JPH04222816A - Phenolic resin composition for laminate - Google Patents
Phenolic resin composition for laminateInfo
- Publication number
- JPH04222816A JPH04222816A JP40547890A JP40547890A JPH04222816A JP H04222816 A JPH04222816 A JP H04222816A JP 40547890 A JP40547890 A JP 40547890A JP 40547890 A JP40547890 A JP 40547890A JP H04222816 A JPH04222816 A JP H04222816A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- resin
- brominated epoxy
- laminate
- epoxy 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.)
- Withdrawn
Links
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 35
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 239000002966 varnish Substances 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011342 resin composition Substances 0.000 abstract 2
- 239000000126 substance Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、プリント配線板などの
絶縁基板となる積層板を製造するために用いられるフェ
ノール樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenolic resin composition used for producing a laminate serving as an insulating substrate such as a printed wiring board.
【０００２】0002
【従来の技術】プリント配線板などの絶縁基板として使
用されるフェノール樹脂積層板は、紙やガラス布等の基
材にフェノール樹脂ワニスを含浸させて乾燥することに
よってプリプレグを作成し、このプリプレグを複数枚重
ねて加熱加圧成形することによって、製造することがで
きる。[Prior Art] Phenolic resin laminates used as insulating substrates such as printed wiring boards are made by impregnating a base material such as paper or glass cloth with phenolic resin varnish and drying it to create a prepreg. It can be manufactured by stacking a plurality of sheets and molding them under heat and pressure.
【０００３】そしてこの積層板の耐熱性や難燃性を高め
るために、従来からフェノール樹脂ワニスにブロム化エ
ポキシ樹脂を添加配合することがおこなわれている。[0003] In order to improve the heat resistance and flame retardancy of this laminate, a brominated epoxy resin has conventionally been added to a phenolic resin varnish.
【０００４】0004
【発明が解決しようとする課題】しかし、従来から使用
されているブロム化エポキシ樹脂では難燃性を確保する
ことはできるが、十分な耐熱性を積層板に確保すること
はできないという問題があった。本発明は上記の点に鑑
みてなされたものであり、積層板の耐熱性を十分に高め
ることができる積層板用フェノール樹脂組成物を提供す
ることを目的とするものである。[Problems to be Solved by the Invention] However, although flame retardancy can be ensured with conventionally used brominated epoxy resins, there is a problem in that it is not possible to ensure sufficient heat resistance in the laminate. Ta. The present invention has been made in view of the above points, and an object of the present invention is to provide a phenolic resin composition for a laminate that can sufficiently improve the heat resistance of the laminate.
【０００５】[0005]
【課題を解決するための手段】本発明に係る積層板用フ
ェノール樹脂組成物は、フェノール樹脂ワニスに、ブロ
ム化エポキシ樹脂成分としてフェノール硬化型ブロム化
エポキシ樹脂を添加配合して成ることを特徴とするもの
である。以下本発明を詳細に説明する。本発明において
ブロム化エポキシ樹脂成分として使用するフェノール硬
化型ブロム化エポキシ樹脂は、３官能以上の多官能エポ
キシ樹脂を含有していてフェノール樹脂ワニス中の未反
応フェノールと容易に反応して硬化するものであり、特
許出願公表昭６１−５０１７１２号公報において開示さ
れているものを使用することができる。従来から使用さ
れているビスフェノール系のブロム化エポキシ樹脂は２
官能性であってフェノールとの反応が遅く、フェノール
とホルマリンとの反応生成物であるメチロールフェノー
ルと優先的に反応するのに対して、フェノール硬化型ブ
ロム化エポキシ樹脂はメチロールフェノールとも反応す
るが未反応フェノールと反応して、フェノール樹脂ワニ
ス中の未反応フェノールモノマーを消費すると共に硬化
速度を速め、フェノール樹脂積層板の耐熱性を高めるこ
とができるものである。積層板の樹脂はそのガラス転移
温度（Ｔｇ）が熱機械分析（ＴＭＡ）法で１３０℃以上
の耐熱性を有するように作成するのが好ましい。[Means for Solving the Problems] The phenolic resin composition for laminates according to the present invention is characterized in that it is made by adding and blending a phenol-curable brominated epoxy resin as a brominated epoxy resin component to a phenolic resin varnish. It is something to do. The present invention will be explained in detail below. The phenol-curable brominated epoxy resin used as the brominated epoxy resin component in the present invention contains a trifunctional or higher-functional epoxy resin and easily reacts with unreacted phenol in the phenolic resin varnish to cure it. The one disclosed in Patent Application Publication No. 1988-501712 can be used. The conventionally used bisphenol-based brominated epoxy resin is 2
It is functional and reacts slowly with phenol, preferentially reacting with methylolphenol, which is a reaction product of phenol and formalin, whereas phenol-curing brominated epoxy resins also react with methylolphenol, but do not react with methylolphenol. It reacts with the reactive phenol to consume unreacted phenol monomers in the phenolic resin varnish, speed up the curing speed, and increase the heat resistance of the phenolic resin laminate. It is preferable that the resin of the laminate is made so that its glass transition temperature (Tg) has a heat resistance of 130° C. or higher as measured by thermomechanical analysis (TMA).
【０００６】フェノール硬化型ブロム化エポキシ樹脂と
して市販に供されているものでは、ダウケミカル社製の
「Ｑｕａｔｒｅｘ５０１０」をその代表例として挙げる
ことができる。この「Ｑｕａｔｒｅｘ５０１０」はエポ
キシ成分として「化１」に示す３官能タイプのものを含
んでおり、硬化時に「化２」に示すテトラブロモビスフ
ェノールＡ（ＴＢＢＡ）と反応する機構になっており、
この反応機構内に未反応フェノールモノマーを取り込ん
で硬化を進めるものと考えられ、また３官能タイプであ
るために三次元架橋反応が迅速に進んで硬化速度を速め
ることができると考えられる。[0006] Among the commercially available phenol-curable brominated epoxy resins, "Quatrex 5010" manufactured by Dow Chemical Company can be cited as a representative example. This "Quatrex 5010" contains the trifunctional type shown in "Chemical formula 1" as an epoxy component, and has a mechanism that reacts with tetrabromobisphenol A (TBBA) shown in "Chemical formula 2" during curing.
It is thought that unreacted phenol monomer is incorporated into this reaction mechanism to promote curing, and since it is a trifunctional type, it is thought that the three-dimensional crosslinking reaction proceeds quickly and the curing rate can be increased.
【０００７】[0007]
【化１】[Chemical formula 1]
【０００８】[0008]
【化２】[Case 2]
【０００９】そして、フェノール樹脂ワニスにフェノー
ル硬化型ブロム化エポキシ樹脂を添加配合して本発明に
係るフェノール樹脂組成物を調製することができる。フ
ェノール硬化型ブロム化エポキシ樹脂の配合量は、フェ
ノール樹脂１００重量部に対して１〜２０重量部が好ま
しい。このように調製されるフェノール樹脂組成物を紙
やガラス布等の基材に含浸して乾燥させることによって
プリプレグを作成し、このプリプレグを複数枚重ねると
共に必要に応じてその片側表面もしくは両側表面に銅箔
等の金属箔を重ね、これを加熱加圧して積層成形をおこ
なうことによって、フェノール樹脂積層板を得ることが
できる。The phenol resin composition according to the present invention can be prepared by adding and blending a phenol-curing type brominated epoxy resin to the phenol resin varnish. The blending amount of the phenol-curable brominated epoxy resin is preferably 1 to 20 parts by weight per 100 parts by weight of the phenol resin. A prepreg is created by impregnating a base material such as paper or glass cloth with the phenolic resin composition prepared in this way and drying it, and by stacking multiple sheets of this prepreg, it is possible to coat one or both surfaces of the prepreg as necessary. A phenolic resin laminate can be obtained by stacking metal foils such as copper foils and performing laminate molding by heating and pressing them.
【００１０】0010
【実施例】以下本発明を実施例によって例証する。
実施例 攪拌機、冷却器及び温度計を備えた反応
容器に桐油を１２００ｇ、フェノールを１５００ｇ、パ
ラトルエンスルホン酸を８ｇ仕込んで８０℃で２時間反
応させ、次いで５０％ホルマリンを９００ｇ、２５％ア
ンモニア水を５０ミリリットル加えて８０℃で４時間反
応させ、そして縮合水を留出することによって、１６０
℃でのゲルタイムが２分のフェノール樹脂を得た。EXAMPLES The present invention will now be illustrated by examples. Example: 1200g of tung oil, 1500g of phenol, and 8g of paratoluenesulfonic acid were placed in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and reacted at 80°C for 2 hours.Then, 900g of 50% formalin and 25% aqueous ammonia were charged. By adding 50 ml of
A phenolic resin with a gel time of 2 minutes at °C was obtained.
【００１１】このフェノール樹脂をメチルアルコールに
溶解してフェノール樹脂ワニスを調製すると共にこれに
フェノール樹脂１０００ｇに対してフェノール硬化型エ
ポキシ樹脂として既出の「Ｑｕａｔｒｅｘ５０１０」を
３０ｇ配合してフェノール樹脂組成物を得た。次に、１
１６ｇ／ｍ２ のクラフト紙にこのフェノール樹脂組成
物を樹脂含量が５０重量％になるように含浸し、１５５
℃の条件で８０秒間乾燥することによってプリプレグを
作成した。そしてこのプリプレグを８枚重ねると共にそ
の片側に接着剤付の厚み３５μの銅箔を１枚重ね、これ
を２ｍｍ厚のプレートに挟んで１６０℃、１００ｋｇ／
ｃｍ２の条件で６０分間加熱加圧成形し、片面銅貼りの
フェノール樹脂積層板を得た。[0011] This phenol resin was dissolved in methyl alcohol to prepare a phenol resin varnish, and to this, 30 g of "Quatrex 5010", which has already been described as a phenol curing epoxy resin, was mixed with 1000 g of phenol resin to obtain a phenol resin composition. Ta. Next, 1
A 16 g/m2 kraft paper was impregnated with this phenolic resin composition so that the resin content was 50% by weight.
A prepreg was prepared by drying at ℃ for 80 seconds. Then, 8 sheets of this prepreg were stacked together, and one sheet of copper foil with an adhesive thickness of 35μ was placed on one side of the prepreg, and this was sandwiched between 2mm thick plates at 160℃ and 100kg/
A phenol resin laminate with copper on one side was obtained by heat-pressing molding for 60 minutes under conditions of cm2.
【００１２】比較例 フェノール樹脂ワニスにフ
ェノール硬化型エポキシ樹脂の代わりに「化３」に示す
ビスフェノールＡ系ブロム化エポキシ樹脂（東都化成社
製ＹＤＢ−４００）を用いて、フェノール樹脂１０００
ｇに対して３０ｇ配合してフェノール樹脂組成物を得た
。後はプリプレグの乾燥時間を９０秒に設定する他は、
実施例と同様にして片面銅貼りのフェノール樹脂積層板
を得た。Comparative Example A bisphenol A-based brominated epoxy resin (YDB-400 manufactured by Toto Kasei Co., Ltd.) shown in "Chemical Formula 3" was used in place of the phenol curing epoxy resin for the phenol resin varnish.
A phenol resin composition was obtained by blending 30g per g. Other than setting the prepreg drying time to 90 seconds,
A phenol resin laminate with copper bonded on one side was obtained in the same manner as in the example.
【００１３】[0013]
【化３】[Chemical formula 3]
【００１４】上記実施例及び比較例における各フェノー
ル樹脂組成物のゲルタイムを測定し、また実施例及び比
較例によって得た積層板についてオーブン耐熱性、半田
耐熱性、吸湿耐熱性を測定した。半田耐熱性の試験は２
６０℃の半田浴に積層板を浸漬して積層板にフクレが発
生するまでの時間を測定することによっておこなった。
吸湿後半田耐熱性は、積層板を６０℃、９５％Ｒｈの雰
囲気に２４時間放置して吸湿させた後に、同様に半田浴
に浸漬して積層板にフクレが発生するまでの時間を測定
することによっておこなった。結果を次表に示す。The gel time of each phenolic resin composition in the above Examples and Comparative Examples was measured, and the oven heat resistance, soldering heat resistance, and moisture absorption heat resistance of the laminates obtained in the Examples and Comparative Examples were measured. Solder heat resistance test is 2
This was done by immersing the laminate in a solder bath at 60°C and measuring the time until blisters appeared on the laminate. The solder heat resistance after moisture absorption is determined by leaving the laminate in an atmosphere of 60°C and 95% Rh for 24 hours to absorb moisture, then immersing it in a solder bath and measuring the time until blistering occurs on the laminate. This was done by The results are shown in the table below.
【００１５】[0015]
【表１】[Table 1]
【００１６】表の結果にみられるように、実施例のもの
は耐熱性が向上していることが確認される。As can be seen from the results in the table, it is confirmed that the heat resistance of the examples is improved.
【００１７】[0017]
【発明の効果】上記のように本発明は、フェノール樹脂
ワニスに、ブロム化エポキシ樹脂成分としてフェノール
硬化型ブロム化エポキシ樹脂を添加配合したので、フェ
ノール硬化型ブロム化エポキシ樹脂は未反応フェノール
と反応して、フェノール樹脂ワニス中の未反応フェノー
ルモノマーを消費すると共に硬化速度を速め、フェノー
ル樹脂積層板の耐熱性を高めることができるものである
。Effects of the Invention As described above, in the present invention, a phenol curing type brominated epoxy resin is added and blended as a brominated epoxy resin component to a phenol resin varnish, so that the phenol curing type brominated epoxy resin reacts with unreacted phenol. As a result, the unreacted phenol monomer in the phenolic resin varnish can be consumed, the curing speed can be increased, and the heat resistance of the phenolic resin laminate can be improved.
Claims (1)
ポキシ樹脂成分としてフェノール硬化型ブロム化エポキ
シ樹脂を添加配合して成ることを特徴とする積層板用フ
ェノール樹脂組成物。1. A phenolic resin composition for a laminate, comprising a phenol resin varnish and a phenol-curable brominated epoxy resin as a brominated epoxy resin component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40547890A JPH04222816A (en) | 1990-12-25 | 1990-12-25 | Phenolic resin composition for laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40547890A JPH04222816A (en) | 1990-12-25 | 1990-12-25 | Phenolic resin composition for laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04222816A true JPH04222816A (en) | 1992-08-12 |
Family
ID=18515080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP40547890A Withdrawn JPH04222816A (en) | 1990-12-25 | 1990-12-25 | Phenolic resin composition for laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04222816A (en) |
-
1990
- 1990-12-25 JP JP40547890A patent/JPH04222816A/en not_active Withdrawn
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