JPS63215734A - Epoxy resin prepreg for laminate - Google Patents
Epoxy resin prepreg for laminateInfo
- Publication number
- JPS63215734A JPS63215734A JP4820887A JP4820887A JPS63215734A JP S63215734 A JPS63215734 A JP S63215734A JP 4820887 A JP4820887 A JP 4820887A JP 4820887 A JP4820887 A JP 4820887A JP S63215734 A JPS63215734 A JP S63215734A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- prepreg
- weight
- epoxy resin
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920003986 novolac Polymers 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002966 varnish Substances 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- UBRZBGHTKKELLW-UHFFFAOYSA-N 3-(2-chlorophenyl)-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=CC=C1Cl UBRZBGHTKKELLW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000003365 glass fiber Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- URZYXZHQFVVPAB-UHFFFAOYSA-N 1-chloro-3,3-dimethyl-1-phenylurea Chemical compound CN(C)C(=O)N(Cl)C1=CC=CC=C1 URZYXZHQFVVPAB-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プリント配線板等に使用される成形性に優れ
た積層板用エポキシ樹脂プリプレグに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an epoxy resin prepreg for laminates that has excellent moldability and is used for printed wiring boards and the like.
近年コンピュータ、無線応用機器、工業計測機器、医療
機器等の産業用機器の発展は目覚しく、それらに使用さ
れるプリント配線板は高密度配線が行われるようになり
、ドリル加工性、耐熱性、寸法安定性の向上を目的とし
た改良がなされている。一方プリント配線板の製造工程
では、製品１枚当りの時間短縮による製造合理化が種々
検討され、中でも積層工程における時間短縮が検討され
。In recent years, the development of industrial equipment such as computers, wireless application equipment, industrial measuring equipment, and medical equipment has been remarkable, and the printed wiring boards used for these have become highly densely wired, with improvements in drillability, heat resistance, and size. Improvements have been made to improve stability. On the other hand, in the manufacturing process of printed wiring boards, various methods of streamlining production by shortening the time per product have been studied, and in particular, shortening the time in the lamination process has been studied.
多段、多数枚プレス成形が行われている。Multi-stage, multi-sheet press molding is performed.
プリント配線板用の積層板は、一般的には次のようにし
て製造されている。すなわち第１図に示すように、回路
加工した内層板（１）の両側に接着用のプリプレグ（２
）および片面接着処理した銅箔（３）を配置した構成品
（４）を、第２図に示すように、多数組の鏡面板（５）
間にはさんで積み重ね、クッション材（６）を使用して
プレス熱盤（７）間に仕込み。Laminated boards for printed wiring boards are generally manufactured as follows. That is, as shown in Fig. 1, adhesive prepregs (2
) and a component (4) with single-sided adhesive treated copper foil (3), as shown in Fig.
Stack them in between, and use the cushioning material (6) to place them between the press heat plates (7).
加熱、加圧を行って製造している。Manufactured by heating and pressurizing.
積層板を製造する場合、一般に加熱は室温よ°す１６０
〜１８０℃に昇温しで、所定温度になるまで低圧（例４
ｋｇｆ／ｃＪ）で保持し、その後高圧（例４０ｋｇｆ／
ａ＃）をかけて成形する。低圧保持時間は最適樹脂流れ
を確保する意味で、非常に重要なファクターとなる。こ
れが最適時間より短すぎると、プリプレグ（２）の樹脂
粘度が低いうちに高圧がかかるため、樹脂の流れすぎに
よる端部かすれ、層間厚み不良が発生する。また長すぎ
ると、プリプレグ（２）の樹脂粘度が高くなった時点で
高圧がかけられるため、均一な樹脂流れが起きずに、回
路間にボイドが発生する。When manufacturing laminates, heating is generally done at room temperature or 160°C.
Raise the temperature to ~180℃ and apply low pressure (Example 4) until the specified temperature is reached.
kgf/cJ) and then high pressure (e.g. 40 kgf/cJ).
a#) and mold. Low pressure holding time is a very important factor in ensuring optimal resin flow. If this time is too short than the optimum time, high pressure will be applied while the resin viscosity of the prepreg (2) is low, resulting in edges being blurred and poor interlayer thickness due to excessive resin flow. Moreover, if it is too long, high pressure will be applied when the resin viscosity of the prepreg (2) becomes high, so that uniform resin flow will not occur and voids will occur between the circuits.
これらの不都合をなくすため、低圧保持時間は昇温速度
ならびにプリプレグ（２）の樹脂流れ特性により決定さ
れる。In order to eliminate these disadvantages, the low pressure holding time is determined by the temperature increase rate and the resin flow characteristics of the prepreg (2).
内層板（１）の両側に、プリプレグ（２）を介して外層
の銅箔（３）を配置した構成品（４）をプレス熱盤（７
）間に４組仕込む役向４枚押しの場合、熱盤（７）側仕
込み製品（１，４枚目の製品）と中央部仕込み製品（２
，３枚目の製品）の昇温速度に大きな差はない。しかし
製品１枚当りの製造時間短縮のため、プレス熱盤（７）
間に８〜１０組を仕込んで多数枚成形を行う場合、大き
な昇温のずれが生じる。A component (4) in which outer layer copper foil (3) is placed on both sides of an inner layer board (1) via a prepreg (2) is pressed onto a hot plate (7).
) In the case of a 4-piece press, with 4 sets placed between
, 3rd product)) There is no big difference in the heating rate. However, in order to shorten the manufacturing time per product, press heating plate (7)
When molding a large number of sheets by preparing 8 to 10 sets in between, a large deviation in temperature rise occurs.
このため従来の樹脂流れ特性を有するプリプレグ（２）
を用いて多数枚成形を行うと、所定の低圧保持時間にお
ける熱盤（７）側製品と、中央部製品の樹脂粘度が大き
く違うため、前者には流れ不足による回路間ボイド、後
者には流れすぎによる製品端部かずれが発生する傾向が
ある。Therefore, prepreg (2) with conventional resin flow characteristics
When molding a large number of sheets using a , the resin viscosity of the product on the hot platen (7) side and the product on the center part at a predetermined low pressure holding time is greatly different, so the former has voids between circuits due to insufficient flow, and the latter has voids due to flow. There is a tendency for the edges of the product to shift due to rinsing.
従来のプリント配線板等の積層板用プリプレグのエポキ
シ樹脂の硬化剤としては、安価でプリプレグとしての保
存安定性の良いジシアンジアミド／アミン触媒系が用い
られてきた。この場合アミン触媒が少なすぎると成形時
、樹脂の流れすぎによる端部かすれ、耐熱低下が起こり
、多すぎると流動性低下によるボイドが発生して多層成
形は難かしいが、アミン触媒量を調節して硬化性、流動
性の調整を行っている。しかし現実にはプリプレグの製
造における乾燥時に、アミン触媒が飛散したり、トリー
タ乾燥条件が少しでも変化すると、アミン触媒の反応性
が高いため、Ｂステージ化の程度が異なり、多数枚成形
に適した安定した性能のプリプレグを得ることが困難で
ある。As a curing agent for epoxy resin in conventional prepregs for laminated boards such as printed wiring boards, dicyandiamide/amine catalyst systems have been used because they are inexpensive and have good storage stability as prepregs. In this case, if the amine catalyst is too small, the resin will flow too much during molding, causing edges to become blurred and heat resistance to deteriorate; if it is too large, voids will occur due to reduced fluidity, making multilayer molding difficult, but the amount of amine catalyst can be adjusted. The curing properties and fluidity are adjusted using However, in reality, if the amine catalyst scatters during drying during prepreg production, or if the treater drying conditions change even slightly, the degree of B-staging will differ due to the high reactivity of the amine catalyst, making it difficult to make it suitable for multi-sheet molding. It is difficult to obtain prepregs with stable performance.
一方ジシアンジアミドの代りに、フェノールノボラック
樹脂もしくはアルキルフェノールノボラック樹脂を硬化
剤とするプリプレグも知られている。しかしこの場合、
そのプリプレグの保存安定性が悪いという問題点があっ
た。On the other hand, prepregs using a phenol novolak resin or an alkylphenol novolac resin as a curing agent instead of dicyandiamide are also known. But in this case,
There was a problem that the prepreg had poor storage stability.
本発明は上記問題点を解決するためのもので、保存安定
性が良く、積層工程における時間短縮のための多段、多
数枚プレスが容易にできるような成形硬化性、流動性を
もち、かつ安定した性能を与える積層板用エポキシ樹脂
プリプレグを得ることを目的とする。The present invention is intended to solve the above problems, and has good storage stability, mold hardening properties and fluidity that allow easy multi-stage and multi-sheet pressing to shorten the time in the lamination process, and stable The purpose of this study is to obtain an epoxy resin prepreg for laminates that provides the desired performance.
本発明の積層板用エポキシ樹脂プリプレグは。 The epoxy resin prepreg for laminates of the present invention is:
エポキシ樹脂１００重量部に対して、ジシアンジアミド
１〜３重量部、フェノールノボラック樹脂またはアルキ
ルフェノールノボラック樹脂１〜６重量部、および硬化
触媒として３−（クロルフェニル）−１，１−ジメチル
尿素０．１〜０．５重量部を有機溶剤に溶解したワニス
を基材に含浸させ、乾燥してなるものである。For 100 parts by weight of epoxy resin, 1 to 3 parts by weight of dicyandiamide, 1 to 6 parts by weight of phenol novolak resin or alkylphenol novolak resin, and 0.1 to 3-(chlorphenyl)-1,1-dimethylurea as a curing catalyst. The base material is impregnated with 0.5 parts by weight of varnish dissolved in an organic solvent and dried.
本発明において用いるエポキシ樹脂は、エポキシ基を分
子当り平均２個以上有する化合物であり、特に限定され
ないが、具体的にはビスフェノール系エポキシ樹脂、ハ
ロゲン化ビスフェノール系エポキシ樹脂、フェノールノ
ボラック系エポキシ樹脂、ハロゲン化フェノールノボラ
ック系エポキシ樹脂、アルキルフェノールノボラック系
エポキシ樹脂、ポリフェノール系エポキシ樹脂、ポリグ
リコール系エポキシ樹脂、脂環系エポキシ樹脂等がある
。これらの樹脂を単独使用してもよく、また２種以上の
併用も可能である。The epoxy resin used in the present invention is a compound having an average of two or more epoxy groups per molecule, and examples thereof include, but are not limited to, bisphenol-based epoxy resins, halogenated bisphenol-based epoxy resins, phenol novolac-based epoxy resins, and halogenated epoxy resins. Examples include chemical phenol novolak epoxy resins, alkylphenol novolak epoxy resins, polyphenol epoxy resins, polyglycol epoxy resins, and alicyclic epoxy resins. These resins may be used alone or in combination of two or more.
本発明におけるジシアンジアミドの配合量は、エポキシ
樹脂１００重量部に対して１〜３重量部であり、１重量
部未満では硬化不良となり、３重斌部を越えるとプリプ
レグ表面にジシアンジアミドの結晶が析出しやすく１反
応が不均一になり、ブラウンスポット等が生じやすくな
るのでいずれも好ましくない。The amount of dicyandiamide blended in the present invention is 1 to 3 parts by weight per 100 parts by weight of the epoxy resin. If it is less than 1 part by weight, curing will be poor, and if it exceeds 3 parts by weight, crystals of dicyandiamide will precipitate on the surface of the prepreg. Both are unfavorable because they tend to cause non-uniform reactions and brown spots.
本発明におけるフェノールノボラック樹脂またはアルキ
ルフェノールノボラック樹脂は、下記の一般式
〔但し、Ｒは水素またはＣ，、、Ｈ２１，、＋□（ｍ＝
１〜９）を示し、平均重合度（重合度＝ｎ＋１）３〜１
０、遊離モノマー量０．５％以下である。〕
で表わされる樹脂である。平均重合度が１０を越えると
エポキシ樹脂に対する反応が不均一となり、３より小さ
くなると硬化物の特性が低下するようになる。またアル
キルフェノールノボラック樹脂を使用する場合において
、フェノール核への置換アルキル基の炭素数が９を越え
ると置換基がバルキーになり過ぎ、アルキルフェノール
ノボラック樹脂の反応性が低下するので、上記の範囲が
好ましい。そしてその配合量は、エポキシ樹脂１（１０
ｆｆｉ斌部に対して１〜６重量部であり、これらの樹脂
はプリプレグに適当な溶融粘度を安定に与えるという役
割を持ち、１重量部未満ではその効果がなく、６重量部
を越えると、Ｂステージ化の際プリプレグの溶融粘度が
高くなりすぎ、成形性が悪くなるためいずれも好ましく
ない。The phenol novolak resin or alkylphenol novolac resin in the present invention has the following general formula [where R is hydrogen or C, , H21,, +□ (m=
1 to 9), and the average degree of polymerization (degree of polymerization = n+1) is 3 to 1.
0, the amount of free monomer is 0.5% or less. ] It is a resin represented by If the average degree of polymerization exceeds 10, the reaction with the epoxy resin will become non-uniform, and if it is less than 3, the properties of the cured product will deteriorate. Further, when using an alkylphenol novolac resin, if the number of carbon atoms in the alkyl group substituted on the phenol nucleus exceeds 9, the substituent becomes too bulky and the reactivity of the alkylphenol novolak resin decreases, so the above range is preferable. The blending amount of the epoxy resin is 1 (10
The amount of these resins is 1 to 6 parts by weight based on the part of ffi, and these resins have the role of stably providing an appropriate melt viscosity to the prepreg, and if it is less than 1 part by weight, it has no effect, and if it exceeds 6 parts by weight, Both are unfavorable because the melt viscosity of the prepreg becomes too high during B-stage formation, resulting in poor moldability.
本発明における硬化触媒は３−（クロルフェニル）−１
，１−ジメチル尿素で、特に３−（ｐ−クロルフェニル
）−１，１−ジメチル尿素が好ましい。その配合量はエ
ポキシ樹脂プリシレグが適当な成形性を持つ配合量で、
エポキシ樹脂１００重量部に対してｏ、１〜０．５重量
部である。この硬化触媒の添加量が少ないとエポキシ樹
脂の硬化が不十分で、プリント配線板の耐熱性に問題が
あり、添加量が多いと多数枚成形を行った場合の昇温の
ずれの影響が大きくなったり、プリプレグの流動性が低
下し、いずれも好ましくない。The curing catalyst in the present invention is 3-(chlorphenyl)-1
, 1-dimethylurea, and 3-(p-chlorophenyl)-1,1-dimethylurea is particularly preferred. The blending amount is such that the epoxy resin Prisireg has suitable moldability.
It is 1 to 0.5 parts by weight based on 100 parts by weight of the epoxy resin. If the amount of this curing catalyst added is small, the curing of the epoxy resin will be insufficient and there will be problems with the heat resistance of the printed wiring board, and if the amount added is too large, the effect of temperature rise deviation will be large when molding a large number of sheets. or the fluidity of the prepreg decreases, both of which are undesirable.
基材としてはガラス繊維１合成育機繊維、石英繊維、ア
ルミナ繊維等の布、マット、ペーパーなどがあげられ、
特に限定されない。Examples of the base material include cloth, mat, paper, etc. such as glass fiber, synthetic fiber, quartz fiber, and alumina fiber.
Not particularly limited.
本発明の積層板用エポキシ材脂プリプレグは、上記各成
分を有機溶剤に溶解したワニスを上記基材に含浸させ、
乾燥させてＢステージ化して製造される。このようなプ
リプレグにより積層板を製造する方法は従来のプリプレ
グと同様である。The epoxy resin prepreg for laminates of the present invention is obtained by impregnating the base material with a varnish in which the above components are dissolved in an organic solvent.
It is manufactured by drying and turning it into a B stage. The method for manufacturing a laminate using such prepreg is the same as that for conventional prepreg.
本発明による積層板用エポキシ樹脂プリプレグにおいて
は、硬化剤としてジシアンジアミド、およびフェノール
ノボラック樹脂またはアルキルフェノールノボラック樹
脂、ならびに硬化触媒として３−（クロルフェニル）−
ｉ、ｉ−ジメチル尿素を適当量配合することにより、保
存安定性が良く、プリプレグのＢステージ化が容易で、
多段、多数枚プレス成形時において適当な硬化性、溶融
粘度を持ち、成形性が向上する。In the epoxy resin prepreg for laminates according to the present invention, dicyandiamide and a phenol novolac resin or an alkylphenol novolak resin are used as a curing agent, and 3-(chlorphenyl)- as a curing catalyst.
By blending an appropriate amount of i,i-dimethylurea, it has good storage stability, and it is easy to B-stage the prepreg.
It has suitable hardenability and melt viscosity and improves moldability during multi-stage, multi-sheet press molding.
以下本発明を実施例によって具体的に説明する。 The present invention will be explained in detail below using examples.
実施例１
ブロム化ビスフェノールＡ系エポキシ樹脂（油化シェル
社製、商品名、エピコート５０４６Ｂ−８０、エポキシ
当量４８０．８０％ＭＥＫ溶液）１１２．５重量部、ブ
レゾールノボラック系エポキシ樹脂（ダウケミカル社製
、商品名、ＥＣＮ−１２７３、エポキシ当量２１７）
１ｏ、０重量部、ジシアンジアミド２．０重量部、アル
キルフェノールノボラック樹脂（大日本インキ工業社製
、商品名、プライオーフェンＶＨ−４１７０、分子量７
２０、ＯＨ当量１１８） ３．０重量部、および３−（
ｐ−クロルフェニル）−１，１−ジメチル尿素０．２５
重量部をメチルセロソルブ４８．０重量部に溶解してワ
ニスを得た。Example 1 112.5 parts by weight of brominated bisphenol A-based epoxy resin (manufactured by Yuka Shell Co., Ltd., trade name, Epicoat 5046B-80, MEK solution with epoxy equivalent of 480.80%), Bresol novolac-based epoxy resin (Dow Chemical Company) (product name, ECN-1273, epoxy equivalent weight 217)
1 o, 0 parts by weight, dicyandiamide 2.0 parts by weight, alkylphenol novolak resin (manufactured by Dainippon Ink Industries, trade name, Pryophen VH-4170, molecular weight 7)
20, OH equivalent 118) 3.0 parts by weight, and 3-(
p-chlorophenyl)-1,1-dimethylurea 0.25
Parts by weight were dissolved in 48.0 parts by weight of methyl cellosolve to obtain a varnish.
このワニスを厚み０．１８ｗｍ平織ガラス布（旭シェー
ベル社製、商品名、 ７６２ｇ−１０５０−ＡＳ４６０
処理）に含浸させた後、１４５℃５分間乾燥してプリプ
レグ（２）を得た。このプリプレグ（２）４枚の両面に
７０μの銅１（３）（日鉱グールド・フォイル社製、商
品名、ＪＴＣ−１０２）を重ね、 １７０℃９０分間プ
レス成形して面面鋼張板を得、残銅約５０％のモデルパ
ターンで回路加工を行い内層板（１）を得た。この内層
板（１）の両面にそれぞれ２枚のプリプレグ（２）およ
び１８μ銅箔（３）を第１図に示すように配置して構成
品（４）とした。製品サイズを４５０ｍｍ Ｘ ４５０
ｍｍとした上記構成品（４）を４組プレス熱盤（７）間
に仕込む膜内４枚押し、ならびに構成品（４）を８ｇプ
レス熱盤（７）間に仕込む役向８枚押しを行った。構成
品（４）は１ＩＩ１１厚鏡面板（５）間に仕込み、クッ
ション材（６）を第２図に示すように配置した。プレス
圧力は４ｋｇｆ／ａ＃の低圧保持時間を１５分間とし、
その後４０ｋｇｆ／ａ＃で９０分間加圧して最高温度を
１７０℃とし、冷却は加圧状態のまま３０分間行った。This varnish was applied to a 0.18w thick plain-woven glass cloth (manufactured by Asahi Shavel Co., Ltd., trade name, 762g-1050-AS460).
Prepreg (2) was obtained by drying at 145° C. for 5 minutes. Copper 1 (3) of 70 μm (manufactured by Nikko Gould Foil Co., Ltd., trade name, JTC-102) was layered on both sides of the four sheets of prepreg (2), and press-formed at 170°C for 90 minutes to obtain a steel-clad plate. , circuit processing was performed using a model pattern with approximately 50% remaining copper to obtain an inner layer board (1). Two sheets of prepreg (2) and 18μ copper foil (3) were arranged on both sides of this inner layer board (1) as shown in FIG. 1 to obtain a component (4). Product size: 450mm x 450
The above-mentioned component (4) with a thickness of mm is placed between 4 sets of press hot plates (7), and 8 sheets of the component (4) are placed between 8 g of press hot plates (7). went. The component (4) was placed between the 1II11 thick mirror plates (5), and the cushioning material (6) was arranged as shown in FIG. The press pressure was 4 kgf/a# with a low pressure holding time of 15 minutes.
Thereafter, it was pressurized at 40 kgf/a# for 90 minutes to reach a maximum temperature of 170° C., and cooling was performed for 30 minutes while maintaining the pressurized state.
得られたプリプレグ（２）の特性ならびに多層板の特性
を表１に示す。成形性はプリント配線板の外側の銅箔（
３）をエツチング除去して、ボイド、かすれの有無を目
視判定した。Table 1 shows the properties of the obtained prepreg (2) and the properties of the multilayer board. Formability is determined by the copper foil on the outside of the printed wiring board (
3) was removed by etching, and the presence or absence of voids and scratches was visually determined.
比較例１
アルキルフェノールノボラック樹脂を除き、３−（ｐ−
クロルフェニル）−１，１−ジメチル尿素の代りにベン
ジルジメチルアミン０．２５重量部を添加したほかは、
実施例１と同樹脂配合でワニスを作製し。Comparative Example 1 Except for the alkylphenol novolak resin, 3-(p-
Except that 0.25 parts by weight of benzyldimethylamine was added instead of chlorphenyl-1,1-dimethylurea.
A varnish was prepared using the same resin formulation as in Example 1.
実施例１と同条件でプリプレグ（２）およびプリント配
線板を作製した。結果を表１に示す。A prepreg (2) and a printed wiring board were produced under the same conditions as in Example 1. The results are shown in Table 1.
比較例２
アルキルフェノールノボラック樹脂を除き、３−（ｐ−
クロルフェニル）−１，１−ジメチル尿素の代りに２−
エチル−４−メチルイミダゾール０．２４重量部を添加
したほかは、実施例１と同樹脂配合でワニスを作製し、
実施例１と同条件でプリプレグ（２）およびプリント配
線板を作製した。結果を表１に示す。Comparative Example 2 Except for the alkylphenol novolac resin, 3-(p-
2-instead of chlorphenyl)-1,1-dimethylurea
A varnish was prepared using the same resin formulation as in Example 1, except that 0.24 parts by weight of ethyl-4-methylimidazole was added.
A prepreg (2) and a printed wiring board were produced under the same conditions as in Example 1. The results are shown in Table 1.
表１
１ ０−・・良好 Δ・・・やや不良 Ｘ・・・不
良■１０ａｗ角５枚 １７０℃ １４０ｋｇｆ／ａ＃
１０分間■１７０℃熱盤
■２６０℃ハンダフロート
表１から実施例１のプリプレグは、成形時の硬化性およ
び溶融粘度が適当であるため１段内８枚押し成形性が良
好であり、耐熱性に異常がないことがわかる。これに対
して比較例１のプリプレグは、同一乾燥条件では実施例
１に比べてゲル化時間が多少遅く、成形時の溶融粘度が
低いため、流れすぎによる端部かずれが発生し、接着強
度不足による耐熱性劣化が見られる。また比較例２のプ
リプレグは、硬化速度が速く、役向８枚押しの場合、熱
盤側製品は中央部製品よりも硬化が進んだ時点で高圧が
かけられるため、回路間にボイドが発生した。Table 1 1 0-...Good Δ...Slightly poor X...Poor■ 10aw square 5 pieces 170℃ 140kgf/a#
10 minutes ■ 170℃ heating plate ■ 260℃ solder float From Table 1, the prepreg of Example 1 has appropriate hardenability and melt viscosity during molding, so it has good moldability by pressing 8 sheets in one stage, and has good heat resistance. It can be seen that there is no abnormality. On the other hand, the prepreg of Comparative Example 1 had a somewhat slower gelation time than Example 1 under the same drying conditions and had a lower melt viscosity during molding, which caused the edges to shift due to excessive flow, resulting in poor adhesive strength. Deterioration of heat resistance is observed due to shortage. In addition, the prepreg of Comparative Example 2 had a fast curing speed, and in the case of 8-sheet pressing, higher pressure was applied to the product on the hot platen side when the curing progressed more than the product on the center side, so voids were generated between the circuits. .
以上説明したように、本発明によれば、硬化剤としてジ
シアンジアミドおよびフェノールノボラック樹脂または
アルキルフェノールノボラック樹脂を配合し、硬化触媒
として３−（クロルフェニル）−１，１−ジメチル尿素
を配合したので、成形時の硬化性および溶融粘度が適当
な値となり、このため多段、多数枚成形が可能なプリプ
レグを得ることができる。As explained above, according to the present invention, dicyandiamide and a phenol novolac resin or an alkylphenol novolak resin are blended as a curing agent, and 3-(chlorphenyl)-1,1-dimethylurea is blended as a curing catalyst. The curing properties and melt viscosity at the time of preparation become appropriate values, and therefore a prepreg that can be molded in multiple stages and in large numbers can be obtained.
第１図および第２図はプリント配線板の製造工程を示す
断面図である。
各図中、同一符号は同一部分を示し、（１）は内層板１
． （２）はプリプレグ、（３）は銅箔、（４）は構成
品、（５）は鏡面板、（６）はクッション材、（７）は
プレス熱盤である。FIGS. 1 and 2 are cross-sectional views showing the manufacturing process of a printed wiring board. In each figure, the same reference numerals indicate the same parts, and (1) indicates the inner layer plate 1.
．． (2) is a prepreg, (3) is a copper foil, (4) is a component, (5) is a mirror plate, (6) is a cushioning material, and (7) is a press hot plate.
Claims (1)
アミド１〜３重量部、フェノールノボラック樹脂または
アルキルフェノールノボラック樹脂１〜６重量部、およ
び硬化触媒として３−（クロルフェニル）−１，１−ジ
メチル尿素０．１〜０．５重量部を有機溶剤に溶解した
ワニスを基材に含浸させ、乾燥してなることを特徴とす
る積層板用エポキシ樹脂プリプレグ。(1) For 100 parts by weight of epoxy resin, 1 to 3 parts by weight of dicyandiamide, 1 to 6 parts by weight of phenol novolak resin or alkylphenol novolak resin, and 0 parts of 3-(chlorophenyl)-1,1-dimethylurea as a curing catalyst. An epoxy resin prepreg for laminates, characterized in that it is obtained by impregnating a base material with a varnish in which 0.1 to 0.5 parts by weight is dissolved in an organic solvent and drying it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4820887A JPS63215734A (en) | 1987-03-03 | 1987-03-03 | Epoxy resin prepreg for laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4820887A JPS63215734A (en) | 1987-03-03 | 1987-03-03 | Epoxy resin prepreg for laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63215734A true JPS63215734A (en) | 1988-09-08 |
Family
ID=12796977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4820887A Pending JPS63215734A (en) | 1987-03-03 | 1987-03-03 | Epoxy resin prepreg for laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63215734A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6231959B1 (en) * | 1995-02-27 | 2001-05-15 | Matsushita Electric Works, Ltd. | Prepreg of epoxy resin, hardener, and organodialkyurea promotor |
-
1987
- 1987-03-03 JP JP4820887A patent/JPS63215734A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6231959B1 (en) * | 1995-02-27 | 2001-05-15 | Matsushita Electric Works, Ltd. | Prepreg of epoxy resin, hardener, and organodialkyurea promotor |
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