JPH0611786B2 - Manufacturing method of metal foil clad laminate - Google Patents
Manufacturing method of metal foil clad laminateInfo
- Publication number
- JPH0611786B2 JPH0611786B2 JP11298689A JP11298689A JPH0611786B2 JP H0611786 B2 JPH0611786 B2 JP H0611786B2 JP 11298689 A JP11298689 A JP 11298689A JP 11298689 A JP11298689 A JP 11298689A JP H0611786 B2 JPH0611786 B2 JP H0611786B2
- Authority
- JP
- Japan
- Prior art keywords
- metal foil
- clad laminate
- butadiene polymer
- weight
- compound
- 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.)
- Expired - Lifetime
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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Landscapes
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、難燃性樹脂組成物を用いた金属箔張り積層板
に関し、プリント配線板用として適したものに関する。TECHNICAL FIELD The present invention relates to a metal foil-clad laminate using a flame-retardant resin composition, which is suitable for a printed wiring board.
従来の技術 近年、電子機器においては、素子の高密度実装、信号の
高速化、高周波数化に伴い、信号の遅延が問題となって
きている。そこで、各種素子を実装するプリント配線板
の基板には、低誘電材料の適用が強く要求されている。
このような低誘電材料の１つにブタジエン重合体があ
り、エポキシ化ブタジエン重合体とテトラブロモビスフ
ェノールＡを必須成分とする樹脂組成物による金属箔張
り積層板が開発されている（特開昭61-192720号公
報）。その樹脂系では、従来のブタジエン重合体の欠点
である積層板製造工程におけるプリプレグの粘着性の問
題は解消しているものの、耐熱性に問題がある。2. Description of the Related Art In recent years, in electronic devices, signal delay has become a problem with high-density mounting of elements, high-speed signals, and high frequencies. Therefore, it is strongly required to apply a low dielectric material to a substrate of a printed wiring board on which various elements are mounted.
One of such low-dielectric materials is a butadiene polymer, and a metal foil-clad laminate made of a resin composition containing epoxidized butadiene polymer and tetrabromobisphenol A as essential components has been developed (JP-A-61). -192720 publication). Although the resin system solves the problem of the tackiness of the prepreg in the laminated plate manufacturing process, which is a drawback of the conventional butadiene polymer, it has a problem of heat resistance.
発明が解決しようとする課題 すなわち、エポキシ化ブタジエン重合体のエポキシ基と
テトラブロモビスフェノールＡの水酸基を反応させ、架
橋させているのであるから、ブタジエン重合体の二重結
合の部分は消化されずに残る。したがって、架橋密度を
上げる上で限界があり、三次元構造が十分形成されな
い。その結果、積層板の性能において耐熱性が不十分と
なり、積層板の厚さ方向の寸法変化率が大きくなるた
め、プリント配線板としたときのスルホール信頼性に劣
っていた。That is, since the epoxy groups of the epoxidized butadiene polymer and the hydroxyl groups of tetrabromobisphenol A are reacted and crosslinked, the double bond portion of the butadiene polymer is not digested. Remain. Therefore, there is a limit to increase the crosslink density, and the three-dimensional structure is not sufficiently formed. As a result, heat resistance becomes insufficient in the performance of the laminated board, and the dimensional change rate in the thickness direction of the laminated board increases, so that the through-hole reliability of the printed wiring board is poor.
本発明の課題は、上記の点に鑑み、プリント配線板の用
途として適した、高周波特性と耐熱性に優れた難燃性樹
脂組成物を用いた金属箔張り積層板を提供することであ
る。In view of the above points, an object of the present invention is to provide a metal foil-clad laminate using a flame-retardant resin composition having excellent high frequency characteristics and heat resistance, which is suitable for use as a printed wiring board.
課題を解決するための手段 本発明に係る難燃性金属箔張り積層板の製造法は、次の
（ａ）〜（ｃ）を必須成分として配合した樹脂組成物を
硬化剤と共にシート状基材に含浸、乾燥してプリプレグ
を得、該プリプレグを表面に載置した金属箔と共に積層
成形するものである。Means for Solving the Problems A method for producing a flame-retardant metal foil-clad laminate according to the present invention is a sheet-shaped substrate together with a curing agent containing a resin composition containing the following (a) to (c) as essential components. Is impregnated and dried to obtain a prepreg, and the prepreg is laminated and formed with a metal foil placed on the surface.
(a)1,2-結合が50％以上であるブタジエン重合体をエポ
キシ化して、100ｇ当りのエポキシ基含有量を0.3モル以
上としたエポキシ化ブタジエン重合体 (b)テトラブロモビスフェノールＡ (c) で示される化合物Ｉ（但し、R1,R2,R3は、ＨまたはCH3
を表す） 上記樹脂組成物において、好ましくは、エポキシ化ブタ
ジエン重合体の配合は、20〜47重量％、化合物Ｉの配合
は60〜10重量％である。(a) Epoxidized butadiene polymer having 1,2-bonds of 50% or more and having an epoxy group content of 0.3 mol or more per 100 g (b) Tetrabromobisphenol A (c) Compound I (wherein R 1 , R 2 and R 3 are H or CH 3
In the above resin composition, preferably, the epoxidized butadiene polymer content is 20 to 47% by weight, and the compound I content is 60 to 10% by weight.
作用 本発明においては、まず、エポキシ化ブタジエン重合体
を用いることにより、硬化反応としてラジカル重合系の
中にエポキシ基の開環反応を併用でき、成形性の優れた
プリプレグを得ることができる。また、エポキシ化ブタ
ジエン重合体と化合物Ｉには、両方とも極性基であるエ
ポキシ基が存在しているため、金属箔の引きはがし強さ
の大きい金属箔張り積層板を得ることができる。Action In the present invention, first, by using an epoxidized butadiene polymer, a ring-opening reaction of an epoxy group can be used in combination in a radical polymerization system as a curing reaction, and a prepreg excellent in moldability can be obtained. Further, since both the epoxidized butadiene polymer and the compound I have an epoxy group which is a polar group, a metal foil-clad laminate having high peel strength of the metal foil can be obtained.
さらに、化合物Ｉは、分子の一方の末端にエポキシ基を
もっているが、他方の末端には二重結合をもつため、こ
れがエポキシ化ブタジエン重合体の二重結合と反応して
架橋密度が大幅に増加するので、耐熱性が良好となる。
化合物Ｉには、臭素分子が導入されているので、難燃性
も十分なレベルを確保できる。Furthermore, since Compound I has an epoxy group at one end of the molecule but has a double bond at the other end, this reacts with the double bond of the epoxidized butadiene polymer, and the crosslink density is greatly increased. Therefore, the heat resistance becomes good.
Since the bromine molecule is introduced into the compound I, it is possible to secure a sufficient level of flame retardancy.
尚、エポキシ化ブタジエン重合体の配合量は、少なすぎ
ると高周波特性の改善に不十分であり、多すぎると耐熱
性が低くなる。また、化合物Ｉの配合量は、少なすぎる
と耐熱性が低くなり、多すぎると高周波特性の改善が不
十分となる。If the blending amount of the epoxidized butadiene polymer is too small, the high frequency characteristics will not be improved, and if it is too large, the heat resistance will be low. Further, if the compounding amount of the compound I is too small, the heat resistance becomes low, and if it is too large, the improvement of the high frequency characteristic becomes insufficient.
実施例 本発明においては、樹脂組成物の硬化剤の一部をフェノ
ールノボラック樹脂、クレゾールノボラック樹脂などの
ノボラック樹脂で置きかえてもかまわず、エポキシ基の
開環反応を起こすものであれば、特に限定しない。ま
た、本発明に使用するラジカル重合開始剤は、ベンゾイ
ルパーオキシド、ジクミルパーオキソド、メチルエチル
ケトンパーオキシド等があげられるが、特に限定するも
のではない。Examples In the present invention, a part of the curing agent of the resin composition may be replaced with a novolac resin such as a phenol novolac resin or a cresol novolac resin, as long as it causes a ring-opening reaction of an epoxy group, it is not particularly limited. do not do. Further, the radical polymerization initiator used in the present invention includes benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, etc., but is not particularly limited.
金属箔張り積層板を製造するとき、樹脂組成物を含浸さ
せるシート状基材としては、ガラス繊維織布、ガラス繊
維不織布、合成繊維織布、合成繊維不織布、紙などがあ
げられるが、特に限定するものではない。また、金属箔
は、銅箔、ニッケル箔、アルミニウム箔などであるが特
に限定しない。When manufacturing the metal foil-clad laminate, examples of the sheet-shaped base material impregnated with the resin composition include glass fiber woven cloth, glass fiber non-woven cloth, synthetic fiber woven cloth, synthetic fiber non-woven cloth, paper and the like, but are not particularly limited. Not something to do. Further, the metal foil is a copper foil, a nickel foil, an aluminum foil or the like, but is not particularly limited.
実施例１〜３，比較例１ エポキシ化ブタジエン重合体（商品名BF-1000、日本曹
達製）、テトラブロモビスフェノールＡ（TBBA）、化合
物Ｉとして臭素化ビスフェノールＡタイプエポキシハー
フメタアクリレート（昭和高分子製）、およびフェノー
ルノボラック樹脂（商品名TD-2093、大日本インキ製）
を、第１表に示す割合（重量部）で配合し、メチルエチ
ルケトンに溶解して固形分75重量％とした。さらに、ラ
ジカル重合開始剤として、ジクミルパーオキシド（商品
名パークミルＤ、日本油脂製）、を前記固形分100重量
部に対して１重量部、硬化促進剤として、２−エチル、
４−メチルイミダゾールを１重量部配合してワニスを調
製した。Examples 1 to 3, Comparative Example 1 Epoxidized butadiene polymer (trade name BF-1000, manufactured by Nippon Soda), tetrabromobisphenol A (TBBA), and compound I as brominated bisphenol A type epoxy half methacrylate (Showa High Polymer) Made), and phenol novolac resin (trade name TD-2093, made by Dainippon Ink)
Was mixed at a ratio (parts by weight) shown in Table 1 and dissolved in methyl ethyl ketone to a solid content of 75% by weight. Further, as a radical polymerization initiator, dicumyl peroxide (trade name Percumil D, manufactured by NOF CORPORATION), 1 part by weight based on 100 parts by weight of the solid content, 2-ethyl as a curing accelerator,
A varnish was prepared by blending 1 part by weight of 4-methylimidazole.
上記ワニスをガラス繊維織布（厚さ0.18mm）に含浸、乾
燥して粘着性のないプリプレグを得た（樹脂量40重量
％）。前記プリプレグを８枚重ね、その両面に35μｍ厚
の銅箔を載置して、温度170℃、圧力30kgｆ／cm2で９０
分間積層成形して、銅張り積層板を得た。A glass fiber woven fabric (thickness: 0.18 mm) was impregnated with the above varnish and dried to obtain a tack-free prepreg (resin amount: 40% by weight). The prepreg 8 layers, by placing the copper foil 35μm thick on both sides, the temperature 170 ° C., at a pressure 30 kgf / cm 2 90
The laminate was molded for a minute to obtain a copper-clad laminate.
得られた積層板の特性を第１表に併せて示す。The properties of the obtained laminate are also shown in Table 1.
従来例１ ブロム化エポキシ樹脂（商品名YDB-500、東都化成製）8
5重量部、クレゾールノボラックエポキシ樹脂（商品名Y
DCN-704、東都化成製）15重量部、ジシアンジアミド（D
ICY）2.5重量部をメチルエチルケトンに溶解し、固形分
75重量％とした。これに、２−エチル、４−メチルイミ
ダゾールを、前記固形分100重量部に対し１重量部配合
して、ワニスとした。Conventional example 1 Brominated epoxy resin (Brand name YDB-500, manufactured by Tohto Kasei) 8
5 parts by weight, cresol novolac epoxy resin (trade name Y
DCN-704, manufactured by Tohto Kasei) 15 parts by weight, dicyandiamide (D
ICY) 2.5 parts by weight dissolved in methyl ethyl ketone
It was set to 75% by weight. To this, 1 part by weight of 2-ethyl and 4-methylimidazole was added to 100 parts by weight of the solid content to prepare a varnish.
上記ワニスを用い、以下実施例と同様にして銅張り積層
板を得た。得られた積層板の特性を第１表に示す。Using the above varnish, a copper clad laminate was obtained in the same manner as in the examples below. The properties of the resulting laminate are shown in Table 1.
発明の効果 第１表から明らかなように、本発明に係る金属箔張り積
層板は、難燃性と共に優れた耐熱性と高周波特性を備え
ており、プリント配線板用として適したものである。 EFFECTS OF THE INVENTION As is clear from Table 1, the metal foil-clad laminate according to the present invention has flame resistance and excellent heat resistance and high frequency characteristics, and is suitable for printed wiring boards.
Claims (2)
合した難燃性樹脂組成物を硬化剤と共にシート状基材に
含浸、乾燥してプリプレグを得、該プリプレグを表面に
載置した金属箔と共に積層成形することを特徴とする金
属箔張り積層板の製造法。 （ａ）１，２−結合が５０％以上であるブタジエン重合
体をエポキシ化して、１００ｇ当りのエポキシ基含有量
を０．３モル以上としたエポキシ化ブタジエン重合体 （ｂ）テトラブロモビスフェノールＡ （ｃ） で示される化合物Ｉ（但し、Ｒ1，Ｒ2，Ｒ3は、Ｈまた
はＣＨ3を表す）1. A sheet-shaped substrate is impregnated with a flame-retardant resin composition containing the following (a) to (c) as an essential component together with a curing agent and dried to obtain a prepreg. The prepreg is provided on the surface. A method for producing a metal foil-clad laminate, which comprises laminating and molding the placed metal foil. (A) Epoxidized butadiene polymer having an epoxy group content of 0.3 mol or more per 100 g by epoxidizing a butadiene polymer having a 1,2-bond content of 50% or more (b) Tetrabromobisphenol A ( c) Compound I represented by (wherein R 1 , R 2 , and R 3 represent H or CH 3 )
〜４７重量％、化合物Ｉの配合が６０〜１０重量％であ
る請求項１記載の金属箔張り積層板の製造法。2. The composition of epoxidized butadiene polymer is 20.
The method for producing a metal foil-clad laminate according to claim 1, wherein the compound I content is 60 to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11298689A JPH0611786B2 (en) | 1989-05-02 | 1989-05-02 | Manufacturing method of metal foil clad laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11298689A JPH0611786B2 (en) | 1989-05-02 | 1989-05-02 | Manufacturing method of metal foil clad laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02292326A JPH02292326A (en) | 1990-12-03 |
| JPH0611786B2 true JPH0611786B2 (en) | 1994-02-16 |
Family
ID=14600552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11298689A Expired - Lifetime JPH0611786B2 (en) | 1989-05-02 | 1989-05-02 | Manufacturing method of metal foil clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611786B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0216170D0 (en) * | 2002-07-12 | 2002-08-21 | Hexcel Composites Ltd | Resin compositions |
-
1989
- 1989-05-02 JP JP11298689A patent/JPH0611786B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02292326A (en) | 1990-12-03 |
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