JPH05493A - Preparation of laminated sheet - Google Patents
Preparation of laminated sheetInfo
- Publication number
- JPH05493A JPH05493A JP15280891A JP15280891A JPH05493A JP H05493 A JPH05493 A JP H05493A JP 15280891 A JP15280891 A JP 15280891A JP 15280891 A JP15280891 A JP 15280891A JP H05493 A JPH05493 A JP H05493A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- curing agent
- diamine
- prepreg
- dicyandiamide
- 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- Withdrawn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
- 239000003822 epoxy resin Substances 0.000 claims abstract description 35
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- 239000002966 varnish Substances 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000004744 fabric Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AFHJYKBGDDJSRR-UHFFFAOYSA-N 1-propan-2-yloxypropan-2-ol Chemical compound CC(C)OCC(C)O AFHJYKBGDDJSRR-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Laminated Bodies (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に
用いられるエポキシ樹脂系の積層板の製造方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxy resin-based laminate used for printed wiring boards and the like.
【０００２】[0002]
【従来の技術】多層プリント配線板などに用いられるエ
ポキシ樹脂系の積層板は、ガラス基材にエポキシ樹脂ワ
ニスを含浸して加熱・乾燥することによってプリプレグ
を調製し、このプリプレグを複数枚重ねると共に必要に
応じて銅箔等の金属箔を重ね、これを加熱加圧して積層
成形することによって、製造されている。そしてこのよ
うなエポキシ樹脂系積層板の製造に用いられるエポキシ
樹脂ワニスとしては、エポキシ樹脂に硬化剤としてジシ
アンジアミドを配合して調製したものが一般的である。2. Description of the Related Art Epoxy resin laminates used for multilayer printed wiring boards and the like are prepared by impregnating a glass base material with epoxy resin varnish and heating and drying to prepare a prepreg. It is manufactured by stacking metal foils such as copper foils as needed, and heating and pressing the foils to form a laminate. The epoxy resin varnish used in the production of such an epoxy resin laminate is generally prepared by mixing dicyandiamide as a curing agent with an epoxy resin.
【０００３】[0003]
【発明が解決しようとする課題】しかし、ジシアンジア
ミドを硬化剤として用いて硬化させたエポキシ樹脂は親
水性が高くなって吸水性や吸湿性が高く、吸水や吸湿に
よるエポキシ樹脂の加水分解などで樹脂とガラス基材と
の界面で剥離が起こり易くなり、この結果、積層板にお
ける耐ＣＡＦ性への信頼性が低下するおそれがあるとい
う問題があった。尚、ＣＡＦ（Conductive Anodic Fila
ment）とは、高湿度環境下において導体間に電位差が生
じた場合に、導体を形成する銅が陽極側から溶け出して
ガラス基材のガラス繊維と樹脂との界面を陰極側に移行
し、導体間が導通して絶縁信頼性が低下する現象をい
う。However, the epoxy resin cured by using dicyandiamide as a curing agent has high hydrophilicity and high water absorption and hygroscopicity, and the resin is formed by hydrolysis of the epoxy resin due to water absorption or moisture absorption. There is a problem that peeling is likely to occur at the interface between the glass substrate and the glass substrate, and as a result, the reliability of the CAF resistance of the laminated plate may decrease. In addition, CAF (Conductive Anodic Fila
ment), when a potential difference occurs between the conductors in a high humidity environment, the copper forming the conductor melts from the anode side and migrates the interface between the glass fiber of the glass base material and the resin to the cathode side, This is a phenomenon in which the conductors are electrically connected and the insulation reliability is reduced.
【０００４】本発明は上記の点に鑑みてなされたもので
あり、耐ＣＡＦ性の信頼性が高い積層板の製造方法を提
供することを目的とするものである。The present invention has been made in view of the above points, and an object of the present invention is to provide a method for manufacturing a laminated plate having high CAF resistance and high reliability.
【０００５】[0005]
【課題を解決するための手段】本発明に係る積層板の製
造方法は、エポキシ樹脂にジアミン系硬化剤を配合して
調製した樹脂ワニスをガラス布基材に含浸させ、これを
乾燥してプレプレグを作成すると共にプレプリグを積層
成形す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。A method for manufacturing a laminated board according to the present invention comprises a glass cloth base material impregnated with a resin varnish prepared by blending an epoxy resin with a diamine-based curing agent, and the prepreg is dried. And prepregs are laminated and molded. Hereinafter, the present invention will be described in detail.
【０００６】エポキシ樹脂としては、積層板の製造用に
提供されている任意のものを用いることができるもので
あり、このエポキシ樹脂の硬化剤としてはジシアンジア
ミドを使用するのが一般的であるが、本発明ではジシア
ンジアミドと併用して、あるいはジシアンジアミドの代
わりにジアミン系硬化剤を配合する。このジアミン系硬
化剤としては芳香族系ジアミンが使用されるものであ
り、中でも次の構造式で示すジアミノジフェニルメタン
系のものが好ましい。As the epoxy resin, any of those provided for producing a laminated plate can be used, and dicyandiamide is generally used as a curing agent for the epoxy resin. In the present invention, a diamine-based curing agent is used in combination with dicyandiamide or instead of dicyandiamide. An aromatic diamine is used as the diamine-based curing agent, and a diaminodiphenylmethane-based curing agent represented by the following structural formula is preferable.
【０００７】[0007]
【化１】 [Chemical 1]
【０００８】尚、式１のものはイハラケミカル社製「キ
ュアハードＭＥＤ」、式２のものはイハラケミカル社製
「ＴＣ−ＤＡＭ」、式３のものは日本化薬社製「カヤボ
ンドＣ−３００」としてそれぞれ市販品が提供されてい
る。ジアミン系硬化剤をジシアンジアミドと併用する場
合、ジシアンジアミドとジアミン系硬化剤との配合割合
は、重量比で７５：２５〜０：１００の範囲が好まし
い。またエポキシ樹脂に対する硬化剤の配合量は、エポ
キシ当量に対してジシアンジアミドとジアミン系硬化剤
の合計量（ジアミン系硬化剤単独の場合はジアミン系硬
化剤のみ）で、１〜０．５当量の範囲が好ましい。Formula 1 is "Cure Hard MED" manufactured by Ihara Chemical Company, formula 2 is "TC-DAM" manufactured by Ihara Chemical Company, and formula 3 is "Kayabond C-300" manufactured by Nippon Kayaku Co., Ltd. The commercial products are provided respectively. When the diamine-based curing agent is used in combination with dicyandiamide, the mixing ratio of the dicyandiamide and the diamine-based curing agent is preferably in the range of 75:25 to 0: 100 by weight. Further, the compounding amount of the curing agent with respect to the epoxy resin is the total amount of dicyandiamide and the diamine-based curing agent with respect to the epoxy equivalent (only the diamine-based curing agent when the diamine-based curing agent alone is used), and is in the range of 1 to 0.5 equivalents. Is preferred.
【０００９】上記のようにエポキシ樹脂にジアミン系硬
化剤及び必要に応じてジシアンジアミドを配合し、さら
に硬化促進剤などの配合資材や溶剤を配合することによ
って、エポキシ樹脂ワニスを調製することができる。そ
してガラス織布やガラス不織布などで形成されるガラス
布基材にこのエポキシ樹脂ワニスを含浸させ、加熱乾燥
することによってプリプレグを調製し、次にこのプリプ
レグを複数枚重ねると共に必要に応じてさらに片側もし
くは両側に銅箔等の金属箔を重ね、これを加熱加圧して
積層成形することによって、エポキシ樹脂系積層板を得
ることができるものである。このようにして製造される
積層板にあって、エポキシ樹脂はジアミン系硬化剤によ
って硬化されているために吸水性が低減されており、樹
脂とガラス基材の界面との間の剥離を防ぐことができ、
この結果、積層板の耐ＣＡＦ性を高めることができるも
のである。As described above, the epoxy resin varnish can be prepared by blending the epoxy resin with the diamine-based curing agent and, if necessary, dicyandiamide, and further blending a compounding material such as a curing accelerator and a solvent. Then, a glass cloth base material formed of glass woven cloth or glass non-woven cloth is impregnated with this epoxy resin varnish to prepare a prepreg by heating and drying. Alternatively, an epoxy resin-based laminate can be obtained by laminating metal foils such as copper foils on both sides and heating and pressing the foils to laminate them. In the laminated board manufactured in this way, the epoxy resin is hardened by the diamine-based curing agent, so the water absorption is reduced, and peeling between the interface of the resin and the glass substrate is prevented. Can
As a result, the CAF resistance of the laminated plate can be improved.
【００１０】[0010]
【実施例】次に、本発明を実施例によって例証する。実施例１
ブロム化ビスフェノールＡ型エポキシ樹脂９０ｐｈｒ、
ノボラック型エポキシ樹脂１０ｐｈｒに、硬化剤として
前記式１のイハラケミカル社製「キュアハードＭＥＤ」
１．５ｐｈｒとジシアンジアミド０．５ｐｈｒ、溶剤と
してジメチルホルムアミド１５ｐｈｒとプロピレングリ
コールモノメチルエチルエーテル１５ｐｈｒ、硬化促進
剤として２−エチル−４−メチルイミダゾール０．１ｐ
ｈｒを配合してエポキシ樹脂ワニスを調製した。次にガ
ラス織布基材にこのエポキシ樹脂ワニスを樹脂含量が５
０重量％になるように含浸させ、１６０℃の熱風乾燥機
で５分間加熱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６枚重ねると共にさらに
両側に銅箔を重ね、これを１７５℃、３０ｋｇ／ｃｍ2
の加熱加圧条件で６０分間積層成形することによって、
エポキシ樹脂系積層板を得た。The invention will now be illustrated by the examples. Example 1 90 phr of brominated bisphenol A type epoxy resin,
"Cure Hard MED" manufactured by Ihara Chemical Co., Ltd. of the above formula 1 as a curing agent on 10 phr of novolac type epoxy resin
1.5 phr and dicyandiamide 0.5 phr, solvent dimethylformamide 15 phr and propylene glycol monomethylethyl ether 15 phr, 2-ethyl-4-methylimidazole 0.1 p as a curing accelerator
An epoxy resin varnish was prepared by blending hr. Next, this epoxy resin varnish was added to a glass woven fabric substrate with a resin content of 5
A prepreg was prepared by impregnating it to 0% by weight and heating and drying with a hot air dryer at 160 ° C. for 5 minutes. And 6 sheets of this prepreg are piled up and copper foil is piled up on both sides, and this is 175 ℃, 30kg / cm 2
By performing lamination molding for 60 minutes under the heating and pressurizing condition of
An epoxy resin-based laminate was obtained.
【００１１】実施例２
硬化剤として前記式１のイハラケミカル社製「キュアハ
ードＭＥＤ」１．０ｐｈｒとジシアンジアミド１．０ｐ
ｈｒを用いてエポキシ樹脂ワニスを調製するようにした
他は、実施例１と同様にしてエポキシ樹脂系積層板を得
た。実施例３
硬化剤として前記式１のイハラケミカル社製「キュアハ
ードＭＥＤ」０．５ｐｈｒとジシアンジアミド１．５ｐ
ｈｒを用いてエポキシ樹脂ワニスを調製するようにした
他は、実施例１と同様にしてエポキシ樹脂系積層板を得
た。 Example 2 As a curing agent, 1.0 phr of "Cure Hard MED" manufactured by Ihara Chemical Co. of the above formula 1 and 1.0 p of dicyandiamide were used.
An epoxy resin laminate was obtained in the same manner as in Example 1 except that the epoxy resin varnish was prepared using hr. Example 3 As a curing agent, 0.5 phr of "Cure Hard MED" manufactured by Ihara Chemical Co. of the formula 1 and 1.5 p of dicyandiamide.
An epoxy resin laminate was obtained in the same manner as in Example 1 except that the epoxy resin varnish was prepared using hr.
【００１２】比較例
硬化剤としてジシアンジアミド２．０ｐｈｒのみを用い
てエポキシ樹脂ワニスを調製するようにした他は、実施
例１と同様にしてエポキシ樹脂系積層板を得た。上記の
ようにして得た積層板について、耐ＣＡＦ性を測定し
た。耐ＣＡＦ性の試験は、積層板を８５℃、８５％ＲＨ
の高温高湿雰囲気に入れ、スルーホールによって積層板
に形成した電極間の絶縁性が１／２に低下するに至る時
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。 Comparative Example An epoxy resin-based laminate was obtained in the same manner as in Example 1 except that 2.0 phr of dicyandiamide was used as a curing agent to prepare an epoxy resin varnish. The CAF resistance of the laminated plate obtained as described above was measured. For the CAF resistance test, the laminated plate was 85 ° C. and 85% RH.
It was conducted by measuring the time until the insulating property between the electrodes formed on the laminated plate by the through holes was reduced to 1/2 by placing the same in a high temperature and high humidity atmosphere. The results are shown in the table below.
【００１３】[0013]
【表１】 [Table 1]
【００１４】表の結果にみられるように、エポキシ樹脂
用硬化剤としてジアミン系硬化剤を用いるようにした各
実施例のものでは、硬化剤としてジシアンジアミドのみ
を用いた比較例のものよりも、耐ＣＡＦ性が著しく高ま
っていることが確認される。As can be seen from the results in the table, in each of the examples in which the diamine-based curing agent was used as the curing agent for the epoxy resin, the resistance was higher than that in the comparative example using only dicyandiamide as the curing agent. It is confirmed that the CAF property is remarkably enhanced.
【００１５】[0015]
【発明の効果】上記のように本発明は、エポキシ樹脂に
ジアミン系硬化剤を配合して調製した樹脂ワニスを用い
るようにしたので、ジアミン系硬化剤で硬化させたエポ
キシ樹脂は吸水性が低く、樹脂とガラス基材の界面との
間の剥離を低減することができるものであり、積層板の
耐ＣＡＦ性を高めることができるものである。As described above, according to the present invention, since the resin varnish prepared by mixing the epoxy resin with the diamine-based curing agent is used, the epoxy resin cured with the diamine-based curing agent has low water absorption. The peeling between the resin and the interface of the glass substrate can be reduced, and the CAF resistance of the laminated plate can be enhanced.
Claims (2)
して調製した樹脂ワニスをガラス布基材に含浸させ、こ
れを乾燥してプレプレグを作成すると共にプレプリグを
積層成形することを特徴とする積層板の製造方法。1. A laminate characterized by impregnating a glass cloth base material with a resin varnish prepared by blending an epoxy resin with a diamine-based curing agent, drying the varnish to prepare a prepreg, and laminating and molding the prepreg. Method of manufacturing a plate.
併用して使用することを特徴とする請求項１に記載の積
層板の製造方法。2. The method for producing a laminated board according to claim 1, wherein a diamine-based curing agent is used in combination with dicyandiamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15280891A JPH05493A (en) | 1991-06-25 | 1991-06-25 | Preparation of laminated sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15280891A JPH05493A (en) | 1991-06-25 | 1991-06-25 | Preparation of laminated sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05493A true JPH05493A (en) | 1993-01-08 |
Family
ID=15548610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15280891A Withdrawn JPH05493A (en) | 1991-06-25 | 1991-06-25 | Preparation of laminated sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05493A (en) |
-
1991
- 1991-06-25 JP JP15280891A patent/JPH05493A/en not_active Withdrawn
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980903 |