JPH04181790A - Prepreg for printed circuit board - Google Patents
Prepreg for printed circuit boardInfo
- Publication number
- JPH04181790A JPH04181790A JP31072190A JP31072190A JPH04181790A JP H04181790 A JPH04181790 A JP H04181790A JP 31072190 A JP31072190 A JP 31072190A JP 31072190 A JP31072190 A JP 31072190A JP H04181790 A JPH04181790 A JP H04181790A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- prepreg
- type epoxy
- weight
- 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
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 46
- 229920003986 novolac Polymers 0.000 claims abstract description 33
- 239000004593 Epoxy Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 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 abstract description 12
- 238000005553 drilling Methods 0.000 abstract description 5
- 238000005476 soldering Methods 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 230000001133 acceleration Effects 0.000 abstract 1
- 239000002075 main ingredient Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 26
- 239000011347 resin Substances 0.000 description 26
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000003860 storage Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 6
- 229930003836 cresol Natural products 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 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 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- -1 Na CO3 Chemical class 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的〕
（産業上の利用分野）
本発明は、印刷配線板におけるドリル加工時のスミアの
発生率か低く耐熱性、耐湿性に優れるとともに、保存安
定性の良好な印刷配線板用プリプレグに関する。[Detailed Description of the Invention] [Objective of the Invention] (Industrial Field of Application) The present invention has a low smear occurrence rate during drilling in printed wiring boards, excellent heat resistance and moisture resistance, and excellent storage stability. This invention relates to a good prepreg for printed wiring boards.
（従来技術）
近年、電子機器の印刷配線板に使用されるカラスエポキ
シ銅張積層板は、コンピュータ、通信機器、工業計測機
器などの産業用機器ばかりでなく、テレビ、ビデオレコ
ーダ、音響機器などの民生用機器への利用も増加し、そ
の生産量は急激に伸びている。これに伴い、ガラスエポ
キシ＠張積層板の要求特性も多様化して、従来有してい
た耐熱性程度では満足し得なくなってきた４特に、印刷
配線板の穴明は時におけるるドリルの高速化により、穴
内温度が高くなって発生するスミア、加工後の吸湿に起
因してハンダ付時に発生するフクレ等が問題とされるよ
うになってきた。(Prior art) In recent years, glass epoxy copper-clad laminates used for printed wiring boards in electronic equipment have been used not only in industrial equipment such as computers, communication equipment, and industrial measuring equipment, but also in televisions, video recorders, audio equipment, etc. Its use in consumer devices is also increasing, and its production volume is rapidly increasing. Along with this, the required characteristics of glass epoxy@clad laminates have diversified, and the conventional heat resistance is no longer sufficient4.In particular, the speed of drilling for printed wiring boards has increased over time. As a result, problems such as smear that occurs when the temperature inside the hole increases and blisters that occur during soldering due to moisture absorption after processing have become problematic.
一般に、ガラスエポキシ＃Ｉ張檀層板に使用されるエポ
キシ樹脂組成物は、ビスフェノールＡ型エポキシ樹脂や
テトラブロムビスフェノールＡ型エポキシ樹脂に、アミ
ン、酸無水物等の硬化前およびラミの硬化促進剤を配合
したものである。この場合、耐熱性を向上させるために
、ノボラック型エポキシ樹脂を配合する方法が行われて
いる。Ｌかし、従来使用されたノボラック型エポキシ樹
脂の平均フェノール核体数は９〜１０と大きく、しがも
ビスフェノールＡ型エポキシ樹脂やテトラブロムビスフ
ェノールＡ型エポキシ樹脂に比へて硬化剤との反応か速
い、従って、これを配合したエポキシ樹脂組成物、特に
難燃性のものは１部分的にゲル化し易く、プリプレグの
保存安定性か悪く、しかもプレス成形条件の管理が難し
くなるため、ノボラック型エポキシ樹脂の配合量を多く
することができないという欠点がある。Generally, the epoxy resin composition used for glass epoxy #I sandal laminate is a bisphenol A type epoxy resin or a tetrabromo bisphenol A type epoxy resin, and a curing accelerator such as an amine or an acid anhydride before curing or during lamination. It is a combination of. In this case, in order to improve heat resistance, a method of blending a novolac type epoxy resin is used. However, the average number of phenol nuclei in conventionally used novolak epoxy resins is as large as 9 to 10, and they react more easily with curing agents than bisphenol A epoxy resins and tetrabromo bisphenol A epoxy resins. Therefore, epoxy resin compositions containing this compound, especially flame-retardant ones, tend to partially gel, resulting in poor prepreg storage stability and difficulty in controlling press molding conditions. There is a drawback that it is not possible to increase the amount of epoxy resin blended.
この欠点を改良する方法として、平均核体数２．３〜１
０のノボラック型エポキシ樹脂とビスフェノールＡ型エ
ポキシ樹脂とテトラブロムビスフェノールＡとを反えさ
せることか特開昭６１−１８８４１３号公報、特開昭６
２−６４８２１号公報によって提案されている。しかし
なから、ノボラック型エポキシ樹脂として、（ａ ）平
均核＃数７〜７０のものを反えさせると樹脂組成物が高
粘度化するため、グリプレグへの含浸性が著しく低下し
て好ましくなく、また（ｂ）平均核体数２．３〜６．９
のものを反損させると樹脂組成物の耐熱性に劣る欠点が
ある、（発明が解決しようとする課題）
本発明は、上記の欠点を解消するためになされたもので
、ドリル加工時のスミアやフクロの発生がなく、耐熱性
、耐湿性、成形性に渣れ、プリプレグの保存安定性か良
好な難燃性印刷配線板用プリプレグを提供することを目
的としている。As a method to improve this drawback, the average number of nuclei is 2.3 to 1.
JP-A-61-188413, JP-A-6
This method is proposed by Japanese Patent No. 2-64821. However, as a novolac type epoxy resin, (a) if the average number of cores is 7 to 70, the resin composition will become highly viscous, so the impregnating property into Gripreg will be significantly reduced, which is not preferable. and (b) average number of nuclear bodies 2.3 to 6.9
If the resin composition is damaged, the heat resistance of the resin composition is poor. (Problem to be solved by the invention) The present invention was made to solve the above-mentioned drawback, and it The purpose of the present invention is to provide a flame-retardant prepreg for printed wiring boards that does not generate any flakes or flakes, has good heat resistance, moisture resistance, and moldability, and has good storage stability.
「発明の構成］
（課題を解決するための手段）
本発明者らは、上記の目的を達成しようと鋭意研究を重
ねた結果、 ３種体ノボラック型エポキシ及び４種体ノ
ボラック型エポキシを主成分として３０重量％以上含有
する低分子量のノボラック型エポキシ樹脂を用いること
によって、上記目的か達成されることを見いだし、本発
明を完成したものである。"Structure of the Invention" (Means for Solving the Problems) As a result of intensive research aimed at achieving the above object, the present inventors have developed a method using 3-part novolak epoxy and 4-part novolac epoxy as main components. The present invention has been completed based on the discovery that the above object can be achieved by using a low molecular weight novolac type epoxy resin containing 30% by weight or more.
すなわち、本発明は、
（Ａ）ヒスフェノールＡ型エポキシＦＭ脂、（Ｂ）テト
ラブロムビスフェノールＡおよび（Ｃ）３種体ノボラッ
ク型エポキシ及び４種体ノボラック型エポキシを主成分
として３０重ｉ％以上含有するノボラック型エポキシ樹
脂
を反応させたエポキシ樹脂組成物を、基材に含浸・乾燥
させてなることを特徴とする印刷配線板用グリプレグで
ある。That is, the present invention comprises (A) hisphenol A type epoxy FM resin, (B) tetrabromobisphenol A, and (C) 3-type novolac-type epoxy and 4-type novolac-type epoxy as main components, and 30% by weight or more. This grippreg for printed wiring boards is characterized in that it is made by impregnating and drying a base material with an epoxy resin composition in which a novolac type epoxy resin contained therein is reacted.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に用いる（Ａ＞ヒスフェノールＡ型エポキシ樹脂
としては、ヒスフェノールＡとエピクロルヒドリンとを
′反応させてなるエポキシ樹脂で液状から固形の樹脂ま
ですべて使用することができる。これらの中でもビスフ
ェノールＡ １分子とエピクロルヒドリン２分子とを反
応させたものを主成分とする液状エポキシ樹脂が好まし
く使用することができる。The (A> hisphenol A type epoxy resin used in the present invention) is an epoxy resin made by reacting hisphenol A with epichlorohydrin, and can be used in all forms from liquid to solid resins. Among these, bisphenol A 1 A liquid epoxy resin whose main component is one obtained by reacting a molecule with two molecules of epichlorohydrin can be preferably used.
本発明に用いる（Ｂ）テトラブロムビスフェノールＡは
通常使用されるものであればよく、特に本発明のため制
限されるものではない。(B) Tetrabromobisphenol A used in the present invention may be any commonly used tetrabromo bisphenol A, and is not particularly limited for the present invention.
本発明に用いる（Ｃ）ノボラック型エポキシ樹脂は、ノ
ボラックのフェノール核数か３ａ体と ４種体とを生成
分とする低分子量のものであり、その３種体ノポラ・Ｖ
り型エポキシ及び４種体ノボラック型エポキシの含有量
は、（Ｃ）成分に対して３０重量％以上である。特に好
ましくは、平均核体数か可及的に小さく、かつ２核体成
分か１０重量％以上のものである。これらの樹脂の核種
として、フェノールノボラック型エポキシ樹脂、クレゾ
ールノボラック型エポキシ樹脂等が挙げられ、これらは
単独又は２種以上混合して使用することができる。The novolac-type epoxy resin (C) used in the present invention is a low molecular weight product containing 3a and 4 phenol nuclei of novolac, and the 3-nucleated epoxy resin is Novolac-V.
The content of the four-type novolac type epoxy and the four-type novolac type epoxy is 30% by weight or more based on component (C). Particularly preferably, the average number of nuclei is as small as possible, and the dinuclear component is 10% by weight or more. Examples of the nuclide of these resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins, etc., and these can be used alone or in a mixture of two or more types.
第１図乃至第５図はクレゾールノボラック型エポキシ樹
脂の液体クロマトグラフのチャートである。第１図及び
第２図は本発明に用いる低分子１ノボラツク型エポキシ
樹脂の液体クロマトグラフチャートである、すなわち、
第１図の樹脂は、３核体が最多成分であって、（Ｃ）成
分中における３核体及び４種体のノボラック型エポキシ
の含有ｌは液体クロマトグラフのチャートから計算する
と５５重ｉ％であり、融点が４２℃である。そのように
平均核体数が小さく融点が４２℃と低いにもかかわらす
２核体数か少ないものである。第２図の樹脂は、４核体
が最多成分（３核体と４核体の含有量４０重量５！ｉ）
であり、平均核体数か比較的小さく継点か６０°Ｃであ
って、２核体数か少ないものて−ある。また第１図で示
される ３核体を最多成分とする樹脂と、第２図で示さ
れる ４核体を最多成分とする樹脂とを任意の割合て゛
混合して３核体及び４核体を主成分として３０重量以上
％含有する樹脂を使用することかできる。1 to 5 are liquid chromatograph charts of cresol novolac type epoxy resin. FIGS. 1 and 2 are liquid chromatography charts of the low molecular weight 1 novolak type epoxy resin used in the present invention, that is,
In the resin shown in Figure 1, trinuclear bodies are the largest component, and the content of trinuclear and quaternary novolac type epoxy in component (C) is 55% by weight, calculated from a liquid chromatograph chart. It has a melting point of 42°C. Although the average number of nuclear bodies is small and the melting point is as low as 42°C, the number of two nuclear bodies is small. In the resin shown in Figure 2, tetranuclear bodies are the largest component (content of trinuclear bodies and tetranuclear bodies: 40 weight 5!i)
The average number of nuclear bodies is relatively small, the junction temperature is 60°C, and the number of dinuclear bodies is small. Alternatively, the resin shown in Fig. 1 containing trinuclear bodies as the largest component and the resin shown in Fig. 2 containing tetranuclear bodies as the largest component may be mixed in arbitrary proportions to form trinuclear bodies and tetranuclear bodies. A resin containing 30% by weight or more as a main component can be used.
第３図、第４図７第５図は従来使用されていたタレゾー
ルノボラック型エポキシ樹脂の液体クロマトグラフチャ
ートである。第３図の樹脂は２核体成分が３５重量％と
ｉし多く（３核体と４核体の含有量２８重量見）、平均
核体数か低く融点が４０°Ｃであって、本発明に用いる
第１図の樹脂と同等の融点を有する。しかし、第３図の
樹脂を用いると。FIGS. 3, 4, 7, and 5 are liquid chromatography charts of Talesol novolac type epoxy resin that has been used conventionally. The resin shown in Figure 3 has a high dinuclear component of 35% by weight (according to the content of trinuclear and tetranuclear bodies, 28% by weight), a low average number of nuclei, and a melting point of 40°C. It has a melting point equivalent to that of the resin shown in FIG. 1 used in the invention. However, if the resin shown in Fig. 3 is used.
含浸性か向上するものの＃Ｉ熟性が劣る樹脂組成物とな
るのに対して、本発明の第１図の１！ｌ脂では含浸性、
耐熱性ともに向上する。第４図の樹脂も第３図の樹脂と
同機に２核体成分が相当存在する一方、５核体成分以上
かまた多く存在して（３核体と４核体の含有量２２重量
％）平均核体数が大きくなり、融点も６０℃となる。第
４図の樹脂と本発明に用いる第２図の樹脂は同等の融点
を有するが、第４図の樹脂には５核体成分以上か５０重
量％と多く存在するため、耐熱性は向上するものの含浸
性に劣る。一方、本発明の第２図の樹脂は、４核体が最
多成分で２核体も少なく、この樹脂を用いることによっ
て耐熱性、含浸性両方の特性を向上させることができる
。第５図の樹脂は、５核体成分以上か７０重量％と多く
存在する（３核体と４核体の含有量１５重量％）ため、
融点も高＜８０℃であり、この樹脂を用いると耐熱性は
向上するものの含浸性が著しく劣る樹脂組成物となる。#I of the present invention shows #1 in Figure 1, whereas #I results in a resin composition with improved impregnation properties but poor maturation properties. l fat has impregnating properties,
Improves both heat resistance. The resin in Figure 4 is the same as the resin in Figure 3, and has a significant amount of dinuclear components, but it also has more than pentanuclear components (the content of trinuclear and tetranuclear components is 22% by weight). The average number of nuclei increases and the melting point also becomes 60°C. The resin in Figure 4 and the resin in Figure 2 used in the present invention have the same melting point, but the resin in Figure 4 has a large amount of pentanuclear components or more, or 50% by weight, so its heat resistance is improved. Poor impregnation properties. On the other hand, the resin shown in FIG. 2 of the present invention has the largest number of tetranuclear bodies and a small number of binuclear bodies, and by using this resin, both heat resistance and impregnation properties can be improved. The resin shown in Figure 5 contains a large amount of pentanuclear components or more, or 70% by weight (the content of trinuclear and tetranuclear components is 15% by weight), so
The melting point is also high, <80° C., and the use of this resin results in a resin composition with improved heat resistance but significantly poor impregnability.
３核体及び４核体を主成分とする低分子量ノボラック型
エポキシ樹脂の配合割合は、樹脂組成物に対して５〜４
０重量％含有するように配合することが望ましい。配合
割合が５重量％未満では特性向上の効果がなく、また、
４０重量％を超えると硬化剤との反応が速くなり部分的
にゲル化しやすく、また反応物の粘度が高く含浸性が悪
くなり、好ましくない。The blending ratio of the low molecular weight novolak type epoxy resin containing trinuclear and tetranuclear bodies as main components is 5 to 4 in the resin composition.
It is desirable that the content be 0% by weight. If the blending ratio is less than 5% by weight, there is no effect of improving properties, and
If it exceeds 40% by weight, the reaction with the curing agent will be rapid and gelation will occur in some areas, and the viscosity of the reactant will be high, resulting in poor impregnating properties, which is not preferable.
本発明に用いるエポキシ樹脂組成物は、ビスフェノール
Ａ型エポキシ樹脂、テトラブロムビスフェノールＡ、特
定のノボラック型エポキシ樹脂の反応をＮ ａ ＯＨ、
Ｎａ ＣＯ３等の無機塩基、無機塩、第３級アミン、
第４級アンモニウム塩−笛４級ホスホニウム塩等の存在
下で反えさせることかできる２本発明に用いるエポキシ
樹脂組成物は、上記の各成分を必須の成分とするが、本
発明の目的に反しない範囲において他の成分を配合する
ことができる。こうして得られたエポキシ樹脂組成物を
、基材に含浸・乾燥させて容易にプリプレグを製造する
ことができる。ここで用いる基材としでは、ガラスクロ
ス、カラスペーパー等、通常使用されるものが使用でき
特に限定されるものではない。The epoxy resin composition used in the present invention includes a reaction of bisphenol A type epoxy resin, tetrabromobisphenol A, and a specific novolac type epoxy resin, with N a OH,
Inorganic bases such as Na CO3, inorganic salts, tertiary amines,
The epoxy resin composition used in the present invention has each of the above-mentioned components as essential components. Other components can be blended as long as they do not interfere with the composition. A prepreg can be easily produced by impregnating and drying the base material with the epoxy resin composition obtained in this way. The base material used here is not particularly limited, and can be any commonly used base material, such as glass cloth or glass paper.
（作用）
本発明は、３核体及び４核体の７ボラツク型エポキシを
主成分として３０重量％以上含有する低分子量ノボラッ
ク型エポキシ樹脂を用いたことによって、耐熱性、耐湿
性、成形性に優れ、保存安定性のよい印刷配線板用プリ
プレグを製造することができる。(Function) The present invention has improved heat resistance, moisture resistance, and moldability by using a low molecular weight novolac type epoxy resin containing 30% by weight or more of trinuclear and tetranuclear hepvolak type epoxy as the main component. It is possible to produce a prepreg for printed wiring boards that is excellent and has good storage stability.
３核体と４核体がノボラック型エポキシｔＭ脂における
３０重置火以上の主成分であるならば一平均核体数を小
さくし、５核体以上の含有Ｉが少なくなって含浸性の悪
さが改良され、また２核体か１５重置火以下という少量
となって耐熱性を向上させることができる。さらに、こ
のエポキシ樹脂組成物の硬化剤との反応においても、５
核体以上の存在を少なくすることにより、反応速度を低
下させることか可能となり、プリプレグとした場合にグ
リプレグの保存安定性を向上させ、がっプレス成形性も
安定となる。If trinuclear bodies and tetranuclear bodies are the main components of novolak type epoxy tM resin with 30 or more superpositions, the average number of nuclei should be reduced, and the I content of pentanuclear bodies or more will be reduced, resulting in poor impregnating properties. is improved, and the heat resistance can be improved by reducing the amount of dinuclear bodies to 15 times or less. Furthermore, in the reaction of this epoxy resin composition with a curing agent, 5
By reducing the presence of more than a nucleus, it is possible to reduce the reaction rate, and when used as a prepreg, the storage stability of the grippreg is improved, and the press moldability is also stabilized.
（実施例）
次に本発明を実施例によって説明するが、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。(Examples) Next, the present invention will be explained by examples, but the present invention is not limited by these examples.
実８１．例 １
コンデンサ付四つロフラスコにビスフェノールＡ型エポ
キシ樹脂（エポキシ当量１８９） ２ｉｏｇ、テトラブ
ロムビスフェノールＡ１３０Ω、３０重量％以上の３核
体を主成分とするクレゾールノボラック型エポキシ樹脂
（第１図、融点４２°Ｃ）６０ｇ、テトラエチルアンモ
ニウムクロライド０．０２ｇを入れてフラスコ内を窒素
置換した０次いで１４０°Ｃの温度で５時間反応させた
後、メチルエチルケトン１３５９を加えてｖ！Ｊｈ固形
分７５重量％、粘度、２ポアス（２５℃）エポキシ当量
４１０、臭素含有率１９％のエポキシａｌｌｌ脂組成物
溶液を製造した０次にジシアンジアミド１１，２９．２
−エチル−４−メチルイミダゾールを０．０５ｇおよび
アセトンを加えて樹脂固形分６５重量％ワニスを調製し
た６
実施例 ２
コンデンサ付四つロフラスコにビスフェノールＡ型エポ
キシ樹脂（エポキシ化ｊｉ １８９） １５０Ｑ、テト
ラブロムビスフェノールＡ１３０Ｑ、３０重量％以上の
４核体を主成分とするクレゾールノボラック型エポキシ
樹脂（第２図、融点６０℃） １２０Ｑ、テトラエチル
アンモニウムクロライド０．０２！Ｊを入れてフラスコ
内を窒素置換した。次いで１４０℃の温度で５時間反応
させた後、メチルエチルケトン１３５Ｑを加えて樹脂固
形分７５重量ｅ。、粘度５．２ボアス（２５°Ｃ）、エ
ポキシ当量４２０、臭素含有率１９％のエポキシ樹脂矧
成物溶液を製造した８次にジシアンジアミド１１．０Ω
、２−エチル−４−メチルイミダゾールを０．０５ｇお
よびアセトンを加えて樹脂固形分６５重量％のワニスを
調製した。Fruit 81. Example 1 Bisphenol A type epoxy resin (epoxy equivalent: 189) in a four-bottle flask with a condenser, 2 iog, tetrabromobisphenol A 130Ω, cresol novolac type epoxy resin whose main component is 30 wt % or more of trinuclear bodies (Fig. 1, melting point 42) °C) and 0.02 g of tetraethylammonium chloride, the inside of the flask was purged with nitrogen, and after reacting at a temperature of 140 °C for 5 hours, methyl ethyl ketone 1359 was added and v! Jh0-order dicyandiamide 11,29.2 to prepare an epoxy all fat composition solution having a solid content of 75% by weight, a viscosity of 2 pores (25°C), an epoxy equivalent of 410, and a bromine content of 19%.
A varnish with a resin solid content of 65% by weight was prepared by adding 0.05 g of -ethyl-4-methylimidazole and acetone6. Bromobisphenol A130Q, cresol novolak type epoxy resin whose main component is 30% by weight or more of tetranuclear bodies (Fig. 2, melting point 60°C) 120Q, tetraethylammonium chloride 0.02! J was added to replace the inside of the flask with nitrogen. After reacting at a temperature of 140° C. for 5 hours, methyl ethyl ketone 135Q was added to give a resin solid content of 75 weight e. , an 8-order dicyandiamide 11.0 ohm solution was prepared with an epoxy resin pellet solution having a viscosity of 5.2 bores (25°C), an epoxy equivalent weight of 420, and a bromine content of 19%.
, 0.05 g of 2-ethyl-4-methylimidazole and acetone were added to prepare a varnish having a resin solid content of 65% by weight.
比較例 １
コンデンサ付四つロフラスコにヒスフェノールＡ型エポ
キシｔ！ｌ脂（エポキシ化ｊＬ １８９） ２１０ａ、
テトラブロムビスフェノールＡ１３０ｇ、クレゾールノ
ボラック型エポキシ樹脂く第５図、融点８０°Ｃ）６０
Ｑ、テトラエチルアンモニウムクロライド０．０２（１
を入れてフラスコ内を窒素置換した４次いで１４０℃の
温度で５時間反応させた後、メチルエチルケトン１３５
Ｑを加えて樹脂固形分７５重量％、粘度９．２ポアズ（
２５℃）エポキシ化１４３０、臭素含有率１９％のエポ
キシ樹脂組成＊ 浴液を製造した９次にジシアンジアミ
ド１１．２ｇ、２−エチル−４−メチルイミダゾールを
Ｏ，ｏｓｇおよびアセトンを加え、樹脂固形分６５重量
％のワニスを調製した。Comparative Example 1 Hisphenol A type epoxy t! in a four-bottle flask with a condenser. L fat (epoxidized jL 189) 210a,
Tetrabromobisphenol A 130g, cresol novolak type epoxy resin (Figure 5, melting point 80°C) 60
Q, tetraethylammonium chloride 0.02 (1
The inside of the flask was replaced with nitrogen. After reacting at a temperature of 140°C for 5 hours, methyl ethyl ketone 135
Q was added to give a resin solid content of 75% by weight and a viscosity of 9.2 poise (
25℃) Epoxidation 1430, bromine content 19% epoxy resin composition A 65% by weight varnish was prepared.
比較例 ２
コンデンサ付四つロフラスコにビスフェノールＡ型エポ
キシ樹脂（エポキシ化ｊＬ １８９） ２１０ｇ、クレ
ゾールノボラック型エポキシ樹脂（第３図、融点４２℃
） ６０Ｑ 、テトラブロムビスフェノールＡ１３０ｇ
、テトラエチルアンモニウムクロライド０，０２Ｑを加
えてフラスコ内を窒素置換した２次いで、１４０”Ｃの
温度で５時間反応させた後、メチルエチルケトン１３５
ｇを加えて樹脂固形分７５重量％、粘度、１ポアズ（２
５℃）エポキシ化１４２０、臭素含有率１９％のエポキ
シ樹脂組成物を製造した２次にジシアンジアミド１１．
２Ｑ 、２−エチル−４−メチルイミダゾールをｏ、
０５Ｑおよびアセトンを加えてＩ［ｌＷ固形分６５重量
％のワニスを調製した。Comparative Example 2 In a four-bottle flask with a condenser, 210 g of bisphenol A type epoxy resin (epoxidized jL 189), cresol novolac type epoxy resin (Fig. 3, melting point 42°C)
) 60Q, tetrabromobisphenol A 130g
, tetraethylammonium chloride 0.02Q was added and the inside of the flask was purged with nitrogen.Next, after reacting at a temperature of 140"C for 5 hours, methyl ethyl ketone 135
g to give a resin solid content of 75% by weight, a viscosity of 1 poise (2
5°C) Epoxidation 1420, secondary dicyandiamide 11. produced an epoxy resin composition with a bromine content of 19%.
2Q, 2-ethyl-4-methylimidazole o,
A varnish with an I[lW solids content of 65% by weight was prepared by adding 05Q and acetone.
実施例１〜２および比較例１〜２で調製したワニスを用
いて、エポキシシランで表面処理した厚さ０．１８ｎｎ
のガラス基材に含浸塗布し、１６０℃の温度で乾燥して
ｖｆＪ脂分が４３重量％の印刷配線板用プリプレグを製
造した。Using the varnishes prepared in Examples 1-2 and Comparative Examples 1-2, the surface was treated with epoxy silane to a thickness of 0.18 nn.
A prepreg for a printed wiring board having a VFJ fat content of 43% by weight was produced by impregnating and coating a glass substrate and drying at a temperature of 160°C.
このプリプレグ８枚を重ね合わせ、その両面に厚さ１８
μｍの銅箔を重ね合わせて、温度１７０°Ｃ１圧力４０
ｋｇ／ ｃｎ２で９０分間、加熱加圧一体に成形して板
厚１．６ｎｉの＠頭槓層板を製造した。8 sheets of prepreg are stacked on top of each other, with a thickness of 18 mm on both sides.
Copper foils of μm are overlapped, temperature 170°C, pressure 40
kg/cn2 for 90 minutes to produce a @head laminate with a thickness of 1.6 ni.
これらの＃４張積層仮について、難燃性、ガラス転位点
、ハンダ耐熱性および耐ミーズリング性を測定しなので
その結果を第１表に示した。The flame retardancy, glass transition point, solder heat resistance and measling resistance of these #4 laminates were measured and the results are shown in Table 1.
第１表
（単位）
＊１ ：ＵＬ９４により測定
＊２：ＤＳＣ（示差走査熱量計）による中点法＊３：２
６０’Ｃのハンダ浴上に表に示した各時間浮かベフクレ
の有無を試験した
◎印・・・全部無し、 ○印・・・一部有り、 △印・
・・大部有り、 ×印・・・全部有り１：１２０℃、２
気圧の水蒸気中で表に示した各時間処理した後、２６０
℃のハンダ洛中に３０秒間浸漬し、フクロの有無を試験
しな
◎印・・・全部無し、 ○印・・・一部有り、 △印・
・・大部有り、 ×印・・・全部有り。Table 1 (Units) *1: Measured according to UL94 *2: Midpoint method using DSC (differential scanning calorimeter) *3: 2
The presence or absence of floating bubbles was tested on a 60'C solder bath for the times shown in the table. ◎ mark: None, ○ mark: Some presence, △ mark.
・・Most of them are available, × mark...All of them are available 1: 120℃, 2
After treatment in water vapor at atmospheric pressure for the times indicated in the table, 260
Immerse it in a soldering solution at ℃ for 30 seconds and test for the presence or absence of bags.◎ mark: None, ○ mark: Some presence, △ mark:
...Most of them are available, × mark...All of them are available.
また、ドリル加工性は、回路層４層（＃ｌ箔厚み１８、
７０．７０．１８μ［）、板厚１．６ｎ＋ｍの回路板を
３枚重ね、ドリル径０．９ｍａ、ドリル回ｋｌｋ６０．
０００ ｒＤＮ、ドリル送り速度２．１（ｔｏ信ｉ／ｌ
ｌ１ｎで試験して、穴あけ数ｂｉｔ （横軸）とスミア
発生率％（縮軸）との関係を求めて、第６図に示した。In addition, the drill workability is 4 circuit layers (#l foil thickness 18,
70.70.18μ[), 3 circuit boards with board thickness 1.6n+m stacked, drill diameter 0.9ma, drill speed klk60.
000 rDN, drill feed rate 2.1 (to communication i/l
The relationship between the number of holes perforated (horizontal axis) and the smear occurrence rate % (reduced axis) was determined by testing with l1n, and is shown in FIG.
次にまた、プリプレグの保存安定性は、プリプレグを３
０日間にわたり４０℃で保存処理して、初期硬化時間に
対する硬化時間の変化率（％）を求めて、第７図に示し
た。Next, the storage stability of prepreg is
After storage treatment at 40° C. for 0 days, the rate of change (%) in curing time with respect to initial curing time was determined and is shown in FIG.
第１表、第６図、第７図の結果をみてわかるとおり、い
ずれの試験においても本発明か優れており、本発明の効
果を確認することかできな。As can be seen from the results in Table 1, FIG. 6, and FIG. 7, the present invention was superior in all tests, and the effects of the present invention cannot be confirmed.
［発明の効果〕
以上の説明によって明らかなように、本発明の印刷配線
板用プリプレグは、耐熱性に優れ、ドリル高速化による
スミアにも十分対応でき、また積層板加工後の吸湿によ
るハンダ付時のフクロの発生もない、更に部分的にゲル
化することもなくプリプレグの保存安定性やプレス成形
条件の管理等がし易くなり、成形性の優れたものである
。[Effects of the Invention] As is clear from the above explanation, the prepreg for printed wiring boards of the present invention has excellent heat resistance, can sufficiently cope with smear caused by high-speed drilling, and also prevents soldering due to moisture absorption after laminated board processing. It has excellent moldability, with no formation of flakes or partial gelation, making it easier to control the storage stability of the prepreg and press molding conditions.
第１図及び第２図は本発明におけるノボラック型エポキ
シ樹脂の組成を示す液体クロマトグラフのチャート、第
３図乃至第５図は従来使用されたノボラック型エポキシ
樹脂の組成を示す液体クロマトグラフのチャート、第６
図は本発明実施例と比較例とのドリル加工性を示すグラ
フ、第７図は本発明実施例と比較例とのプリプレグの保
存安定性を示すグラフである。
第１図
第２図
館３図
第４図
第５図
第６図
＠７図
−へ７９Figures 1 and 2 are liquid chromatograph charts showing the composition of the novolak epoxy resin in the present invention, and Figures 3 to 5 are liquid chromatograph charts showing the composition of the novolak epoxy resin conventionally used. , 6th
The figure is a graph showing the drill workability of the present invention example and the comparative example, and FIG. 7 is the graph showing the storage stability of the prepreg of the present invention example and the comparative example. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 @Figure 7-79
Claims (1)
型エポキシを主成分として３０重量％以上含有するノボ
ラック型エポキシ樹脂を反応させたエポキシ樹脂組成物
を、基材に含浸・乾燥させてなることを特徴とする印刷
配線板用プリプレグ。[Claims] 1. A novolac containing 30% by weight or more of (A) bisphenol A epoxy resin, (B) tetrabromobisphenol A and (C) trinuclear novolak epoxy and nuclear novolac epoxy as main components. A prepreg for printed wiring boards, characterized in that it is made by impregnating and drying a base material with an epoxy resin composition in which a type epoxy resin is reacted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2310721A JPH0760921B2 (en) | 1990-11-16 | 1990-11-16 | Prepreg for printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2310721A JPH0760921B2 (en) | 1990-11-16 | 1990-11-16 | Prepreg for printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04181790A true JPH04181790A (en) | 1992-06-29 |
| JPH0760921B2 JPH0760921B2 (en) | 1995-06-28 |
Family
ID=18008681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2310721A Expired - Lifetime JPH0760921B2 (en) | 1990-11-16 | 1990-11-16 | Prepreg for printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0760921B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04220422A (en) * | 1990-12-20 | 1992-08-11 | Nippon Kayaku Co Ltd | Epoxy resin, resin composition containing same, and cured article prepared from the composition |
| JPH04318017A (en) * | 1991-04-15 | 1992-11-09 | Yuka Shell Epoxy Kk | Novolak type epoxy resin |
| JPH06100660A (en) * | 1992-09-22 | 1994-04-12 | Sumitomo Chem Co Ltd | Epoxy resin composition and copper-clad laminate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6253342A (en) * | 1985-09-03 | 1987-03-09 | Mitsubishi Gas Chem Co Inc | Manufacturing method of epoxy resin laminate |
| JPS63260933A (en) * | 1987-04-20 | 1988-10-27 | Mitsubishi Petrochem Co Ltd | Copper-clad laminate |
-
1990
- 1990-11-16 JP JP2310721A patent/JPH0760921B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6253342A (en) * | 1985-09-03 | 1987-03-09 | Mitsubishi Gas Chem Co Inc | Manufacturing method of epoxy resin laminate |
| JPS63260933A (en) * | 1987-04-20 | 1988-10-27 | Mitsubishi Petrochem Co Ltd | Copper-clad laminate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04220422A (en) * | 1990-12-20 | 1992-08-11 | Nippon Kayaku Co Ltd | Epoxy resin, resin composition containing same, and cured article prepared from the composition |
| JPH04318017A (en) * | 1991-04-15 | 1992-11-09 | Yuka Shell Epoxy Kk | Novolak type epoxy resin |
| JPH06100660A (en) * | 1992-09-22 | 1994-04-12 | Sumitomo Chem Co Ltd | Epoxy resin composition and copper-clad laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0760921B2 (en) | 1995-06-28 |
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