JP2003266596A - Copper-clad laminated sheet - Google Patents

Copper-clad laminated sheet

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Publication number
JP2003266596A
JP2003266596A JP2002072983A JP2002072983A JP2003266596A JP 2003266596 A JP2003266596 A JP 2003266596A JP 2002072983 A JP2002072983 A JP 2002072983A JP 2002072983 A JP2002072983 A JP 2002072983A JP 2003266596 A JP2003266596 A JP 2003266596A
Authority
JP
Japan
Prior art keywords
epoxy resin
halogen
copper
weight
resin composition
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.)
Withdrawn
Application number
JP2002072983A
Other languages
Japanese (ja)
Inventor
Yusuke Tanahashi
祐介 棚橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Chemical Corp
Original Assignee
Kyocera Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kyocera Chemical Corp filed Critical Kyocera Chemical Corp
Priority to JP2002072983A priority Critical patent/JP2003266596A/en
Publication of JP2003266596A publication Critical patent/JP2003266596A/en
Withdrawn legal-status Critical Current

Links

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper-clad laminated sheet having a low dielectric constant and a low dielectric loss tangent capable of making the propagation frequency high, capable of being manufactured by an existing manufacturing apparatus and excellent in moldability, adhesiveness, multi-ply lamination, processability or the like. <P>SOLUTION: A glass-epoxy copper-clad laminated sheet is constituted by laminating a plurality of prepregs, each of which is formed by impregnating a glass fiber substrate material with an epoxy resin composition and drying the impregnated glass fiber substrate material, and supperposing a copper foil on at least the single surface of the formed laminate to integrally mold the whole. The epoxy resin composition contains an epoxy resin (A) containing no halogen, a curing agent (B), a fire retardant (C) containing no halogen and a benzooxazine compound (D). The weight of the solid component of the benzooxazine compound (D) is 20-80% with respect to the sum total weight of the epoxy resin (A) containing no halogen, the curing agent (B), the fire retardant (C) containing no halogen and the benzooxanine compound (D). <P>COPYRIGHT: (C)2003,JPO

Description

【発明の詳細な説明】 【0001】 【産業上の利用分野】本発明は、難燃化手法としてハロ
ゲンを用いておらず、かつ低誘電率、低誘電正接の銅張
積層板であり、既存の製造装置で製造可能であり、成形
性、接着性、多層化、加工性等にも良好な積層板に関す
る。 【0002】 【従来の技術】電子機器における情報処理の高速化は際
限なく進行しているが、高速の伝搬速度を安定に保つに
は、伝搬周波数の高周波化が必要となる。その際、導電
体を支持する絶縁体の電気特性が重要な要素となり、具
体的には絶縁体の誘電率および誘電正接が低いほど良
い。従来、このような用途の絶縁体には、PTFE(ポ
リテトラフルオロエチレン)や熱硬化型PPE(ポリフ
ェニレンエーテル)等が使用されていた。 【0003】しかしながら、これらの樹脂からなる絶縁
体を用いて基板を作製する場合、これまでのガラスエポ
キシ基板の作製に用いられた製造設備をそのまま使用す
ることができず、特別な製造設備が必要なほか、加工特
性等にも劣り、広く使われるには多くの課題があった。 【0004】 【発明が解決しようとする課題】本発明は、上記の事情
に鑑みてなされたもので、低誘電率、低誘電正接の銅張
積層板を、ガラスエポキシ基板で実現したものであり、
PTFE基板やPPE基板に比べて、製造性、成形性、
接着性、多層化、加工性等が容易であり、さらに難燃化
手法としてハロゲンを用いておらず、燃焼時有毒ガスを
発生させることのない銅張積層板を提供するものであ
る。 【0005】 【課題を解決するための手段】本発明者は、上記の目的
を達成しようと鋭意研究をすすめた結果、エポキシ樹脂
組成物中に、ベンゾオキサジン化合物を添加することに
より、上記目的が達成できることを見いだし、本発明を
完成したものである 【0006】即ち、本発明は、ガラス繊維基材にエポキ
シ樹脂組成物を含浸、乾燥させたプリプレグを複数枚積
層し、その少なくとも片面に銅箔を重ね合わせて一体に
成形されたガラスエポキシ銅張積層板であって、前記エ
ポキシ樹脂組成物は、(A)ハロゲンを含まないエポキ
シ樹脂、(B)硬化剤、(C)ハロゲンを含まない難燃
剤および(D)ベンゾオキサジン化合物を必須成分とし
て含有し、かつ前記(A)ハロゲンを含まないエポキシ
樹脂、(B)硬化剤、(C)ハロゲンを含まない難燃剤
および(D)ベンゾオキサジン化合物の固形分の合計重
量に対する前記(D)ベンゾオキサジン化合物の固形分
の重量が20〜80%であることを特徴とする。 【0007】 【発明の実施の形態】以下、本発明を詳細に説明する。 【0008】本発明の銅張積層板は、ガラス繊維基材に
エポキシ樹脂組成物を含浸、乾燥させたプリプレグを複
数枚積層し、その少なくとも片面に銅箔を重ね合わせて
一体に成形された銅張積層板であって、含浸に使用され
るエポキシ樹脂組成物としてベンゾオキサジン化合物を
含む樹脂組成物を使用することを特徴とするものであ
る。 【0009】ベンゾオキサジン化合物を含むエポキシ樹
脂組成物をガラス繊維基材に含浸させてプリプレグを作
製し、これを用いて銅張積層板を作製することで、製造
性、成形性、接着性、多層化、加工性等を良好にするこ
とができるとともに、誘電率・誘電正接も低くすること
ができ、伝搬周波数の高周波化も可能となる。さらに、
本発明ではハロゲンを用いずに難燃化しているため、燃
焼時有毒ガスの発生も抑制することが可能となってい
る。 【0010】本発明に用いられるエポキシ樹脂組成物の
構成成分である(A)ハロゲンを含まないエポキシ樹脂
としては、ハロゲンを含んでおらず、かつ1分子に2個
以上のエポキシ基を有するものであれば、分子構造、分
子量などは特に制限されるものではなく、一般に使用さ
れているものを広く使用することができる。 【0011】具体的には、ビスフェノールA型エポキシ
樹脂、ビスフェノールF型エポキシ樹脂、ノボラック型
エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペ
ンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹
脂、多官能型エポキシ樹脂等が挙げられる。 【0012】これらの中でも特に接着強度や成形性を向
上させたい場合には、エポキシ当量が170〜1000
程度のビスフェノールA型エポキシ樹脂やビスフェノー
ルF型エポキシ樹脂を使用することが好ましい。また、
耐熱性を向上させたい場合には、ノボラック型エポキシ
樹脂等の多官能エポキシを使用することが好ましい。こ
れらのエポキシ樹脂は、単独または2種以上混合して使
用することができる。 【0013】本発明に用いられるエポキシ樹脂組成物の
構成成分である(B)硬化剤としては、一般的にエポキ
シ樹脂の硬化剤として使用されている化合物であればよ
く、特に制限なく使用することができる。具体的な硬化
剤としては、例えばアミン硬化系として、ジシアンジア
ミド、芳香族アミン等が挙げられ、フェノール硬化系と
して、フェノールノボラック樹脂、クレゾールノボラッ
ク樹脂、ビスフェノールA型ノボラック樹脂等が挙げら
れる。これらの硬化剤は、単独または2種以上混合して
使用することができる。 【0014】本発明に用いられるエポキシ樹脂組成物の
構成成分である(C)ハロゲンを含まない難燃剤として
は、一般的に難燃剤として使用されているものであれば
特に制限なく使用することができる。無機系充填型難燃
剤としては、例えばタルク、シリカ、アルミナ、水酸化
アルミニウム、水酸化マグネシウム等が挙げられ、これ
らは単独または2種以上混合して使用することができ
る。 【0015】有機系難燃剤としては、トリフェニルフォ
スフェート等のリン酸エステル系難燃剤、フェノキシフ
ォスファゼン類、メラミン化合物、ベンゾグアナミン化
合物、9,10−ジヒドロ−9−オキサ−10−ホスフ
ォフェナントレン−10−オキシド等が挙げられ、これ
らは単独または2種以上混合して使用することができ
る。無機系および有機系難燃剤は混合して使用してもよ
く、その配合割合は樹脂組成物全体に対して5〜50重
量%とすることが好ましい。 【0016】本発明に用いられるエポキシ樹脂組成物の
構成成分である(D)ベンゾオキサジン化合物にはいく
つかのタイプがあるが、例えば下記化学式(1)で示さ
れるようなものを使用することが好ましい。なかでも、
目的とする特性を得るためには、下記化学式(2)や化
学式(3)で表されるようなB−A型(ビスフェノール
A型)あるいはB−F型(ビスフェノールF型)のベン
ゾオキサジン化合物を使用することが、好ましい。 【0017】 【式1】 【0018】 【式2】 【0019】 【式3】 【0020】これら(D)ベンゾオキサジン化合物の配
合割合は、(A)ハロゲンを含まないエポキシ樹脂、
(B)硬化剤、(C)ハロゲンを含まない難燃剤および
(D)ベンゾオキサジン化合物の固形分の合計重量に対
して、(D)ベンゾオキサジン化合物の固形分の含有量
が20〜80%となるようにすることが好ましい。 【0021】すなわち、(A)ハロゲンを含まないエポ
キシ樹脂、(B)硬化剤、(C)ハロゲンを含まない難
燃剤および(D)ベンゾオキサジン化合物のそれぞれの
固形分の重量を[A]、[B]、[C]および[D]とすると、
(D)ベンゾオキサジン化合物の固形分の含有量は以下
のように示される。 20≦([D]/([A]+[B]+[C]+[D]))×100
≦80 【0022】(D)ベンゾオキサジン化合物の含有量が
少なすぎると、誘電率や誘電正接等の特性が所定の値に
ならず、難燃化効果も少なく、逆に多すぎると、硬化に
時間がかかりすぎたり、接着強度が低下したりする。 【0023】(D)ベンゾオキサジン化合物のより好ま
しい配合割合は、(A)ハロゲンを含まないエポキシ樹
脂、(B)硬化剤、(C)ハロゲンを含まない難燃剤お
よび(D)ベンゾオキサジン化合物の固形分の合計重量
に対して、(D)ベンゾオキサジン化合物の固形分の含
有量が30〜60%となるようにすることが好ましい
(30≦([D]/([A]+[B]+[C]+[D]))×10
0≦60)。 【0024】本発明に用いられるガラス繊維基材として
は、ガラス不織布およびガラス織布等を用いることがで
き、ガラスエポキシ銅張積層板に通常使用されるもので
あれば特に制限なく使用することができる。また、銅箔
も、通常ガラスエポキシ銅張積層板に使用されるもので
あれば特に制限なく使用することができる。 【0025】本発明の銅張積層板は、例えば以下のよう
にして作製することができる。まず、上記した(A)ハ
ロゲンを含まないエポキシ樹脂、(B)硬化剤、(C)
ハロゲンを含まない難燃剤、および(D)ベンゾオキサ
ジン化合物を所定の割合で配合した後、プロピレングリ
コールモノメチルエーテル等の好適な有機溶剤で希釈し
てワニスとし、これをガラス不織布やガラス織布等の多
孔質ガラス繊維基材に塗布、含浸させた後、加熱するこ
とによりプリプレグを作製する。 【0026】このプリプレグ複数枚を重ね合わせ、その
積層構造の片面あるいは両面に銅箔を重ね合わせた後、
加熱・加圧して一体に成形し、銅張積層板を製造する。 【0027】 【実施例】次に本発明を実施例によって説明する。本発
明はこれらの実施例によって限定されるものではない。
以下の実施例および比較例において、「部」とは「重量
部」を意味する。 【0028】実施例1 ビスフェノールA型エポキシ樹脂(エポキシ当量49
0、固形分75重量%)585部、クレゾールノボラッ
クエポキシ樹脂(エポキシ当量210、固形分70重量
%)70部、ジシアンジアミド(固形分15重量%のジ
メチルホルムアミド溶液)66部、B−A型ベンゾオキ
サジン化合物203部(固形分75重量%のメチルエチ
ルケトン溶液)、2−エチル−4メチルイミダゾール
0.2部およびジメチルホルムアミドを加えて樹脂固形
分65重量%のエポキシ樹脂ワニスを調整した。 【0029】実施例2 クレゾールノボラックエポキシ樹脂(エポキシ当量21
0、固形分70重量%)242部、フェノールノボラッ
ク樹脂(水酸基価118、固形分70重量%)76部、
縮合型リン酸エステル(固形分50重量%のメチルエチ
ルケトン溶液)289部、B−F型ベンゾオキサジン化
合物(固形分75重量%のメチルエチルケトン溶液)3
80部、2−エチル−4メチルイミダゾール0.1部お
よびシクロヘキサノンを加えて樹脂固形分65重量%の
エポキシ樹脂ワニスを調整した。 【0030】実施例3 クレゾールノボラックエポキシ樹脂(エポキシ当量21
0、固形分70重量%)411部、メラミン含有フェノ
ールノボラック樹脂(水酸基価148、固形分70重量
%)65部、フェノキシホファゼンオリゴマー(固形分
50重量%のメチルエチルケトン溶液)150部、B−
F型ベンゾオキサジン化合物(固形分75重量%のメチ
ルエチルケトン溶液)322部、2−エチル−4メチル
イミダゾール0.1部およびシクロヘキサノンを加えて
樹脂固形分65重量%のエポキシ樹脂ワニスを調整し
た。 【0031】比較例1 臭素化エポキシ樹脂(エポキシ当量490、固形分75
重量%)760部、クレゾールノボラックエポキシ樹脂
(エポキシ当量210、固形分70重量%)90部、ジ
シアンジアミド15部、2−エチル−4メチルイミダゾ
ール0.1部およびジメチルホルムアミドを加えて樹脂
固形分65重量のエポキシ樹脂ワニスを調整した。 【0032】実施例1〜3および比較例1で調整したエ
ポキシ樹脂ワニスを用いてガラス織布に連続的に含浸塗
布し、160℃の温度で乾燥しプリプレグを作製した。
このときのガラスクロスに対する樹脂分は55%とし
た。このプリプレグ5枚を重ね合わせ、その両面に厚さ
35μmの銅箔を重ね合わせて、170℃、圧力4MP
a(40kg/cm)で90分間、加熱加圧一体に成
形して、板厚1.2mmのガラスエポキシ銅張積層板を
製造した。 【0033】これらの銅張積層板について、誘電率、誘
電正接等を測定した。また、比較のために熱硬化型PP
E樹脂基板についても同様の試験を行った。これらの結
果を表1に示す。 【0034】 【表1】【0035】表1に示されるように、本発明の実施例に
おける銅張積層板は、誘電率、誘電正接等の特性に優
れ、かつボイド・カスレの発生も抑制されていることが
認められ、比較例1における銅張積層板や熱硬化型PP
E樹脂基板に比べて優れていることが認められた。 【0036】 【発明の効果】以上の説明および表1から明らかなよう
に、本発明ではエポキシ樹脂組成物中にベンゾオキサジ
ン化合物を配合することにより、製造性、成形性、接着
性、多層化、加工性等を向上させることができるととも
に、銅張積層板の高周波化に必要な低誘電率・低誘電正
接を得ることも可能となる。
Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper-clad laminate which does not use halogen as a flame-retardant method, has a low dielectric constant and a low dielectric loss tangent. The present invention relates to a laminated plate which can be manufactured by the manufacturing apparatus of (1) and has good moldability, adhesiveness, multilayering, workability and the like. 2. Description of the Related Art Although the speed of information processing in electronic devices has been increasing without limit, it is necessary to increase the propagation frequency in order to stably maintain a high propagation speed. At that time, the electrical characteristics of the insulator supporting the conductor are important factors. Specifically, the lower the dielectric constant and the dielectric loss tangent of the insulator, the better. Conventionally, PTFE (polytetrafluoroethylene), thermosetting PPE (polyphenylene ether), and the like have been used as insulators for such applications. However, when a substrate is manufactured using an insulator made of such a resin, the manufacturing equipment used for manufacturing a glass epoxy substrate cannot be used as it is, and special manufacturing equipment is required. In addition, they have poor processing characteristics and the like, and have had many problems to be widely used. SUMMARY OF THE INVENTION [0004] The present invention has been made in view of the above circumstances, and has been realized by realizing a copper-clad laminate having a low dielectric constant and a low dielectric loss tangent using a glass epoxy substrate. ,
Compared to PTFE and PPE substrates, manufacturability, moldability,
An object of the present invention is to provide a copper-clad laminate that is easy in adhesion, multilayering, workability, and the like, does not use halogen as a flame-retardant method, and does not generate toxic gas during combustion. Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, by adding a benzoxazine compound to an epoxy resin composition, the above object has been achieved. That is, the present invention has been completed, and the present invention has been completed. That is, the present invention relates to a method in which a glass fiber base material is impregnated with an epoxy resin composition and a plurality of dried prepregs are laminated, and at least one surface thereof is coated with a copper foil. Wherein the epoxy resin composition comprises (A) an epoxy resin containing no halogen, (B) a curing agent, and (C) a hardened resin containing no halogen. An epoxy resin containing a flame retardant and (D) a benzoxazine compound as essential components, and (A) a halogen-free epoxy resin; The weight of the solid content of the benzoxazine compound (D) is 20 to 80% based on the total weight of the solid content of the flame retardant and the benzoxazine compound not containing. Hereinafter, the present invention will be described in detail. [0008] The copper-clad laminate of the present invention is formed by laminating a plurality of prepregs obtained by impregnating and drying a glass fiber base material with an epoxy resin composition, and laminating a copper foil on at least one surface thereof to form a copper molded body. It is a laminated laminate, characterized in that a resin composition containing a benzoxazine compound is used as an epoxy resin composition used for impregnation. [0009] A glass fiber substrate is impregnated with an epoxy resin composition containing a benzoxazine compound to prepare a prepreg, and a copper-clad laminate is prepared using the prepreg. And the workability can be improved, the dielectric constant and the dielectric loss tangent can be reduced, and the propagation frequency can be increased. further,
In the present invention, since flame is not used without using halogen, it is possible to suppress generation of toxic gas during combustion. The (A) halogen-free epoxy resin, which is a component of the epoxy resin composition used in the present invention, is a halogen-free epoxy resin having two or more epoxy groups per molecule. If so, the molecular structure, molecular weight, and the like are not particularly limited, and generally used materials can be widely used. Specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, and polyfunctional type epoxy resin. Can be Among these, when it is desired to improve the adhesive strength and moldability, the epoxy equivalent is preferably from 170 to 1000.
It is preferable to use bisphenol A type epoxy resin or bisphenol F type epoxy resin to a certain extent. Also,
To improve heat resistance, it is preferable to use a polyfunctional epoxy such as a novolak type epoxy resin. These epoxy resins can be used alone or in combination of two or more. The curing agent (B), which is a component of the epoxy resin composition used in the present invention, may be any compound generally used as a curing agent for epoxy resins, and is not particularly limited. Can be. Specific curing agents include, for example, dicyandiamide, aromatic amines and the like as amine curing systems, and phenol novolak resins, cresol novolak resins, bisphenol A type novolak resins and the like as phenol curing systems. These curing agents can be used alone or in combination of two or more. The halogen-free flame retardant (C) which is a component of the epoxy resin composition used in the present invention can be used without any particular limitation as long as it is generally used as a flame retardant. it can. Examples of the inorganic filled flame retardant include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide and the like, and these can be used alone or in combination of two or more. Examples of the organic flame retardant include phosphoric ester flame retardants such as triphenyl phosphate, phenoxyphosphazenes, melamine compounds, benzoguanamine compounds, 9,10-dihydro-9-oxa-10-phosphophenanthrene. -10-oxide and the like, and these can be used alone or in combination of two or more. The inorganic and organic flame retardants may be used as a mixture, and the mixing ratio is preferably 5 to 50% by weight based on the whole resin composition. There are several types of the benzoxazine compound (D) which is a component of the epoxy resin composition used in the present invention. For example, it is possible to use a compound represented by the following chemical formula (1). preferable. Above all,
In order to obtain desired properties, a BA (bisphenol A) or BF (bisphenol F) benzoxazine compound represented by the following chemical formula (2) or (3) is used. It is preferred to use. [Equation 1] [Equation 2] [Equation 3] The compounding ratio of these (D) benzoxazine compounds is (A) an epoxy resin containing no halogen,
The solid content of the (D) benzoxazine compound is 20 to 80% based on the total weight of the solid content of the (B) curing agent, the (C) halogen-free flame retardant, and the (D) benzoxazine compound. Preferably. That is, the weights of the solid contents of (A) a halogen-free epoxy resin, (B) a curing agent, (C) a halogen-free flame retardant and (D) a benzoxazine compound are represented by [A], [ B], [C] and [D],
(D) The solid content of the benzoxazine compound is shown as follows. 20 ≦ ([D] / ([A] + [B] + [C] + [D])) × 100
≦ 80 (D) If the content of the benzoxazine compound is too small, the properties such as dielectric constant and dielectric loss tangent will not reach predetermined values, and the flame retardant effect will be small. It takes too much time and the adhesive strength is reduced. The more preferable mixing ratio of (D) the benzoxazine compound is (A) a halogen-free epoxy resin, (B) a curing agent, (C) a halogen-free flame retardant and (D) a solid of the benzoxazine compound. It is preferable that the content of the solid content of the (D) benzoxazine compound is 30 to 60% based on the total weight of the benzoxazine compound (30 ≦ ([D] / ([A] + [B] + [C] + [D])) × 10
0 ≦ 60). As the glass fiber substrate used in the present invention, a glass nonwoven fabric and a glass woven fabric can be used, and any glass fiber substrate usually used for a glass epoxy copper clad laminate can be used without any particular limitation. it can. The copper foil can be used without any particular limitation as long as it is usually used for a glass epoxy copper clad laminate. The copper clad laminate of the present invention can be produced, for example, as follows. First, (A) the halogen-free epoxy resin, (B) a curing agent, and (C)
After blending a halogen-free flame retardant and (D) a benzoxazine compound in a predetermined ratio, the mixture is diluted with a suitable organic solvent such as propylene glycol monomethyl ether to form a varnish, which is then used as a glass woven fabric or glass woven fabric. A prepreg is prepared by applying and impregnating a porous glass fiber base material and then heating. After laminating a plurality of prepregs and laminating copper foil on one or both sides of the laminated structure,
It is heated and pressed to form a single piece, producing a copper-clad laminate. Next, the present invention will be described by way of examples. The present invention is not limited by these examples.
In the following Examples and Comparative Examples, “parts” means “parts by weight”. Example 1 Bisphenol A type epoxy resin (epoxy equivalent 49
585 parts of cresol novolac epoxy resin (epoxy equivalent 210, solid content 70% by weight) 70 parts, dicyandiamide (dimethylformamide solution of solid content 15% by weight) 66 parts, BA benzoxazine An epoxy resin varnish having a resin solid content of 65% by weight was prepared by adding 203 parts of a compound (a 75% by weight solid content of methyl ethyl ketone solution), 0.2 part of 2-ethyl-4-methylimidazole and dimethylformamide. Example 2 Cresol novolak epoxy resin (epoxy equivalent 21
242 parts, phenol novolak resin (hydroxyl value 118, solid content 70% by weight) 76 parts,
289 parts of condensed phosphoric acid ester (solid content 50% by weight in methyl ethyl ketone solution), BF type benzoxazine compound (solid content 75% by weight in methyl ethyl ketone solution) 3
80 parts, 0.1 part of 2-ethyl-4-methylimidazole and cyclohexanone were added to prepare an epoxy resin varnish having a resin solid content of 65% by weight. Example 3 Cresol novolak epoxy resin (epoxy equivalent 21
0, solid content 70% by weight) 411 parts, melamine-containing phenol novolak resin (hydroxyl value 148, solid content 70% by weight) 65 parts, phenoxyphosphazene oligomer (methyl ethyl ketone solution with solid content 50% by weight) 150 parts, B-
322 parts of an F-type benzoxazine compound (solid content 75% by weight of methyl ethyl ketone solution), 0.1 part of 2-ethyl-4-methylimidazole and cyclohexanone were added to prepare an epoxy resin varnish having a resin solid content of 65% by weight. Comparative Example 1 Brominated epoxy resin (epoxy equivalent: 490, solid content: 75
760 parts by weight), 90 parts of cresol novolak epoxy resin (epoxy equivalent: 210, solid content: 70% by weight), 15 parts of dicyandiamide, 0.1 part of 2-ethyl-4-methylimidazole and dimethylformamide are added to obtain a resin solid content of 65 parts by weight. Was prepared. Using the epoxy resin varnishes prepared in Examples 1 to 3 and Comparative Example 1, a glass woven fabric was continuously impregnated and coated, and dried at a temperature of 160 ° C. to prepare a prepreg.
At this time, the resin content relative to the glass cloth was 55%. Five prepregs are superimposed, and a copper foil having a thickness of 35 μm is superimposed on both surfaces thereof.
a (40 kg / cm 2 ) for 90 minutes to form a glass epoxy copper clad laminate having a thickness of 1.2 mm. The dielectric constant, dielectric loss tangent, etc. of these copper-clad laminates were measured. For comparison, thermosetting PP
The same test was performed on the E resin substrate. Table 1 shows the results. [Table 1] As shown in Table 1, it was confirmed that the copper-clad laminate according to the embodiment of the present invention had excellent properties such as a dielectric constant and a dielectric loss tangent, and also suppressed the occurrence of voids and blurs. Copper-clad laminate and thermosetting PP in Comparative Example 1
It was recognized that it was superior to the E resin substrate. As is clear from the above description and Table 1, in the present invention, by blending the benzoxazine compound into the epoxy resin composition, the productivity, moldability, adhesiveness, multilayering, Workability and the like can be improved, and a low dielectric constant and a low dielectric loss tangent required for increasing the frequency of the copper-clad laminate can be obtained.

───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4F072 AA04 AA07 AB09 AB30 AD23 AD28 AE01 AE07 AF15 AF26 AF27 AF30 AG03 AH02 AH22 AJ04 AK05 AK14 AL13 4F100 AB17A AG00B AH02B AH03B AK53B BA02 CA02B CA08B DG01B EJ82B GB43 JG05 JK06 JL01    ────────────────────────────────────────────────── ─── Continuation of front page    F term (reference) 4F072 AA04 AA07 AB09 AB30 AD23                       AD28 AE01 AE07 AF15 AF26                       AF27 AF30 AG03 AH02 AH22                       AJ04 AK05 AK14 AL13                 4F100 AB17A AG00B AH02B AH03B                       AK53B BA02 CA02B CA08B                       DG01B EJ82B GB43 JG05                       JK06 JL01

Claims (1)

【特許請求の範囲】 【請求項1】 ガラス繊維基材にエポキシ樹脂組成物を
含浸、乾燥させたプリプレグを複数枚積層し、その少な
くとも片面に銅箔を重ね合わせて一体に成形されたガラ
スエポキシ銅張積層板であって、前記エポキシ樹脂組成
物は、(A)ハロゲンを含まないエポキシ樹脂、(B)
硬化剤、(C)ハロゲンを含まない難燃剤および(D)
ベンゾオキサジン化合物を必須成分として含有し、かつ
前記(A)ハロゲンを含まないエポキシ樹脂、(B)硬
化剤、(C)ハロゲンを含まない難燃剤および(D)ベ
ンゾオキサジン化合物の固形分の合計重量に対する前記
(D)ベンゾオキサジン化合物の固形分の重量が20〜
80%であることを特徴とする銅張積層板。
Claims: 1. A glass epoxy formed by laminating a plurality of prepregs impregnated and dried with an epoxy resin composition on a glass fiber base material and laminating a copper foil on at least one surface thereof. A copper-clad laminate, wherein the epoxy resin composition comprises: (A) an epoxy resin containing no halogen;
Curing agent, (C) halogen-free flame retardant and (D)
Total weight of the solid content of (A) halogen-free epoxy resin, (B) curing agent, (C) halogen-free flame retardant, and (D) benzoxazine compound, which contains a benzoxazine compound as an essential component Weight of the solid content of the (D) benzoxazine compound with respect to
A copper-clad laminate characterized by being 80%.
JP2002072983A 2002-03-15 2002-03-15 Copper-clad laminated sheet Withdrawn JP2003266596A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102069615A (en) * 2010-11-11 2011-05-25 广东生益科技股份有限公司 Fabrication method of copper-clad plate
US20130161080A1 (en) * 2011-12-22 2013-06-27 Yu-Te Lin Halogen-free resin composition and its application for copper clad laminate and printed circuit board
CN105437668A (en) * 2015-12-25 2016-03-30 广东生益科技股份有限公司 Ultrathin copper clad laminate and production method thereof
CN110204857A (en) * 2019-06-06 2019-09-06 江门建滔积层板有限公司 A kind of preparation method of the low dielectric copper-clad plate based on benzoxazine resin
JP2020007487A (en) * 2018-07-11 2020-01-16 日鉄ケミカル&マテリアル株式会社 Oxazine resin composition and cured product thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102069615A (en) * 2010-11-11 2011-05-25 广东生益科技股份有限公司 Fabrication method of copper-clad plate
US20130161080A1 (en) * 2011-12-22 2013-06-27 Yu-Te Lin Halogen-free resin composition and its application for copper clad laminate and printed circuit board
US9005761B2 (en) * 2011-12-22 2015-04-14 Elite Material Co., Ltd. Halogen-free resin composition and its application for copper clad laminate and printed circuit board
CN105437668A (en) * 2015-12-25 2016-03-30 广东生益科技股份有限公司 Ultrathin copper clad laminate and production method thereof
JP2020007487A (en) * 2018-07-11 2020-01-16 日鉄ケミカル&マテリアル株式会社 Oxazine resin composition and cured product thereof
JP7026591B2 (en) 2018-07-11 2022-02-28 日鉄ケミカル&マテリアル株式会社 Oxazine resin composition and its cured product
CN110204857A (en) * 2019-06-06 2019-09-06 江门建滔积层板有限公司 A kind of preparation method of the low dielectric copper-clad plate based on benzoxazine resin

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