present invention comprises (A) a cyanate ester compound represented by the formula (1) and (B) a cyanate ester compound represented by the formula (2).
The essential components are a phenolic compound, (C) a dicyclopentadiene resin, (D) a flame retardant having no reactivity with the cyanate ester compound, and (E) a metal-based reaction catalyst. The (A) cyanate ester compound according to the present invention has two cyanate groups in one molecule as shown in the formula (1).
This is a cyanate ester compound having two or more cyanate esters. Equation (1)
Examples of the compound represented by are bis (4-cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, , 2-Bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-
Examples include diisopropylbenzene and cyanate esterified products of phenol-added dicyclopentadiene polymer. Among them, 2,2-bis (4-cyanatophenyl) propane and bis (3,5-dimethyl-4-cyanatophenyl) methane are more preferred. As the cyanate ester compound (A), one type may be used alone, or two or more types may be used in combination.
【００２６】本発明における（Ｂ）１価フェノール類化
合物は、式（２）で示される１価フェノール類であり、
耐熱性の良好な化合物が好ましい。式（２）で示される
化合物としては、例えば、ｐ−（α−クミル）フェノー
ルが挙げらる。なお、（Ｂ）１価フェノール類化合物
は、一種類を単独で用いてもよく、又は二種類以上を混
合して用いてもよい。The (B) monohydric phenol compound in the present invention is a monohydric phenol represented by the formula (2):
Compounds having good heat resistance are preferred. Examples of the compound represented by the formula (2) include p- (α-cumyl) phenol. As the (B) monohydric phenol compound, one kind may be used alone, or two or more kinds may be used in combination.
【００２７】本発明における（Ｂ）１価フェノール類化
合物の配合量は、（Ａ）シアネートエステル類化合物１
００重量部に対して４〜３０重量部とするのが好まし
く、５〜３０重量部とすることがより好ましく、５〜２
５重量部とすることが特に好ましい。（Ｂ）１価フェノ
ール類化合物の配合量が４重量部未満では十分な誘電特
性が得られず、特に高周波帯域での誘電正接が十分に低
くならない傾向がある。また３０重量部を超えるとかえ
って誘電正接が高くなるという傾向があり望ましくな
い。したがって、本発明が提供する高周波帯において誘
電正接の低いシアネートエステル系樹脂硬化物を得るた
めには、（Ａ）シアネートエステル類化合物に対して適
切な配合量の（Ｂ）１価フェノール類化合物を配合する
必要がある。In the present invention, the compounding amount of the (B) monohydric phenol compound is (A) the cyanate ester compound 1
The amount is preferably 4 to 30 parts by weight, more preferably 5 to 30 parts by weight, and
Particularly preferred is 5 parts by weight. If the amount of the (B) monohydric phenol compound is less than 4 parts by weight, sufficient dielectric properties cannot be obtained, and the dielectric loss tangent particularly in a high frequency band tends not to be sufficiently low. If it exceeds 30 parts by weight, the dielectric loss tangent tends to be rather high, which is not desirable. Therefore, in order to obtain a cured product of a cyanate ester-based resin having a low dielectric tangent in the high frequency band provided by the present invention, an appropriate amount of the (B) monohydric phenol compound is added to the (A) cyanate ester compound. It needs to be blended.
【００２８】本発明における（Ａ）シアネートエステル
類化合物と（Ｂ）１価フエノール類化合物は、通常、そ
れぞれを反応させて得られる変性シアネートエステル樹
脂として用いられる。すなわち、（Ａ）シアネートエス
テル類化合物のプレポリマ化とともに、（Ａ）シアネー
トエステル類化合物に（Ｂ）１価フェノール類化合物を
付加させたイミドカーボネート化変性樹脂として用いら
れる。In the present invention, (A) the cyanate ester compound and (B) the monovalent phenol compound are generally used as a modified cyanate ester resin obtained by reacting each compound. That is, it is used as an imide carbonate-modified resin in which (A) a cyanate ester compound is prepolymerized and (B) a monohydric phenol compound is added to (A) a cyanate ester compound.
【００２９】（Ａ）シアネートエステル類化合物と
（Ｂ）１価フェノール類化合物を反応させる際には、
（Ｂ）１価フェノール類化合物を反応初期から上記の適
正配合量の全部を投入して反応させて変性シアネートエ
ステル樹脂としても良いし、反応初期は上記の適正配合
量の一部を反応させ、冷却後残りの（Ｂ）１価フェノー
ル類化合物を投入して、Ｂステージ化時あるいは硬化時
に反応させて変性シアネートエステル樹脂としても良
い。When reacting (A) a cyanate ester compound with (B) a monohydric phenol compound,
(B) A modified cyanate ester resin may be prepared by charging the monohydric phenolic compound from the initial stage of the reaction and then reacting by adding all of the above proper amount, or a part of the above proper amount may be reacted at the beginning of the reaction, After cooling, the remaining (B) monohydric phenol compound may be charged and reacted at the time of B-stage or at the time of curing to obtain a modified cyanate ester resin.
【００３０】本発明における（Ｃ）ジシクロペンタジエ
ン樹脂としては、エステル基や水酸基を含有するポリマ
であることがシアネートエステル類化合物との相溶性が
向上するため好ましい。本発明における（Ｃ）ジシクロ
ペンタジエン樹脂の配合量は、（Ａ）シアネートエステ
ル類化合物１００重量部に対して５〜３００重量部とす
ることが好ましく、１０〜２００重量部とすることがよ
り好ましく、１５〜１００重量部とすることが特に好ま
しい。（Ｃ）ジシクロペンタジエン樹脂の配合量が５重
量部未満では十分な誘電特性が得られなくなる傾向があ
り、３００重量部を超えると樹脂の溶融粘度が高くなっ
て流動性が不足するため成形性が悪くなり、また（Ａ）
シアネートエステル類の反応性も悪くなる傾向がある。The (C) dicyclopentadiene resin in the present invention is preferably a polymer containing an ester group or a hydroxyl group, because the compatibility with the cyanate ester compound is improved. In the present invention, the compounding amount of the (C) dicyclopentadiene resin is preferably from 5 to 300 parts by weight, more preferably from 10 to 200 parts by weight, per 100 parts by weight of the (A) cyanate ester compound. It is particularly preferred that the amount be 15 to 100 parts by weight. (C) If the amount of the dicyclopentadiene resin is less than 5 parts by weight, sufficient dielectric properties tend not to be obtained. If the amount exceeds 300 parts by weight, the melt viscosity of the resin becomes high and fluidity becomes insufficient, so that moldability is poor. Worsens and (A)
The reactivity of cyanate esters also tends to be poor.
【００３１】本発明における（Ｄ）シアネートエステル
類化合物と反応性を有しない難燃剤としては、例えば、
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ヘキサン、ヘキサブ
ロモシクロドデカン、ポリブロモジフェニルエーテル、
臭素化ポリスチレン、臭素化ポリカーボネート及び式
（３）で示される臭素化トリフェニルシアヌレート系難
燃剤等が挙げられ、その中でも、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、ヘキサブロモシクロドデカン、
２，４，６−トリス（トリブロモフェノキシ）−１，
３，５−トリアジン等が得られる硬化物の誘電特性が良
好であるのでより好ましい。Examples of the flame retardant having no reactivity with the cyanate ester compound (D) in the present invention include:
1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclohexane, hexabromocyclododecane, polybromodiphenyl ether,
Brominated polystyrene, brominated polycarbonate, brominated triphenyl cyanurate-based flame retardant represented by the formula (3), and the like, among which 1,2-dibromo-4,
-(1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane,
2,4,6-tris (tribromophenoxy) -1,
It is more preferable because the cured product from which 3,5-triazine or the like is obtained has good dielectric properties.
【００３２】[0032]
【化６】 Embedded image
【００３３】本発明における（Ｄ）シアネートエステル
類化合物と反応性を有しない難燃剤の配合量は、（Ａ）
シアネートエステル類化合物、（Ｂ）１価フェノール類
化合物及び（Ｃ）ジシクロペンタジエン樹脂の総量１０
０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特に好ましい。（Ｄ）シアネー
トエステル類化合物と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 having no reactivity with the cyanate ester compound (D) is (A)
Total amount of cyanate ester compound, (B) monohydric phenol compound and (C) dicyclopentadiene resin is 10
It is preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight, and more preferably 0 to 10 parts by weight.
Particularly preferred is 20 parts by weight. (D) If the compounding amount of the flame retardant having no reactivity with the cyanate ester compound is less than 5 parts by weight, the flame resistance tends to be insufficient,
If it exceeds 30 parts by weight, the heat resistance of the resin tends to decrease.
【００３４】本発明の（Ｅ）金属系反応触媒は、（Ａ）
シアネートエステル類化合物と（Ｂ）１価フェノール類
化合物との反応を促進するものであり、変性シアネート
系樹脂組成物を製造する際の反応触媒及び積層板を製造
する際の硬化促進剤として用いられる。金属系反応触媒
類としては、マンガン、鉄、コバルト、ニッケル、銅、
亜鉛等の金属触媒類が用いられ、具体的には、２−エチ
ルヘキサン酸塩やナフテン酸塩等の有機金属塩化合物及
びアセチルアセトン錯体などの有機金属錯体として用い
られる。変性シアネート系樹脂組成物を製造する際の反
応促進剤と積層板を製造する際の硬化促進剤で同一の金
属系反応触媒を単独で用いてもよく、又はそれぞれ別の
二種類以上を用いてもよい。The (E) metal-based reaction catalyst of the present invention comprises (A)
It promotes the reaction between the cyanate ester compound and the (B) monohydric phenol compound, and is used as a reaction catalyst when producing a modified cyanate-based resin composition and a curing accelerator when producing a laminate. . Metal-based reaction catalysts include manganese, iron, cobalt, nickel, copper,
A metal catalyst such as zinc is used, and specifically, an organic metal salt compound such as 2-ethylhexanoate and naphthenate and an organic metal complex such as an acetylacetone complex are used. The same metal-based reaction catalyst may be used alone in the reaction accelerator for producing the modified cyanate-based resin composition and the curing accelerator for producing the laminate, or using two or more different types each. Is also good.
【００３５】本発明における（Ｅ）金属系反応触媒の配
合量は、（Ａ）シアネートエステル類化合物１（ｇ）に
対して１〜３００ｐｐｍとすることが好ましく、２〜２
００ｐｐｍとすることがより好ましく、２〜１５０ｐｐ
ｍとすることがさらに好ましい。（Ｅ）金属系反応触媒
の配合量が、１ｐｐｍ未満では反応性及び硬化性が不十
分となる傾向があり、３００ｐｐｍを超えると反応の制
御が難しくなったり、硬化が速くなりすぎて成形性が悪
くなる傾向がある。また、本発明における（Ｅ）金属系
反応触媒の配合時期は、変性シアネート系樹脂組成物を
製造する際に反応促進剤及び硬化促進剤として必要な量
を同時にまとめて配合してもよいし、変性シアネート系
樹脂組成物を製造する際に変性反応の促進に必要な量を
用い、反応終了後残りの触媒又は別の金属系触媒を硬化
促進剤として添加混合してもよい。The amount of the metal-based reaction catalyst (E) in the present invention is preferably from 1 to 300 ppm, and more preferably from 2 to 2 ppm, based on 1 g of the cyanate ester compound (A).
More preferably, the concentration is set to 00 ppm.
m is more preferable. (E) If the amount of the metal-based reaction catalyst is less than 1 ppm, the reactivity and the curability tend to be insufficient. If the amount exceeds 300 ppm, the control of the reaction becomes difficult, and the curing becomes too fast, resulting in poor moldability. Tends to be worse. In addition, in the compounding time of the metal-based reaction catalyst (E) in the present invention, the amounts required as a reaction accelerator and a curing accelerator in producing the modified cyanate-based resin composition may be simultaneously combined, and When producing the modified cyanate-based resin composition, an amount necessary for accelerating the modification reaction may be used, and after completion of the reaction, the remaining catalyst or another metal-based catalyst may be added and mixed as a curing accelerator.
【００３６】本発明の積層板用変性シアネートエステル
系硬化性樹脂組成物には、上記必須成分以外に必要に応
じて無機充填剤及びその他添加剤を配合することができ
る。充填剤としては、シリカ、アルミナ、水酸化アルミ
ニウム、炭酸カルシウム、クレイ、タルク、窒化珪素、
窒化ホウ素、酸化チタン、チタン酸バリウム、チタン酸
鉛、チタン酸ストロンチウム等を使用することができ
る。この配合量としては、本発明の樹脂組成物の総量１
００重量部に対して、２５０重量部以下とすることが本
発明の樹脂組成物ワニスをガラス布などの基材に含浸す
る場合に、均一な樹脂付着量で、かつ、良好な外観を得
るため好ましい。The modified cyanate ester-based curable resin composition for a laminated board of the present invention may contain, if necessary, an inorganic filler and other additives in addition to the above essential components. As fillers, silica, alumina, aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride,
Boron nitride, titanium oxide, barium titanate, lead titanate, strontium titanate and the like can be used. The compounding amount may be set to 1
When the resin composition varnish of the present invention is impregnated into a substrate such as a glass cloth with respect to 00 parts by weight to 250 parts by weight or less, in order to obtain a uniform resin adhesion amount and a good appearance. preferable.
【００３７】以上説明した本発明の積層板用変性シアネ
ートエステル系硬化性樹脂組成物は、例えば、以下に示
すようにしてプリプレグ又は金属張り積層板の製造に供
せられる。すなわち本発明の積層板用変性シアネートエ
ステル系硬化性樹脂組成物を溶剤に溶解してワニスと
し、ガラス布など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。ついでこのプリプレグを１
枚若しくは任意の枚数重ねその上下面又は片面に金属箔
を重ねて加熱加圧成形することにより両面又は片面の金
属張り積層板とすることができる。The above-described modified cyanate ester-based curable resin composition for a laminate according to the present invention is used, for example, for producing a prepreg or a metal-clad laminate as shown below. That is, the modified cyanate ester-based curable resin composition for a laminate of the present invention is dissolved in a solvent to form a varnish, which is impregnated into a substrate such as a glass cloth and dried to prepare a prepreg. Then add this prepreg to 1
A double-sided or single-sided metal-clad laminate can be formed by stacking a metal foil on the upper or lower surface or one surface thereof and heating and pressing the same.
【００３８】本発明の積層板用変性シアネートエステル
系硬化性樹脂組成物をワニス化する場合に用いられる溶
剤の具体例としては、ベンゼン、トルエン、キシレン等
の芳香族炭化水素類、トリクロロエチレン、クロロベン
ゼン等のハロゲン化炭化水素類、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系
やＮ−メチルピロリドンなどの窒素系溶剤などが用いら
れる。特にベンゼン、トルエン、キシレン等の芳香族炭
化水素類がより好ましい。これらの溶剤類は一種類単独
で用いてもよく又は二種類以上を混合して用いてもよ
い。芳香族炭化水素系溶剤の配合量は、（Ｃ）ジシクロ
ペンタジエン樹脂１００重量部に対して１５０〜５００
重量部が好ましく、１５０〜４００重量部がより好まし
く、１５０〜３００重量部が特に好ましい。さらにアセ
トン、メチルエチルケトン、メチルイソブチルケトン、
シクロヘキサノン等のケトン類は、本発明の樹脂組成物
に対する溶解度は低いが、上記の溶媒類と併用した場合
は本発明の樹脂組成物の懸濁溶液を生成し、高濃度でか
つ粘度の低い溶液が得られるという利点がある。この観
点から、本発明の樹脂組成物をワニス化する場合に用い
る溶剤としては、ベンゼン、トルエン、キシレン等の芳
香族炭化水素類とアセトン、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と
の混合溶媒が特に好ましい。ケトン系溶剤の配合量は、
芳香族炭化水素系溶剤１００重量部に対して５０〜５０
０重量部用いるのが好ましく、５０〜４００重量部がよ
り好ましく、５０〜３００重量部が特に好ましい。Specific examples of the solvent used when the modified cyanate ester-based curable resin composition for a laminate of the present invention is varnished include aromatic hydrocarbons such as benzene, toluene and xylene, trichloroethylene, chlorobenzene and the like. Halogenated hydrocarbons, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and nitrogen solvents such as N-methylpyrrolidone. Particularly, aromatic hydrocarbons such as benzene, toluene and xylene are more preferable. These solvents may be used alone or as a mixture of two or more. The blending amount of the aromatic hydrocarbon solvent is 150 to 500 parts by weight based on 100 parts by weight of the dicyclopentadiene resin (C).
A weight part is preferable, 150-400 weight part is more preferable, and 150-300 weight part is especially preferable. In addition, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone have low solubility in the resin composition of the present invention, but when used in combination with the above solvents, form a suspension of the resin composition of the present invention, and have a high concentration and a low viscosity. Is obtained. From this viewpoint, as a solvent used when varnishing the resin composition of the present invention, a mixture of aromatic hydrocarbons such as benzene, toluene and xylene with ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone is used. Solvents are particularly preferred. The compounding amount of the ketone solvent is
50 to 50 with respect to 100 parts by weight of the aromatic hydrocarbon solvent
It is preferable to use 0 parts by weight, more preferably 50 to 400 parts by weight, and particularly preferably 50 to 300 parts by weight.
【００３９】本発明の金属張り積層板は、金属箔とし
て、主に銅箔やアルミ箔が用いられるが、他の金属箔を
用いても良い。用いられる金属箔の厚みは通常５〜２０
０μｍである。積層板製造時の加熱温度は、通常１５０
〜２５０℃の範囲で、場合によっては１００〜３５０℃
の範囲で、また、通常１〜４ＭＰａの範囲で、場合によ
っては０．１〜２０ＭＰａの範囲で、１０〜３００分間
加圧加熱して製造する。In the metal-clad laminate of the present invention, copper foil or aluminum foil is mainly used as the metal foil, but other metal foils may be used. The thickness of the metal foil used is usually 5 to 20.
0 μm. The heating temperature during the production of the laminate is usually 150
In the range of ~ 250 ° C, in some cases 100 ~ 350 ° C
And in a range of usually 1 to 4 MPa, and sometimes in a range of 0.1 to 20 MPa, under pressure and heating for 10 to 300 minutes.
【００４０】[0040]
【実施例】以下、実施例により本発明をより具体的に説
明する。表１に示す配合量に従い積層板用変性シアネー
トエステル系硬化性樹脂組成物ワニスを製造した。The present invention will be described more specifically with reference to the following examples. According to the compounding amount shown in Table 1, a modified cyanate ester-based curable resin composition varnish for a laminate was produced.
【００４１】（実施例１）温度計、冷却管、攪拌装置を
備えた５リットルの４つ口セパラブルフラスコに、トル
エン４５０ｇと（Ｃ）ジシクロペンタジエン樹脂として
ＸＥＯＮＥＸ４８０（日本ゼオン株式会社製商品名）２
１０ｇを投入し、８０℃に加熱し攪拌溶解した。次に
（Ａ）シアネートエステル類化合物として２，２−ビス
（４−シアナトフェニル）プロパン（ＡｒｏｃｙＢ−１
０、旭チバ株式会社製商品名）７００ｇ、（Ｂ）１価フ
ェノール類化合物としてｐ−（α−クミル）フェノール
（サンテクノケミカル株式会社製）６４ｇ、（Ｄ）シア
ネートエステル類化合物と反応性を有しない難燃剤とし
て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）１３５ｇを投
入溶解後、（Ｅ）金属系反応触媒としてナフテン酸コバ
ルト（Ｃｏ含有量：８重量％、日本化学産業株式会社
製）の１０重量％トルエン溶液４ｇを添加し還流温度で
１時間反応させた。ついで反応液を冷却し、内温が９０
℃になったらメチルエチルケトン（ＭＥＫ）６００ｇを
攪拌しながら投入し懸濁化させた。さらに室温まで冷却
した後、（Ｅ）金属系反応触媒としてナフテン酸亜鉛
（Ｚｎ含有量＝８重量％、日本化学産業株式会社製）の
１０重量％トルエン溶液１ｇを添加し攪拌溶解して積層
板用変性シアネートエステル系硬化性樹脂組成物のワニ
ス（固形分濃度＝５１重量％）を製造した。Example 1 A 5-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer was charged with 450 g of toluene and XEONEX 480 (trade name of Zeon Corporation) as dicyclopentadiene resin (C). ) 2
10 g was added, and the mixture was heated to 80 ° C. and dissolved by stirring. Next, (A) 2,2-bis (4-cyanatophenyl) propane (ArocyB-1) is used as a cyanate ester compound.
0, trade name of Asahi Ciba Co., Ltd.) 700 g, (B) 64 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical Co.) as a monohydric phenol compound, and (D) a reactivity with cyanate ester compound. Brominated triphenyl cyanurate (Piroguard SR-
245, trade name (Daiichi Kogyo Seiyaku Co., Ltd.) 135 g was added and dissolved, and then (E) 10% by weight of cobalt naphthenate (Co content: 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) as a metal-based reaction catalyst 4 g of the solution was added and reacted at reflux temperature for 1 hour. Then, the reaction solution was cooled and the internal temperature was 90
When the temperature reached ° C, 600 g of methyl ethyl ketone (MEK) was added with stirring to suspend. After further cooling to room temperature, (E) 1 g of a 10% by weight toluene solution of zinc naphthenate (Zn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added as a metal-based reaction catalyst, and the mixture was dissolved by stirring. A varnish (solid content concentration = 51% by weight) of a modified cyanate ester-based curable resin composition for use was produced.
【００４２】（実施例２）温度計、冷却管、攪拌装置を
備えた５リットルの４つ口セパラブルフラスコに、トル
エン３００ｇとジシクロペンタジエン樹脂（ＸＥＯＮＥ
Ｘ４８０、日本ゼオン株式会社製）１４０ｇを投入し、
８０℃に加熱し攪拌溶解した。次に２，２−ビス（４−
シアナトフェニル）プロパン（ＡｒｏｃｙＢ−１０、旭
チバ株式会社製商品名）７００ｇ、ｐ−（α−クミル）
フェノール（サンテクノケミカル株式会社製）１０ｇ、
臭素化トリフェニルシアヌレート（ピロガードＳＲ−２
４５、第一工業製薬株式会社製商品名）１２５ｇを投入
溶解後、ナフテン酸マンガン（Ｍｎ含有量：８重量％、
日本化学産業株式会社製）の１０重量％トルエン溶液３
ｇを添加し還流温度で１時間反応させた。ついで反応液
を冷却し、内温が９０℃になったらメチルエチルケトン
（ＭＥＫ）６００ｇを攪拌しながら投入し懸濁化させ
た。さらに室温まで冷却した後、ｐ−（α−クミル）フ
ェノール７５ｇ、ナフテン酸亜鉛（Ｚｎ含有量：８重量
％、日本化学産業株式会社製）の１０重量％トルエン溶
液１ｇを添加し攪拌溶解して積層板用変性シアネートエ
ステル系硬化性樹脂組成物ワニス（固形分濃度：５４重
量％）を製造した。Example 2 300 g of toluene and a dicyclopentadiene resin (XEONE) were placed in a 5-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer.
X480, manufactured by Zeon Corporation)
The mixture was heated to 80 ° C. and dissolved by stirring. Next, 2,2-bis (4-
Cyanatophenyl) propane (ArocyB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 700 g, p- (α-cumyl)
10 g of phenol (manufactured by San Techno Chemical Co., Ltd.)
Brominated triphenyl cyanurate (Piroguard SR-2
45, 125 g of Daiichi Kogyo Seiyaku Co., Ltd.), and after dissolving, manganese naphthenate (Mn content: 8% by weight)
10% by weight toluene solution 3 of Nippon Chemical Industry Co., Ltd.)
g was added and reacted at reflux temperature for 1 hour. Then, the reaction solution was cooled, and when the internal temperature reached 90 ° C., 600 g of methyl ethyl ketone (MEK) was added with stirring to suspend. After further cooling to room temperature, 75 g of p- (α-cumyl) phenol and 1 g of a 10% by weight toluene solution of zinc naphthenate (Zn content: 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) were added, and the mixture was stirred and dissolved. A modified cyanate ester-based curable resin composition varnish for a laminate (solid content: 54% by weight) was produced.
【００４３】（実施例３）温度計、冷却管、攪拌装置を
備えた５リットルの４つ口セパラブルフラスコに、トル
エン３００ｇとジシクロペンタジエン樹脂（ＸＥＯＮＥ
Ｘ４８０、日本ゼオン株式会社製商品名）８０ｇを投入
し、８０℃に加熱し攪拌溶解した。次に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（ＲＴＸ−３６６、旭チバ株式会社製商品名）８００
ｇ、ｐ−（α−クミル）フェノール（サンテクノケミカ
ル株式会社製）１０ｇを投入溶解後、ナフテン酸鉄（鉄
含有量＝５重量％、日本化学産業株式会社製）の１０重
量％トルエン溶液２ｇを添加し還流温度で１時間反応さ
せ、ついで１，２−ジブロモ−４−（１，２−ジブロモ
エチル）シクロヘキサン（ＳａｙｔｅｘＢＣＬ−４６
２、アルベマール社製商品名）１１０ｇを投入溶解させ
た。反応液を冷却し、内温が９０℃になったらメチルエ
チルケトン（ＭＥＫ）６００ｇを攪拌しながら投入し懸
濁化させた。さらに室温まで冷却した後、ｐ−（α−ク
ミル）フェノール７５ｇ、ナフテン酸銅（銅含有量＝５
重量％、日本化学産業株式会社製）の１０重量％トルエ
ン溶液２ｇを添加し攪拌溶解して積層板用変性シアネー
トエステル系硬化性樹脂組成物のワニス（固形分濃度＝
５４重量％）を製造した。Example 3 300 g of toluene and a dicyclopentadiene resin (XEONE) were placed in a 5-liter 4-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer.
X480 (trade name, manufactured by Nippon Zeon Co., Ltd.) (80 g) was charged, heated to 80 ° C., and dissolved by stirring. Next, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene (RTX-366, trade name, manufactured by Asahi Ciba Corporation) 800
g, 10 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical Co., Ltd.), and after dissolution, 2 g of a 10 wt% toluene solution of iron naphthenate (iron content = 5 wt%, manufactured by Nippon Chemical Industry Co., Ltd.) was added. The reaction was carried out at reflux temperature for 1 hour, and then 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane (Saytex BCL-46)
2, Albemarl product name) (110 g) was charged and dissolved. The reaction solution was cooled, and when the internal temperature reached 90 ° C., 600 g of methyl ethyl ketone (MEK) was added with stirring to suspend. After further cooling to room temperature, 75 g of p- (α-cumyl) phenol and copper naphthenate (copper content = 5
2% of a 10% by weight toluene solution of 10% by weight, manufactured by Nippon Chemical Industry Co., Ltd. was added and dissolved by stirring, and a varnish (solid content =
54% by weight).
【００４４】（実施例４）温度計、冷却管、攪拌装置を
備えた５リットルの４つ口セパラブルフラスコに、トル
エン６００ｇとジシクロペンタジエン樹脂（ＸＥＯＮＥ
Ｘ４８０、日本ゼオン株式会社製商品名）３００ｇを投
入し、８０℃に加熱し攪拌溶解した。次にビス（３，５
−ジメチル−４−シアナトフェニル）メタン（Ａｒｏｃ
ｙＭ−１０、旭チバ株式会社製商品名）６００ｇ、ｐ−
（α−クミル）フェノール（サンテクノケミカル社製）
３０ｇを投入溶解後、ナフテン酸コバルト（Ｃｏ含有量
＝８重量％、日本化学産業株式会社製）の１０重量％ト
ルエン溶液４ｇを添加し還流温度で１時間反応させ、つ
いで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）１５０ｇを投入溶解させた。
反応液を冷却し、内温が９０℃になったらメチルエチル
ケトン（ＭＥＫ）７５０ｇを攪拌しながら投入し懸濁化
させた。さらに室温まで冷却した後、Ｐ−（α−クミ
ル）フェノール１２０ｇを添加し攪拌溶解して積層板用
変性シアネートエステル系硬化性樹脂組成物のワニス
（固形分濃度＝４７重量％）を製造した。Example 4 A 5-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer was charged with 600 g of toluene and dicyclopentadiene resin (XEONE).
X480 (trade name, manufactured by Zeon Corporation) (300 g) was charged, and the mixture was heated to 80 ° C. and dissolved by stirring. Next, screw (3,5
-Dimethyl-4-cyanatophenyl) methane (Aroc
yM-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 600 g, p-
(Α-cumyl) phenol (manufactured by San Techno Chemical)
After charging and dissolving 30 g, 4 g of a 10% by weight toluene solution of cobalt naphthenate (Co content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added and reacted at reflux temperature for 1 hour, and then hexabromocyclododecane (CD 150 g of -75P (trade name, manufactured by Great Lakes Co.) was charged and dissolved.
The reaction solution was cooled, and when the internal temperature reached 90 ° C., 750 g of methyl ethyl ketone (MEK) was added with stirring to suspend. After further cooling to room temperature, 120 g of P- (α-cumyl) phenol was added and dissolved by stirring to produce a varnish (solids concentration = 47% by weight) of a modified cyanate ester-based curable resin composition for a laminate.
【００４５】（実施例５）温度計、冷却管、攪拌装置を
備えた５リットルの４つ口セパラブルフラスコに、トル
エン７５０ｇとジシクロペンタジエン樹脂（ＸＥＯＮＥ
Ｘ４８０、日本ゼオン株式会社製商品名）４００ｇを投
入し、８０℃に加熱し攪拌溶解した。次に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（ＡｒｏｃｙＦ−１０、旭チバ
株式会社製商品名）５００ｇ、ｐ−（α−クミル）フェ
ノール（サンテクノケミカル社製）２８ｇを投入溶解
後、ナフテン酸銅（Ｃｕ含有量＝５重量％、日本化学産
業株式会社製）の１０重量％トルエン溶液６ｇを添加し
還流温度で１時間反応させ、ついでテトラブロモシクロ
オクタン（ＳａｙｔｅｘＢＣ−４８、アルベマール社製
商品名）１５０ｇを投入溶解させた。ついで反応液を冷
却し、内温が９０℃になったらメチルエチルケトン（Ｍ
ＥＫ）５００ｇを攪拌しながら投入し懸濁化させた。室
温まで冷却した後、ナフテン酸マンガン（Ｍｎ含有量＝
８重量％、日本化学産業株式会社製）の１０重量％トル
エン溶液１ｇを添加し攪拌溶解して積層板用変性シアネ
ートエステル系硬化性樹脂組成物のワニス（固形分濃度
＝４６重量％）を製造した。Example 5 A 750 g of toluene and a dicyclopentadiene resin (XEONE) were placed in a 5-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer.
X480 (trade name, manufactured by Zeon Corporation) (400 g) was charged, and the mixture was heated to 80 ° C. and dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-
After adding and dissolving 500 g of hexafluoropropane (ArocyF-10, trade name of Asahi Ciba Co., Ltd.) and 28 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical Co.), copper naphthenate (Cu content = 5% by weight, 6 g of a 10% by weight toluene solution of Nippon Chemical Industry Co., Ltd. was added and reacted at reflux temperature for 1 hour, and then 150 g of tetrabromocyclooctane (Saytex BC-48, trade name of Albemarle) was charged and dissolved. Then, the reaction solution was cooled, and when the internal temperature reached 90 ° C., methyl ethyl ketone (M
EK) 500 g was added with stirring and suspended. After cooling to room temperature, manganese naphthenate (Mn content =
1 g of a 10% by weight toluene solution of 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd. was added and dissolved by stirring to produce a varnish (solid content = 46% by weight) of a modified cyanate ester-based curable resin composition for a laminate. did.
【００４６】（比較例１）実施例１において、トルエン
１８００ｇにジシクロペンタジエン樹脂（ＸＥＯＮＥＸ
４８０、日本ゼオン株式会社製商品名）２１０ｇ、２，
２−ビス（４−シアナトフェニル）プロパン（Ａｒｏｃ
ｙＢ−１０、旭チバ株式会社製商品名）７００ｇ及びｐ
−（α−クミル）フェノールの代わりに２，２−ビス
（４−ヒドロキシフェニル）プロパン（ＢＰＡ；ビスフ
ェノールＡ、三井東圧化学株式会社製）６９ｇを投入
し、攪拌溶解後ナフテン酸コバルト（Ｃｏ含有量＝８重
量％、日本化学産業株式会社製）の１０重量％トルエン
希釈溶液３ｇを添加して還流温度で１時間反応させた。
ついで、難燃剤としてシアネナト基と反応性を有する臭
素化ビスフェノールＡ型エポキ樹脂（ＥＳＢ４００、住
友化学工業株式会社製商品名）２００ｇを投入溶解し冷
却した。しかし常温付近で樹脂溶液が固化（グリース
状）したため、トルエン１２００ｇをさらに添加して攪
拌溶解し積層板用変性シアネートエステル系硬化性樹脂
組成物のワニス（固形分濃度＝２８重量％）を製造し
た。Comparative Example 1 In Example 1, 1800 g of toluene was added to a dicyclopentadiene resin (XEONEX).
480, Nippon Zeon Co., Ltd. 210 g, 2,
2-bis (4-cyanatophenyl) propane (Aroc
yB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 700 g and p
In place of-(α-cumyl) phenol, 69 g of 2,2-bis (4-hydroxyphenyl) propane (BPA; bisphenol A, manufactured by Mitsui Toatsu Chemicals, Inc.) was added, and after stirring and dissolving, cobalt naphthenate (containing Co) was added. 3 g of a 10% by weight toluene diluted solution (amount = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added, and the mixture was reacted at a reflux temperature for 1 hour.
Next, 200 g of a brominated bisphenol A type epoxy resin (ESB400, trade name, manufactured by Sumitomo Chemical Co., Ltd.) having a reactivity with a cyanate group as a flame retardant was charged and dissolved and cooled. However, since the resin solution was solidified (grease-like) at around normal temperature, 1200 g of toluene was further added and dissolved by stirring to produce a varnish (solid content = 28% by weight) of a modified cyanate ester-based curable resin composition for a laminate. .
【００４７】（比較例２）実施例１において、トルエン
１８００ｇにジシクロペンタジエン樹脂（ＸＥＯＮＥＸ
４８０、日本ゼオン株式会社製商品名）２１０ｇ、２，
２−ビス（４−シアナトフェニル）プロパン（Ａｒｏｃ
ｙＢ−１０、旭チバ株式会社製商品名）７００ｇ及びｐ
−（α−クミル）フェノールの代わりにノニルフェノー
ル（三井東圧化学株式会社製）１１ｇを投入し、攪拌溶
解後ナフテン酸コバルト（Ｃｏ含有量＝８重量％、日本
化学産業株式会社製）の１０重量％トルエン希釈溶液４
ｇを添加して還流温度で１時間反応させた。ついで、難
燃剤としてシアネナト基と反応性を有する臭素化ビスフ
ェノールＡ型エポキ樹脂（ＥＳＢ４００、住友化学工業
株式会社製商品名）１９０ｇを投入溶解し冷却した。し
かし常温付近で樹脂溶液が固化（グリース状）したた
め、トルエン９００ｇをさらに添加して攪拌溶解し積層
板用変性シアネートエステル系硬化性樹脂組成物のワニ
ス（固形分濃度＝２９重量％）を製造した。Comparative Example 2 In Example 1, 1800 g of toluene was added to a dicyclopentadiene resin (XEONEX).
480, Nippon Zeon Co., Ltd. 210 g, 2,
2-bis (4-cyanatophenyl) propane (Aroc
yB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 700 g and p
11 g of nonylphenol (manufactured by Mitsui Toatsu Chemicals, Inc.) is introduced instead of (α-cumyl) phenol, and after stirring and dissolving, 10% by weight of cobalt naphthenate (Co content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) % Toluene diluted solution 4
g was added and reacted at reflux temperature for 1 hour. Then, 190 g of a brominated bisphenol A type epoxy resin (ESB400, trade name, manufactured by Sumitomo Chemical Co., Ltd.) having a reactivity with a cyanate group as a flame retardant was introduced, dissolved and cooled. However, since the resin solution was solidified (grease-like) at around normal temperature, 900 g of toluene was further added and dissolved by stirring to produce a varnish (solid content = 29% by weight) of a modified cyanate ester-based curable resin composition for a laminate. .
【００４８】（比較例３）実施例１において、トルエン
１５００ｇにジシクロペンタジエン樹脂（ＸＥＯＮＥＸ
４８０、日本ゼオン株式会社製商品名）２１０ｇを投入
し８０℃に加熱して攪拌溶解し、次に２，２−ビス（４
−シアナトフェニル）プロパン（ＡｒｏｃｙＢ−１０、
旭チバ株式会社製商品名）の代わりに２，２−ビス（４
−シアナトフェニル）プロパンのオリゴマ（Ａｒｏｃｙ
Ｂ−３０、旭チバ株式会社製商品名）７００ｇ，ｐ−
（α−クミル）フェノールの代わりにノニルフェノール
６７ｇ及び難燃剤としてシアネナト基と反応性を有する
臭素化ビスフェノールＡ型エポキ樹脂（ＥＳＢ４００、
住友化学工業株式会社製商品名）２００ｇを投入して８
０℃で１時間加熱溶解した。ついで常温まで冷却し、ナ
フテン酸亜鉛（Ｚｎ含有量＝８重量％、日本化学産業株
式会社製）の１０重量％トルエン溶液３ｇを添加して積
層板用変性シアネートエステル系硬化性樹脂組成物のワ
ニス（固形分濃度＝４４重量％）を製造した。しかし、
この樹脂ワニスは２日後にジシクロペンタジエン樹脂の
凝集分離物が観察された。Comparative Example 3 In Example 1, 1500 g of toluene was added to a dicyclopentadiene resin (XEONEX).
480, trade name (manufactured by Nippon Zeon Co., Ltd.) (210 g), heated to 80 ° C. and dissolved by stirring, and then 2,2-bis (4
-Cyanatophenyl) propane (ArocyB-10,
Asahi Ciba Co., Ltd. instead of 2,2-bis (4
-Cyanatophenyl) propane oligomer (Arocy)
B-30, trade name, manufactured by Asahi Ciba Co., Ltd.) 700 g, p-
67 g of nonylphenol in place of (α-cumyl) phenol and a brominated bisphenol A type epoxy resin having a reactivity with a cyanate group as a flame retardant (ESB400,
Sumitomo Chemical Co., Ltd. brand name) 200g and 8
The mixture was dissolved by heating at 0 ° C. for 1 hour. Then, the mixture was cooled to room temperature, and 3 g of a 10% by weight toluene solution of zinc naphthenate (Zn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added, and a varnish of a modified cyanate ester-based curable resin composition for laminates was added. (Solid content = 44% by weight). But,
In this resin varnish, an agglomerated and separated product of dicyclopentadiene resin was observed after 2 days.
【００４９】（比較例４）実施例４において、トルエン
１６００ｇとジシクロペンタジエン樹脂（ＸＥＯＮＥＸ
４８０、日本ゼオン株式会社製商品名）３００ｇ、ビス
（３，５−ジメチル−４−シアナトフェニル）メタン
（ＡｒｏｃｙＭ−１０、旭チバ株式会社製商品名）６０
０ｇ及びｐ−（α−クミル）フェノール（サンテクノケ
ミカル社製商品名）の代わりにノニルフェノール９ｇを
投入し、攪拌溶解後ナフテン酸マンガン（Ｍｎ含有量＝
８重量％、日本化学産業株式会社製）の１０重量％トル
エン溶液３ｇを添加して還流温度で１時間反応させた。
ついで、難燃剤としてシアネナト基と反応性を有するテ
トラブロモビスフェノールＡ（ファイヤガードＦＧ−２
０００、帝人化成株式会社製商品名）１５０ｇを投入溶
解し冷却した。しかし常温付近で樹脂溶液が固化（グリ
ース状）したため、トルエン１２００ｇをさらに添加し
て攪拌溶解し積層板用変性シアネートエステル系硬化性
樹脂組成物のワニス（固形分濃度＝２７重量％）を製造
した。Comparative Example 4 In Example 4, 1600 g of toluene and dicyclopentadiene resin (XEONEX) were used.
480, Nippon Zeon Co., Ltd. 300 g, bis (3,5-dimethyl-4-cyanatophenyl) methane (ArocyM-10, Asahi Ciba Co., Ltd.) 60
0 g and 9 g of nonylphenol instead of p- (α-cumyl) phenol (trade name, manufactured by Sun Techno Chemical Co., Ltd.), and after stirring and dissolving, manganese naphthenate (Mn content =
3 g of a 10% by weight toluene solution of 8% by weight (manufactured by Nippon Chemical Industry Co., Ltd.) was added and reacted at reflux temperature for 1 hour.
Then, tetrabromobisphenol A (Fireguard FG-2) having a reactivity with a cyanate group as a flame retardant is used.
000, trade name (manufactured by Teijin Chemicals Limited) (150 g) was introduced, dissolved and cooled. However, since the resin solution was solidified (grease-like) at around normal temperature, 1200 g of toluene was further added and dissolved by stirring to produce a varnish (solids concentration = 27% by weight) of a modified cyanate ester-based curable resin composition for a laminate. .
【００５０】[0050]
【表１】 [Table 1]
【００５１】（Ａ）Ｂ−１０（旭チバ株式会社製商品
名）；２，２−ビス（４−シアナトフェニル）プロパン Ｍ−１０（旭チバ株式会社製商品名）；ビス（３，５−
ジメチル−４−シアナトフェニル）メタン Ｆ−１０（旭チバ株式会社製商品名）；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 ＲＴＸ−３６６（旭チバ株式会社製商品名）；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 Ｂ−３０（旭チバ株式会社製商品名）；２，２−ビス
（４−シアナトフェニル）プロパンのオリゴマ （Ｂ）ＰＣＰ（サンテクノケミカル社製）；ｐ−（α−
クミル）フェノール ＢＰＡ（ビスフェノールＡ、三井東圧化学株式会社
製）；２，２−ビス（４−ヒドロキシフェニル）プロパ
ン ＮＰ（三井東圧化学学株式会社製）；ノニルフェノール （Ｃ）ＤＣＰＤ（ＸＥＯＮＥＸ４８０、日本ゼオン株式
会社製商品名）；ジシクロペンタジエン樹脂 （Ｄ）ＢＣＬ−４６２（アルベマール社製商品名）；
１，２−ジブロモ−４−（１，２−ジブロモエチル）シ
クロヘキサン ＢＣ−４８（アルベマール社製商品名）；テトラブロモ
シクロオクタン ＣＤ−７５Ｐ（グレートレイクス社製商品名）；ヘキサ
ブロモシクロドデカン ＳＲ−２４５（第一工業製薬株式会社製）；２，４，６
−トリス（トリブロモフェノキシ）−１，３，５−トリ
アジン ＥＳＢ−４００（住友化学工業株式会社製商品名）；臭
素化ビスフェノールＡ型エポキシ樹脂 ＴＢＡ（ＦＧ−２０００、帝人化成株式会社製商品
名）；臭素化ビスフェノールＡ （Ｅ）Ｃｏ；ナフテン酸コバルト（Ｃｏ＝８％、日本化
学産業株式会社製）の１０重量％トルエン溶液 Ｚｎ；ナフテン酸亜鉛（Ｚｎ＝重量８％、日本化学産業
株式会社製）の１０重量％トルエン溶液 Ｍｎ；ナフテン酸マンガン（Ｍｎ＝８重量％、日本化学
産業株式会社製）の１０重量％トルエン溶液 Ｆｅ；ナフテン酸鉄（Ｆｅ＝重量５％、日本化学産業株
式会社製）の１０重量％トルエン溶液 Ｃｕ；ナフテン酸銅（Ｃｕ＝５重量％、日本化学産業株
式会社製）の１０重量％トルエン溶液(A) B-10 (trade name, manufactured by Asahi Ciba Co., Ltd.); 2,2-bis (4-cyanatophenyl) propane M-10 (trade name, manufactured by Asahi Ciba Co., Ltd.); −
Dimethyl-4-cyanatophenyl) methane F-10 (trade name, manufactured by Asahi Ciba Co., Ltd.); 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-
Hexafluoropropane RTX-366 (trade name, manufactured by Asahi Ciba Corporation); α, α '
-Bis (4-cyanatophenyl) -m-diisopropylbenzene B-30 (trade name, manufactured by Asahi Ciba Corporation); an oligomer of 2,2-bis (4-cyanatophenyl) propane (B) PCP (San Techno Chemical Co., Ltd.) P- (α-
Cumyl) phenol BPA (bisphenol A, manufactured by Mitsui Toatsu Chemicals, Inc.); 2,2-bis (4-hydroxyphenyl) propane NP (manufactured by Mitsui Toatsu Chemicals, Inc.); nonylphenol (C) DCPD (XEONEX480, Japan Dicyclopentadiene resin (D) BCL-462 (trade name by Albemarle);
1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane BC-48 (trade name of Albemarle); tetrabromocyclooctane CD-75P (trade name of Great Lakes); hexabromocyclododecane SR- 245 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.);
-Tris (tribromophenoxy) -1,3,5-triazine ESB-400 (trade name, manufactured by Sumitomo Chemical Co., Ltd.); Brominated bisphenol A type epoxy resin TBA (FG-2000, trade name, manufactured by Teijin Chemicals Limited) Brominated bisphenol A (E) Co; 10% by weight toluene solution of cobalt naphthenate (Co = 8%, manufactured by Nippon Chemical Industry Co., Ltd.) Zn; zinc naphthenate (Zn = 8%, manufactured by Nippon Chemical Industry Co., Ltd.) ) Of 10% by weight toluene solution Mn; manganese naphthenate (Mn = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) 10% by weight toluene solution Fe; Iron naphthenate (Fe = 5%, manufactured by Nippon Chemical Industry Co., Ltd.) )) 10% by weight toluene solution Cu; 10% by weight toluene solution of copper naphthenate (Cu = 5% by weight, manufactured by Nippon Chemical Industry Co., Ltd.)
【００５２】得られた積層板用変性シアネートエステル
系硬化性樹脂組成物のワニスを０．２ｍｍ厚のＥガラス
布（坪量２０９ｇ／ｍ2）に含浸し、１４０℃で５〜１
０分（ゲル化時間（１７０℃）が５〜７分になるよう
に）加熱して樹脂付着量４０〜４５重量％のプリプレグ
を得た。なお、比較例１，２及び４の積層板用変性シア
ネートエステル系硬化性樹脂組成物のワニスの場合は、
固形分濃度が低いため上記含浸塗工作業を繰り返し２回
行って樹脂付着量４０〜４５重量％のプリプレグを得
た。また比較例３のプリプレグは、シアネートエステル
樹脂とジシクロペンタジエン樹脂の分離が観察された。A varnish of the resulting modified cyanate ester-based curable resin composition for a laminate was impregnated into a 0.2 mm-thick E glass cloth (basis weight: 209 g / m 2 ).
Heating was performed for 0 minutes (so that the gel time (170 ° C.) was 5 to 7 minutes) to obtain a prepreg having a resin adhesion amount of 40 to 45% by weight. In the case of the varnish of the modified cyanate ester-based curable resin composition for laminates of Comparative Examples 1, 2, and 4,
Since the solid content was low, the above impregnation coating operation was repeated twice to obtain a prepreg having a resin adhesion amount of 40 to 45% by weight. In the prepreg of Comparative Example 3, separation of the cyanate ester resin and the dicyclopentadiene resin was observed.
【００５３】次にプリプレグ４枚と両側に１８μｍ厚の
銅箔を積層し、１７０℃、２．５ＭＰａの条件で６０分
プレス成形した後、２３０℃で１２０分加熱処理して銅
張り積層板を作製した。得られた銅張り積層板について
以下に示す測定方法により誘電特性、はんだ耐熱性、銅
箔引き剥がし強さ及び耐燃性を測定評価した。その結果
を表２に示す。Next, four prepregs and 18 μm-thick copper foil were laminated on both sides, press-formed at 170 ° C. and 2.5 MPa for 60 minutes, and then heat-treated at 230 ° C. for 120 minutes to form a copper-clad laminate. Produced. The dielectric properties, solder heat resistance, copper foil peeling strength and flame resistance of the obtained copper-clad laminate were measured and evaluated by the following measurement methods. Table 2 shows the results.
【００５４】＜特性評価方法＞ ・比誘電率及び誘電正接／１ＧＨｚ：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：銅箔をエッチング除去した試験片をＰ
ＣＴ（１２１℃、０．２２ＭＰａ）中に保持した後、２
６０℃の溶融はんだに２０秒浸漬して、外観を調べた。
表中のＯＫとは、ミーズリング及びふくれの発生が無い
ことを示し、ＮＧとはミーズリング及びふくれが発生し
たことを示す。 ・銅箔引き剥がし強さ：ＪＩＳ−Ｃ−６４８１に準拠し
て測定した。 ・耐燃性：ＵＬ−９４垂直試験法に準拠して測定した。<Characteristics Evaluation Method> Relative dielectric constant and dielectric loss tangent / 1 GHz: Measured by a triplate structure straight line resonator method.・ Solder heat resistance: Test piece with copper foil etched away
After holding in CT (121 ° C, 0.22 MPa), 2
It was immersed in molten solder at 60 ° C. for 20 seconds, and the appearance was examined.
"OK" in the table indicates that no measling and blistering occurred, and "NG" indicates that measling and blistering occurred. -Copper foil peel strength: Measured according to JIS-C-6481. -Flame resistance: Measured according to the UL-94 vertical test method.
【００５５】[0055]
【表２】 [Table 2]
【００５６】表２から明らかなように、実施例１〜５の
積層板用変性シアネートエステル系硬化性樹脂組成物を
用いた積層板は、何れも１ＧＨｚでの比誘電率、誘電正
接が低く、吸湿時のはんだ耐熱性、銅箔引き剥がし強さ
が良好である。これに対して比較例は、本発明以外のフ
ェノール類を用いたり、従来の難燃剤を用いると１ＧＨ
ｚの比誘電率及び誘電正接が高くなり、耐熱性などに劣
る。As is clear from Table 2, the laminates using the modified cyanate ester-based curable resin compositions for laminates of Examples 1 to 5 all have low relative dielectric constant and dielectric loss tangent at 1 GHz, and Good soldering heat resistance at the time of moisture absorption and good copper foil peeling strength. On the other hand, the comparative example shows that when a phenol other than the present invention is used or a conventional flame retardant is used, 1 GH
The dielectric constant and dielectric loss tangent of z are high, and the heat resistance is poor.
【００５７】[0057]
【発明の効果】本発明の積層板用変性シアネートエステ
ル系硬化性樹脂組成物を用いた積層板は、高周波帯域で
の誘電率や誘電正接が低く、かっはんだ耐熱性、接着
性、耐燃性が良好であり、高周波信号を扱う機器の印刷
配線板に用いる積層板用樹脂組成物として好適である。
また本発明の積層板用プリプレグ及び金属張り積層板
は、高周波帯域での誘電正接が低く低損失性に優れ、無
線通信関連の端末機器やアンテナ、マイクロプロセッサ
の動作周波数が数百ＭＨｚを超えるような高速コンピュ
ータなどに用いられる印刷配線板用基板に好適である。The laminate using the modified cyanate ester-based curable resin composition for a laminate of the present invention has a low dielectric constant and a low dielectric loss tangent in a high frequency band, and has low solder heat resistance, adhesiveness, and flame resistance. It is good and is suitable as a resin composition for a laminate used for a printed wiring board of a device that handles high-frequency signals.
The prepreg for a laminate and the metal-clad laminate of the present invention have a low dielectric loss tangent in a high-frequency band and an excellent low-loss property, and the operating frequency of a wireless communication-related terminal device, an antenna, and a microprocessor exceeds several hundred MHz. It is suitable for a printed wiring board substrate used in a high-speed computer or the like.
Claims (11)
ステル類化合物、（Ｂ）式（２）で示される１価フェノ
ール類、（Ｃ）ジシクロペンタジエン樹脂、（Ｄ）シア
ネートエステル類化合物と反応性を有しない難燃剤及び
（Ｅ）金属系反応触媒を必須成分として含有することを
特徴とする積層板用変性シアネートエステル系硬化性樹
脂組成物。 【化１】 【化２】 1. (A) a cyanate ester compound represented by the formula (1), (B) a monohydric phenol represented by the formula (2), (C) a dicyclopentadiene resin, and (D) a cyanate ester compound A modified cyanate ester-based curable resin composition for a laminate, comprising, as essential components, a flame retardant having no reactivity with (A) and (E) a metal-based reaction catalyst. Embedded image Embedded image
（Ａ）シアネートエステル類化合物の１００重量部に対
して（Ｂ）１価フェノール類化合物を４〜３０重量部配
合することを特徴とする請求項１に記載の積層板用変性
シアネートエステル系硬化性樹脂組成物。2. The modified cyanate ester-based resin,
The modified cyanate ester-based curable composition for a laminate according to claim 1, wherein 4 to 30 parts by weight of the (B) monohydric phenol compound is blended with respect to 100 parts by weight of the (A) cyanate ester compound. Resin composition.
（Ｂ）１価フェノール類化合物の一部又は全部を反応さ
せて得られる変性シアネートエステル樹脂と、（Ｃ）ジ
シクロペンタジエン樹脂、（Ｄ）シアネートエステル類
化合物と反応性を有しない難燃剤及び（Ｅ）金属系反応
触媒を必須成分として含有することを特徴とする請求項
１または請求項２に記載の積層板用変性シアネートエス
テル系硬化性樹脂組成物。3. A modified cyanate ester resin obtained by reacting (A) a cyanate ester compound with part or all of a (B) monohydric phenol compound, (C) a dicyclopentadiene resin, and (D) a cyanate The modified cyanate ester-based curable resin for a laminate according to claim 1 or 2, comprising a flame retardant having no reactivity with the ester compound and (E) a metal-based reaction catalyst as essential components. Composition.
０重量部に対して（Ｂ）１価フェノール類化合物を４〜
３０重量部、（Ｃ）ジシクロペンタジエン樹脂５〜３０
０重量部、（Ｄ）シアネートエステル類化合物と反応性
を有しない難燃剤を（Ａ），（Ｂ），（Ｃ）の総量１０
０重量部に対して５〜３０重量部及び（Ｅ）金属系反応
触媒を（Ａ）１（ｇ）に対して１〜３００ｐｐｍ、必須
成分として含有することを特徴とする請求項１ないし請
求項３のいずれかに記載の積層板用変性シアネートエス
テル系硬化性樹脂組成物。4. The compound (A) of the cyanate ester compound
4 parts by weight of (B) the monohydric phenol compound to 0 parts by weight
30 parts by weight, (C) dicyclopentadiene resin 5 to 30
0 parts by weight, the flame retardant having no reactivity with the cyanate ester compound (D) was added to the total amount of (A), (B) and (C) 10
5 to 30 parts by weight based on 0 parts by weight and 1 to 300 ppm of (E) a metal-based reaction catalyst based on 1 (g) of (A) as an essential component. 3. The modified cyanate ester-based curable resin composition for a laminate according to any one of 3.
２，２−ビス（４−シアナトフェニル）プロパンまたは
ビス（３，５−ジメチル−４−シアナトフェニル）メタ
ンのいずれかの１種又は両者の混合物である請求項１な
いし請求項４のいずれかに記載の積層板用変性シアネー
トエステル系硬化性樹脂組成物。5. The method according to claim 1, wherein (A) the cyanate ester compound is
The method according to any one of claims 1 to 4, wherein the compound is one of 2,2-bis (4-cyanatophenyl) propane or bis (3,5-dimethyl-4-cyanatophenyl) methane or a mixture of both. The modified cyanate ester-based curable resin composition for a laminate described in the item (1).
（α−クミル）フェノールである請求項１ないし請求項
５のいずれかに記載の積層板用変性シアネートエステル
系硬化性樹脂組成物。6. The method of claim 1, wherein (B) the monohydric phenol compound is p-
The modified cyanate ester-based curable resin composition for a laminate according to any one of claims 1 to 5, which is (α-cumyl) phenol.
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及びヘキサブロモシクロドデカンか
ら選ばれる脂環式難燃剤の１種又はこれらの２種類以上
の混合物である請求項１ないし請求項６のいずれかに記
載の積層板用変性シアネートエステル系硬化性樹脂組成
物。7. The flame retardant having no reactivity with the (D) cyanate ester compound is 1,2-dibromo-4-
7. An alicyclic flame retardant selected from (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane and hexabromocyclododecane, or a mixture of two or more thereof. The modified cyanate ester-based curable resin composition for a laminate according to the above.
性を有しない難燃剤が、式（３）で示される臭素化トリ
フェニルシアヌレート系難燃剤又はこれら少なくとも１
種類以上とその他のシアネートエステル類化合物と反応
性を有しない難燃剤との２種類以上の混合物である請求
項１ないし請求項６のいずれかに記載の積層板用変性シ
アネートエステル系硬化性樹脂組成物。 【化３】 8. The flame retardant having no reactivity with the cyanate ester compound (D) is a brominated triphenyl cyanurate flame retardant represented by the formula (3) or at least one of these flame retardants.
The modified cyanate ester-based curable resin composition for a laminate according to any one of claims 1 to 6, wherein the mixture is a mixture of two or more types of flame retardants having no reactivity with other types of cyanate ester compounds. Stuff. Embedded image
コバルト、ニッケル、銅及び亜鉛の２−エチルヘキサン
酸塩、ナフテン酸塩及びアセチルアセトン錯体から選ば
れる１種類又は２種類以上である請求項１ないし請求項
８のいずれかに記載の積層板用変性シアネートエステル
系硬化性樹脂組成物。9. (E) The metal-based reaction catalyst is manganese, iron,
The modified cyanate for laminates according to any one of claims 1 to 8, wherein the modified cyanate is one or more selected from 2-ethylhexanoate, naphthenate, and acetylacetone complex of cobalt, nickel, copper, and zinc. An ester-based curable resin composition.
記載の積層板用変性シアネートエステル系硬化性樹脂組
成物を溶剤に溶解又は分散してワニスとし、このワニス
を基材に含浸後、８０〜２００℃で乾燥させて得られる
プリプレグ。10. A varnish obtained by dissolving or dispersing the modified cyanate ester-based curable resin composition for a laminate according to any one of claims 1 to 9 in a solvent, and impregnating the substrate with the varnish. A prepreg obtained by drying at 80 to 200 ° C.
グを１枚ないし複数枚重ね、さらにその上下面又は片面
に金属箔を積層し、加熱加圧して得られる金属張り積層
板。11. A metal-clad laminate obtained by laminating one or more laminate prepregs according to claim 10, further laminating metal foil on the upper or lower surface or one surface thereof, and heating and pressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36022597A JP3981847B2 (en) | 1997-12-26 | 1997-12-26 | Modified cyanate ester-based curable resin composition for laminates, and prepreg and metal-clad laminate using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36022597A JP3981847B2 (en) | 1997-12-26 | 1997-12-26 | Modified cyanate ester-based curable resin composition for laminates, and prepreg and metal-clad laminate using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11189718A true JPH11189718A (en) | 1999-07-13 |
| JP3981847B2 JP3981847B2 (en) | 2007-09-26 |
Family
ID=18468458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36022597A Expired - Fee Related JP3981847B2 (en) | 1997-12-26 | 1997-12-26 | Modified cyanate ester-based curable resin composition for laminates, and prepreg and metal-clad laminate using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3981847B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001081322A (en) * | 1999-09-17 | 2001-03-27 | Hitachi Chem Co Ltd | Modified cyanate ester resin composition and prepreg and laminate using the same |
| JP2006273950A (en) * | 2005-03-28 | 2006-10-12 | Sumitomo Bakelite Co Ltd | Resin composition, laminated article and circuit board and method for producing circuit board |
-
1997
- 1997-12-26 JP JP36022597A patent/JP3981847B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001081322A (en) * | 1999-09-17 | 2001-03-27 | Hitachi Chem Co Ltd | Modified cyanate ester resin composition and prepreg and laminate using the same |
| JP2006273950A (en) * | 2005-03-28 | 2006-10-12 | Sumitomo Bakelite Co Ltd | Resin composition, laminated article and circuit board and method for producing circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3981847B2 (en) | 2007-09-26 |
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