JPS61118463A - Epoxy resin varnish for production of laminated board - Google Patents
Epoxy resin varnish for production of laminated boardInfo
- Publication number
- JPS61118463A JPS61118463A JP23992284A JP23992284A JPS61118463A JP S61118463 A JPS61118463 A JP S61118463A JP 23992284 A JP23992284 A JP 23992284A JP 23992284 A JP23992284 A JP 23992284A JP S61118463 A JPS61118463 A JP S61118463A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- varnish
- acid
- curing
- organic acid
- 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
Abstract
Description
【発明の詳細な説明】
［技術分野］
本発明は、プリント配線板の基板となる積層板を！ｌｔ
造するにあたつでプリプレグを１１１１！するためのエ
ポキシ樹脂ワニスに関するものである。[Detailed Description of the Invention] [Technical Field] The present invention relates to a laminate that serves as a substrate for a printed wiring board! lt
1111 prepregs for manufacturing! It relates to epoxy resin varnishes for
［背景技術１
エポキシ樹脂系積層板を製造するにあたりては、まずエ
ポキシＵ）脂や硬化剤その他種化促進Ｍなどを有Ｗ１ｆ
Ｉ＃削に溶解してエポキシ樹脂ワニスを調製し、そして
このエポキシ樹脂ワニスを紙やガラス繊維布などの基材
に含浸させ、これを乾燥してプリプレグを調製する１次
ぎにこの複数枚のプリプレグをｔＲＭなとの金属箔とと
もに重ねてこれを１岨とし、さらにこれの多数坦みを多
段に積み重ね、モして熱圧装置でこれを加熱加圧によろ
積層成形することによっておこなわれる。[Background technology 1] In manufacturing an epoxy resin-based laminate, first, epoxy resin, curing agent, seeding accelerator M, etc.
Prepare an epoxy resin varnish by dissolving it in I# shavings, impregnate a base material such as paper or glass fiber cloth with this epoxy resin varnish, and dry it to prepare a prepreg. This is done by layering them together with a metal foil such as tRM to make one layer, stacking many layers of this in multiple stages, and then laminating them by heating and pressing in a thermopressing machine.
ここで、エポキシ樹脂ワニス（二あってはその保存安定
性が望まれているところであるが、保存安定性は一般的
に）ニス中の硬化剤やさらには硬化促進剤の配合量に主
として依存する。すなわち保存安定性を向上させろには
硬化剤やさらには硬化促進剤の配合量を低減すればよい
ことになる。しかしこのように硬化剤や硬化促進剤の配
合量を低減すると、積層成形時のエポキシ樹脂の硬化特
性が低下し、成形サイクルが長くなって成形性が悪くな
ると共に、エポキシ樹脂の反応性が低下するために８［
Ｍ板の耐熱性が低下することになる。これら成形性や耐
熱性は硬化剤さらには硬化促進剤の増量によって向上さ
れるのは勿論であり、従ってエポキシ耐脂ワニスの保存
安定性と成形性及び耐熱性とは相反する特性といえるも
のである。従ってエポキシ樹脂ワニスの保存安定性を向
上させ、同時に積層成形時の成形性や積層板の耐熱性を
向上させることは極めて困難である。Here, storage stability of epoxy resin varnishes (in general, storage stability is desired) mainly depends on the amount of curing agent and curing accelerator in the varnish. . In other words, in order to improve storage stability, it is sufficient to reduce the amount of the curing agent and furthermore the curing accelerator. However, if the amount of curing agent or curing accelerator is reduced in this way, the curing characteristics of the epoxy resin during laminated molding will decrease, the molding cycle will become longer, the moldability will deteriorate, and the reactivity of the epoxy resin will decrease. 8[
The heat resistance of the M plate will decrease. Of course, these moldability and heat resistance can be improved by increasing the amount of curing agent and curing accelerator, and therefore, the storage stability and moldability and heat resistance of epoxy oil-resistant varnish can be said to be contradictory characteristics. be. Therefore, it is extremely difficult to improve the storage stability of epoxy resin varnishes and at the same time improve the moldability during lamination molding and the heat resistance of the laminate.
［発明の目的］
本発明は、上記の点に鑑みて為されたものであり、ワニ
スの保存安定性を向上させ、同時に積層成形時の成形性
や積層板の耐熱性を向上させることので終る積層板ｌＩ
Ｒ用エポキシ樹脂フェワニ提供することを目的とするも
のである。[Object of the Invention] The present invention has been made in view of the above points, and ends by improving the storage stability of varnish, and at the same time improving the formability during lamination molding and the heat resistance of the laminate. Laminated board II
The purpose of this invention is to provide an epoxy resin for R.
［発明の開示１
しかして本発明に係る積層板贅造用エポキシ樹脂ワニス
にあっては、ワニスに有機酸を添加して配合するように
したことを特徴とするものであり、以下本発明を詳述す
る。[Disclosure of the Invention 1 The epoxy resin varnish for extravagant laminates according to the present invention is characterized in that an organic acid is added to the varnish. Explain in detail.
本発明においてエポキシ樹脂としてはビス７ヱノール八
〇エピクロルヒドリン系エポキシ樹脂、／ボラック型エ
ポキシ樹脂など一般に積層板において使用されるものを
用いることができる。また硬化剤としては主としてアミ
ン系硬化剤を用いるもので、例えばノシ７ンノ７ミド、
ノエチレントリアミン、）７ミ７ノフエニルメタンなど
を使用することができる。さらに必要に応じて用いる硬
化促進剤としては２エチル４メチルイミグゾールなどの
ようなイミグゾール順を使用することができる。 ゛
これらエポキシ樹脂、硬化剤及１必要に応じて硬化促進
剤を７七トン、メチルエチルケトン、ジノチルホルムア
ミドなどの溶剤に溶解してエポキシ樹脂ワニスが調製さ
れるが、このとｂ本発明にありでは有機酸を添加して配
合する。有ｍｅとしては酢酸、オレイン酸、マレイン酸
などが用いられ、酸無水物でないものが゛望ましい、そ
して待に積層成形の際の加熱温度、例えば１２０〜１３
０℃程度以下の温度条件下でのみ安定しているものがよ
い、すなわち１２０〜１３０℃以上の温度条件下では分
解されたり気化飛散されたりあるいは酸としての効力が
低下乃至消滅され、系に対して酸としての作用が及ぼさ
れないようになる有Ｗ１酸であることが望ましい、また
有機酸の配合量はワニスの溶剤成分以外の成分の０．０
０１〜０．１重１％程度が望ましい、ｏ、ｏｏｉ重量％
未満であると有機酸の配合による効果が朋待できず、ま
た０、１重量％を超えろと有＊＊によって硬化剤の作用
が着しく減じられ、積層成形の際の成形性や積層板の耐
熱性が低下する傾向がある。In the present invention, as the epoxy resin, those commonly used in laminated boards, such as bis7enol80epichlorohydrin epoxy resin and borac type epoxy resin, can be used. In addition, as a curing agent, an amine-based curing agent is mainly used, such as Nosy7inno7mide,
Noethylenetriamine, )7-7nophenylmethane, etc. can be used. Further, as a curing accelerator to be used as necessary, an imiguzole such as 2-ethyl-4-methyl imiguzole can be used.゛An epoxy resin varnish is prepared by dissolving these epoxy resins, a curing agent, and, if necessary, a curing accelerator in a solvent such as methyl ethyl ketone or dinotyl formamide. Add organic acid and blend. As the acid, acetic acid, oleic acid, maleic acid, etc. are used, and those that are not acid anhydrides are preferable, and the heating temperature during lamination molding, for example, 120-13
It is best to use one that is stable only under temperature conditions of about 0℃ or below.In other words, under temperature conditions of 120 to 130℃ or higher, it will be decomposed, vaporized, and lost, or its effectiveness as an acid will decrease or disappear, and it will not affect the system. It is preferable that the organic acid is a W1 acid that does not act as an acid, and the amount of the organic acid is 0.0% of the varnish other than the solvent component.
01~0.1 weight 1% is desirable, o, ooi weight%
If the amount is less than 0.1% by weight, the effect of the organic acid cannot be expected, and if it exceeds 0.1% by weight, the effect of the curing agent will be severely reduced, and the formability during lamination molding and the laminate quality will be affected. Heat resistance tends to decrease.
しかしてエポキシ樹脂、硬化剤、硬化促進剤及び有機酸
を溶解することによって調製したエポキシ樹脂ワニスに
あっては、有機酸によって硬化剤のアルカリ度が低下さ
れて硬化剤の硬化性能が低下し、従って硬化剤の配合量
が多くても保存時にエポキシ樹脂の硬化が進行すること
を抑制することができることになり、保存安定性を向上
させることができる。ここで、有機酸の代わりに塩酸な
どの無機酸を用いることも考えられるが、例えば塩酸の
場合、塩素がイオンとして遊離して積層板の絶縁抵抗性
を低下させたりするなどの問題を有し、さらにＪ！！１
ｌｆｉ酸は高温においても酸としての効力を有すること
が多いために実用的ではない。However, in an epoxy resin varnish prepared by dissolving an epoxy resin, a curing agent, a curing accelerator, and an organic acid, the organic acid lowers the alkalinity of the curing agent and reduces the curing performance of the curing agent. Therefore, even if the amount of the curing agent is large, the progress of curing of the epoxy resin during storage can be suppressed, and storage stability can be improved. Here, it is possible to use an inorganic acid such as hydrochloric acid instead of an organic acid, but for example, in the case of hydrochloric acid, there are problems such as chlorine being liberated as ions and reducing the insulation resistance of the laminate. , and more J! ! 1
lfi acid is not practical because it often remains effective as an acid even at high temperatures.
そしてこのように調製したエポキシ樹脂ワニスを〃ラス
繊維布、紙などの基材に含浸させ、これを加熱して乾燥
することによりＢステージのプリプレグを調製する１次
ぎにこのプリプレグを複数枚重ねると共にさらにその外
側に銅箔などの金属箔を重ね、これを１組として多数組
みを多段に積載し、熱圧装置の熱盤間にセットして常法
に従い加熱加圧による積層成形をおこない、金属箔張り
積層板を得るものであろ、この積層成形において、プリ
プレグは多段に積載されているために加熱の初期におい
ては熱盤に近いプリプレグと熱盤から遠いプリプレグと
では加熱のスピードが異なり、所定の温度に達するまで
の時間がそれぞれ異なることになるが、このまだ高（な
い温度域では有機酸の効力によって硬化剤の硬化性能が
抑制されているため、エポキシ樹脂には硬化反応が進行
せず各プリプレグにおいてエポキシ樹脂の硬化度にばら
つきが生じることが防止される。またエポキシ樹脂はま
ず溶融されてこの後硬化して固化することになるが、基
材における樹脂の分布が均一になるには溶融粘度が低く
かつ溶融時間が長いことが望ましいところ、エポキシ樹
脂の溶融の温度域では有機酸の効力で硬化剤の硬化性能
が抑制されていて、エポキシ樹脂の溶融粘度を低（Ｊｌ
持できると共に溶融時間を長く維持できることになる。Then, the epoxy resin varnish prepared in this way is impregnated into a base material such as lath fiber cloth or paper, and this is heated and dried to prepare a B-stage prepreg. Furthermore, a metal foil such as copper foil is layered on the outside, and multiple sets are stacked in multiple tiers, set between the hot platens of a heat-pressing device, and laminated by heating and pressurizing according to the usual method. In this laminated molding process, whether it is to obtain a foil-clad laminate, the prepregs are stacked in multiple stages, so at the beginning of heating, the heating speed is different between prepregs closer to the heating plate and prepregs farther from the heating plate, and the heating speed is different for prepregs that are far from the heating plate. The time it takes to reach this temperature will vary, but in this still high temperature range, the curing performance of the curing agent is suppressed by the effect of the organic acid, so the curing reaction does not proceed for the epoxy resin. This prevents variations in the degree of curing of the epoxy resin in each prepreg.In addition, the epoxy resin is first melted and then cured and solidified, but the melt viscosity is necessary for uniform distribution of the resin in the base material. Although it is desirable to have a low viscosity and a long melting time, the curing performance of the curing agent is suppressed by the effect of the organic acid in the melting temperature range of the epoxy resin, and the melt viscosity of the epoxy resin is low (Jl
This means that the melting time can be maintained for a long time.
そして各プリプレグがそれぞれ所定の温度にまで昇温さ
れエポキシ樹脂が硬化される温度にまで上昇すると、こ
の１１１ｉ温域では有機酸は分解されたり気化飛散され
たりあるいは酸としての効力が低下乃至消滅され、系に
対して酸としての作用をなさない状態にあろため、硬化
Ｍの硬化性能が良好に発揮されてエポキシ樹脂は急速に
硬化される。待に有機酸によりでエポキシ街脂ワニスの
保存安定性が向上されており硬化剤は多量に配合するこ
とが可能になっているため、多量の硬化剤の作用で硬化
反応が迅速に進行し、成形のサイクルを短くして成形性
を向上させることがで終るものであり、またエポキシ樹
脂の硬化が完全になされて積層板の耐熱性が向上される
ことになる。When each prepreg is heated to a predetermined temperature and the temperature is raised to the temperature at which the epoxy resin is cured, the organic acid is decomposed, vaporized and scattered, or its effectiveness as an acid decreases or disappears in this 111i temperature range. Since the epoxy resin is in a state where it does not act as an acid on the system, the curing performance of curing M is exhibited well and the epoxy resin is rapidly cured. The storage stability of epoxy street varnish has been improved by organic acids, and it is now possible to incorporate a large amount of hardening agent, so the curing reaction proceeds rapidly due to the action of a large amount of hardening agent. This results in improved moldability by shortening the molding cycle, and the epoxy resin is completely cured, improving the heat resistance of the laminate.
次ぎに本発明を実施例及び比較例によって例証する。The invention will now be illustrated by examples and comparative examples.
エポキシ樹脂としてシェル化学社製Ｅ９−１０４５を、
硬化剤としてノシ７ンゾ７ミドを、硬化促進剤として２
エチル４メチルイミグゾールをそれぞれ用い、さらに有
機酸としてオレイン酸、酢酸、マレイン酸を用い、＃１
１表の配合量でこれらをメチルエチルケトンに溶解する
ことによってエポキシ樹脂ワニスを調製した（比較例で
は有機酸は配合せず）。E9-1045 manufactured by Shell Chemical Co., Ltd. was used as the epoxy resin.
Nosy7inzo7mide as a curing agent and 2 as a curing accelerator.
Using ethyl 4 methyl imiguzole respectively, and using oleic acid, acetic acid, and maleic acid as organic acids, #1
An epoxy resin varnish was prepared by dissolving these in methyl ethyl ketone in the blending amounts shown in Table 1 (in the comparative example, no organic acid was blended).
このようにして得たエポキシ餠脂ワニ大の保存安定性を
評価するためにワニスのデルタイムを測定した。測定は
１６０℃の熱板にワニスを流し、ワニスがゲル化するに
要する時間を計測することによっておこなった。結果を
＃Ｉ２表に示す。In order to evaluate the storage stability of the epoxy crocodile-sized epoxy resin obtained in this way, the deltime of the varnish was measured. The measurement was performed by pouring varnish onto a hot plate at 160°C and measuring the time required for the varnish to gel. The results are shown in Table #I2.
また上記のようにしで得たエポキシ樹脂ワニスをｆ？ス
繊維布に含浸して加熱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８枚重ねさらにその上下に
銅箔を重ね、５０Ｋｇ／ｅ曽２．１７０℃、３０分の条
件で加熱加圧による積層成形をおこなって銅張りプラス
エポキシ積層板を得た。In addition, the epoxy resin varnish obtained as described above was applied to f? A prepreg is created by impregnating a fiber cloth and heating and drying it. 8 sheets of this prepreg are stacked, and copper foil is layered on top and bottom of the prepreg. Laminate molding was performed to obtain a copper-clad plus epoxy laminate.
このようにして得た積層板の耐熱性を評価するために、
積層板を第２表に示す時間煮沸処理し、さらに溶融半田
浴に２０秒間ディップして試験をおこなった。結果を第
２表に示す、また成形性を測定するために上記ワニスを
所定ノ（ターンのキャビティーで成形をおこな−１、充
填性や硬化時間を総合評価することにより成形性を評価
した、結果第 １ 表（重量部）
第 ２ 表
第２表の結果、有機酸を配合した実施例１〜４のエポキ
シ樹脂ワニスはデルタイムを長くすることができると共
に経時におけるデルタイムの短縮も抑えることができ、
有ｌｆｉ酸を配合しない比較例のものよりも保存安定性
が着しく向上していることが確認される。また成形性や
耐熱性についても実施例１〜４のものは比較例のものよ
り向上している二とが確認される。In order to evaluate the heat resistance of the laminate obtained in this way,
Tests were conducted by boiling the laminates for the times shown in Table 2 and then dipping them in a molten solder bath for 20 seconds. The results are shown in Table 2. In order to measure the moldability, the above varnish was molded in the cavity of a predetermined number of turns (-1), and the moldability was evaluated by comprehensively evaluating the filling property and curing time. , Results Table 1 (parts by weight) Table 2 The results shown in Table 2 show that the epoxy resin varnishes of Examples 1 to 4 containing organic acids can lengthen the del time and also suppress the shortening of the del time over time. I can do it,
It is confirmed that the storage stability is significantly improved compared to the comparative example which does not contain lfiic acid. It is also confirmed that the moldability and heat resistance of Examples 1 to 4 are improved over those of Comparative Examples.
［発明の効果Ｊ
上述のように本発明にあっては、エポキシ樹脂及び硬化
剤が配合されたワニスに有機酸が添加配合しであるので
、有機酸によって硬化剤の硬化性能を低下させることが
でき、硬化剤の配合量が多くても保存時にエポキシ樹脂
の硬化の進行を抑制できて保存安定性を向上させること
ができるものであり、しかもエポキシ樹脂が硬化される
高温域では有８！酸は分解されたり気化飛散されたりあ
るいは酸としての効力が低下乃至消滅され、系に対して
酸としての作用をなさない状態になりで硬化反応が迅速
に進行し、成形のサイクルを短くして成形性を向上させ
ることができるものであり、またエポキシ樹脂の硬化が
完全になされて積層板の耐熱性が向上されることになる
ものである。[Effect of the invention J As described above, in the present invention, since an organic acid is added to the varnish containing an epoxy resin and a hardening agent, the curing performance of the hardening agent is not reduced by the organic acid. Even if the amount of curing agent is large, the progress of curing of the epoxy resin can be suppressed during storage and the storage stability can be improved.Moreover, it can be used in the high temperature range where the epoxy resin is cured. The acid is decomposed, vaporized and scattered, or its effectiveness as an acid is reduced or eliminated, and it no longer acts as an acid on the system, allowing the curing reaction to proceed rapidly and shortening the molding cycle. The moldability can be improved, and the epoxy resin is completely cured, thereby improving the heat resistance of the laminate.
Claims (2)
って、このワニスには有機酸が添加配合されて成ること
を特徴とする積層板製造用エポキシ樹脂ワニス。(1) An epoxy resin varnish for manufacturing laminates, which is a varnish containing an epoxy resin and a curing agent, and an organic acid is added to the varnish.
特許請求の範囲第１項記載の積層板製造用エポキシ樹脂
ワニス。(2) The epoxy resin varnish for producing a laminate according to claim 1, wherein the curing agent is an amine-based curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23992284A JPS61118463A (en) | 1984-11-14 | 1984-11-14 | Epoxy resin varnish for production of laminated board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23992284A JPS61118463A (en) | 1984-11-14 | 1984-11-14 | Epoxy resin varnish for production of laminated board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61118463A true JPS61118463A (en) | 1986-06-05 |
| JPH0238122B2 JPH0238122B2 (en) | 1990-08-29 |
Family
ID=17051839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23992284A Granted JPS61118463A (en) | 1984-11-14 | 1984-11-14 | Epoxy resin varnish for production of laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61118463A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01201339A (en) * | 1987-12-15 | 1989-08-14 | Ciba Geigy Ag | Production of laminate |
| JP2002161191A (en) * | 2000-11-27 | 2002-06-04 | Sumitomo Bakelite Co Ltd | Flame retardant resin composition, prepreg and laminated sheet which use the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50112497A (en) * | 1974-02-15 | 1975-09-03 | ||
| JPS54148098A (en) * | 1978-05-13 | 1979-11-19 | Asahi Chem Ind Co Ltd | Novel epoxy resin composition |
| JPS5761020A (en) * | 1980-09-30 | 1982-04-13 | Ube Ind Ltd | Curing agent for epoxy resin |
-
1984
- 1984-11-14 JP JP23992284A patent/JPS61118463A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50112497A (en) * | 1974-02-15 | 1975-09-03 | ||
| JPS54148098A (en) * | 1978-05-13 | 1979-11-19 | Asahi Chem Ind Co Ltd | Novel epoxy resin composition |
| JPS5761020A (en) * | 1980-09-30 | 1982-04-13 | Ube Ind Ltd | Curing agent for epoxy resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01201339A (en) * | 1987-12-15 | 1989-08-14 | Ciba Geigy Ag | Production of laminate |
| JP2002161191A (en) * | 2000-11-27 | 2002-06-04 | Sumitomo Bakelite Co Ltd | Flame retardant resin composition, prepreg and laminated sheet which use the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0238122B2 (en) | 1990-08-29 |
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