JPH11228669A - Epoxy resin composition, prepreg, copper-clad laminate and multilayer laminate - Google Patents
Epoxy resin composition, prepreg, copper-clad laminate and multilayer laminateInfo
- Publication number
- JPH11228669A JPH11228669A JP3179298A JP3179298A JPH11228669A JP H11228669 A JPH11228669 A JP H11228669A JP 3179298 A JP3179298 A JP 3179298A JP 3179298 A JP3179298 A JP 3179298A JP H11228669 A JPH11228669 A JP H11228669A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- copper foil
- prepreg
- copper
- resin composition
- 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 title claims abstract description 105
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 105
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011889 copper foil Substances 0.000 claims abstract description 61
- 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 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000005751 Copper oxide Substances 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 abstract description 16
- 230000001070 adhesive effect Effects 0.000 abstract description 16
- 238000012986 modification Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 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 5
- 239000011521 glass Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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 2
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プリント配線板の
製造に用いられるエポキシ樹脂組成物、プリプレグ、銅
張り積層板、多層積層板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition, a prepreg, a copper-clad laminate, and a multilayer laminate used for manufacturing a printed wiring board.
【０００２】[0002]
【従来の技術】プリプレグは、ガラス布等の基材にエポ
キシ樹脂組成物のワニスを含浸した後、これを加熱乾燥
してエポキシ樹脂を半硬化させことによって調製されて
いる。そしてこのプリプレグを所要枚重ねると共に必要
に応じてその片側あるいは両側に銅箔１を重ね、これを
加熱加圧して積層成形することによって、図１に示すよ
うな、プリプレグのエポキシ樹脂が完全硬化して形成さ
れる絶縁層２に銅箔１を積層一体化した銅張り積層板Ａ
を得ることができる。この銅張り積層板Ａは、表面の銅
箔１をプリント加工して回路を形成することによって、
プリント配線板の製造に用いられる。2. Description of the Related Art A prepreg is prepared by impregnating a base material such as a glass cloth with a varnish of an epoxy resin composition and then heating and drying the varnish to semi-harden the epoxy resin. Then, the required number of the prepregs are laminated, and if necessary, the copper foil 1 is laminated on one or both sides of the prepreg, and the laminate is formed by applying heat and pressure, whereby the epoxy resin of the prepreg is completely cured as shown in FIG. Laminated board A in which copper foil 1 is laminated and integrated on insulating layer 2 formed by
Can be obtained. The copper-clad laminate A is formed by printing a copper foil 1 on the surface to form a circuit.
Used in the manufacture of printed wiring boards.
【０００３】また、このようにして得た銅張り積層板Ａ
の表面の銅箔１をプリント加工して内層回路３を形成す
ることによって内層用回路板４を作製し、この内層用回
路板４の表面にプリプレグを介して銅箔１（あるいは外
層用回路板）を重ね、これを加熱加圧して積層成形する
ことによって、図２に示すような、内層用回路板４にプ
リプレグのエポキシ樹脂が完全硬化して形成される絶縁
層２を介して銅箔１（あるいは外層用回路板）を積層一
体化した多層積層板Ｂを得ることができる。この多層積
層板Ｂは、表面の銅箔１をプリント加工して外層回路を
形成することによって、多層プリント配線板の製造に用
いられる。[0003] The copper-clad laminate A thus obtained
The inner layer circuit board 4 is produced by printing the copper foil 1 on the surface of the inner layer circuit 3 to form the inner layer circuit 3. The copper foil 1 (or the outer layer circuit board) is formed on the surface of the inner layer circuit board 4 via a prepreg. ) Are stacked and formed by heating and pressurizing to form a copper foil 1 through an insulating layer 2 formed by completely curing an epoxy resin of a prepreg on an inner layer circuit board 4 as shown in FIG. (Or an outer layer circuit board) can be obtained as a multilayer laminated board B. The multilayer laminate B is used for manufacturing a multilayer printed wiring board by forming an outer layer circuit by printing the copper foil 1 on the surface.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記のような
銅張り積層板Ａにあって、プリプレグによる絶縁層２と
銅箔１との間の接着強度が低いと、銅箔１をプリント加
工して形成される回路が絶縁層２から剥離するおそれが
あり、回路の信頼性に問題が生じると共に、電子部品を
表面実装する際の実装信頼性に問題が生じるものであっ
た。However, in the copper-clad laminate A as described above, if the adhesive strength between the insulating layer 2 and the copper foil 1 by the prepreg is low, the copper foil 1 is printed. There is a possibility that the formed circuit may be peeled off from the insulating layer 2, causing a problem in the reliability of the circuit and a problem in the mounting reliability when the electronic component is surface-mounted.
【０００５】また上記のような多層積層板Ｂにあって、
内層用回路板４の内層回路３とプリプレグによる絶縁層
２との接着強度が低いと、半田処理の際など高温が作用
するとこの部分が剥離してフクレが生じるおそれがあ
り、耐熱性が大きく低下する。そこで従来では内層回路
３の表面に黒化処理と通称される酸化処理を施し、内層
回路３の表面に銅酸化物層を形成して、内層回路３の表
面と絶縁層２との間の接着強度を高めるようにしてい
る。しかし、黒化処理は何工程もの処理が必要であって
非常に手間がかかるという問題があった。[0005] In the multilayer laminate B as described above,
If the bonding strength between the inner layer circuit 3 of the inner layer circuit board 4 and the insulating layer 2 by the prepreg is low, when a high temperature is applied, such as during a soldering process, this portion may be peeled off and blisters may occur, and the heat resistance is greatly reduced. I do. Therefore, conventionally, the surface of the inner circuit 3 is subjected to an oxidation treatment commonly referred to as blackening treatment, and a copper oxide layer is formed on the surface of the inner circuit 3 to bond the surface between the inner circuit 3 and the insulating layer 2. I try to increase the strength. However, there has been a problem that the blackening process requires a number of processes and is very troublesome.
【０００６】本発明は上記の点に鑑みてなされたもので
あり、銅箔や銅の内層回路の接着強度を高く得ることが
できるエポキシ樹脂組成物、プリプレグ、銅張り積層
板、多層積層板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 has been made of an epoxy resin composition, a prepreg, a copper-clad laminate, and a multilayer laminate capable of obtaining a high adhesive strength of a copper foil or a copper inner layer circuit. It is intended to provide.
【０００７】[0007]
【課題を解決するための手段】本発明に係るエポキシ樹
脂組成物は、ビスフェノールＡ型エポキシ樹脂をカルボ
キシル末端アクリロニトリルブタジエン共重合体で変性
した変性エポキシ樹脂、この変性エポキシ樹脂以外のエ
ポキシ樹脂、硬化剤としてジシアンジアミド、硬化促進
剤を含有し、上記変性エポキシ樹脂としてカルボキシル
末端アクリロニトリルブタジエン共重合体による変性量
がエポキシ樹脂総量１００重量部に対して３〜１５重量
部のものを用いることを特徴とするものである。The epoxy resin composition according to the present invention comprises a modified epoxy resin obtained by modifying a bisphenol A type epoxy resin with a carboxyl-terminated acrylonitrile-butadiene copolymer, an epoxy resin other than the modified epoxy resin, and a curing agent. Wherein dicyandiamide and a curing accelerator are used as the modified epoxy resin, and the amount of modification with the carboxyl-terminal acrylonitrile butadiene copolymer is 3 to 15 parts by weight based on 100 parts by weight of the total amount of the epoxy resin. It is.
【０００８】本発明に係るプリプレグは、上記のエポキ
シ樹脂組成物が基材に含浸されていると共に半硬化状態
にあることを特徴とするものである。本発明に係る銅張
り積層板は、上記のプリプレグと銅箔とが積層一体化さ
れていると共にエポキシ樹脂組成物が完全硬化状態にあ
ることを特徴とするものである。[0008] The prepreg according to the present invention is characterized in that the base material is impregnated with the epoxy resin composition and is in a semi-cured state. The copper-clad laminate according to the present invention is characterized in that the prepreg and the copper foil are laminated and integrated, and the epoxy resin composition is in a completely cured state.
【０００９】本発明に係る多層積層板は、上記の表面未
処理の銅箔で内層回路が形成された内層用回路板の表面
に、上記のプリプレグが完全硬化して形成される絶縁層
が積層一体化されていることを特徴とするものである。
また請求項５の発明は、表面未処理の銅箔が、表面に銅
酸化物層を形成していない銅箔であることを特徴とする
ものである。In the multilayer laminate according to the present invention, an insulating layer formed by completely curing the above prepreg is laminated on the surface of the inner layer circuit board having the inner layer circuit formed of the untreated copper foil. It is characterized by being integrated.
The invention of claim 5 is characterized in that the untreated copper foil is a copper foil having no copper oxide layer formed on the surface.
【００１０】[0010]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。本発明においてエポキシ樹脂としては、ビスフェ
ノールＡ型エポキシ樹脂をカルボキシル末端アクリロニ
トリルブタジエン共重合体（ＣＴＢＮ：carboxyl termi
nated butadiene acrylonitrile copolymers）で変性し
た変性エポキシ樹脂と、この変性エポキシ樹脂以外のエ
ポキシ樹脂とを併用するものであり、全エポキシ樹脂１
００重量部中に変性エポキシ樹脂が５〜９５重量部を占
めるように、両者の配合量を調整するのが好ましい。Embodiments of the present invention will be described below. In the present invention, as the epoxy resin, a bisphenol A type epoxy resin is a carboxyl termi- yl acrylonitrile butadiene copolymer (CTBN).
A modified epoxy resin modified with nated butadiene acrylonitrile copolymers) and an epoxy resin other than this modified epoxy resin are used in combination.
It is preferable to adjust the blending amount of the modified epoxy resin so that the modified epoxy resin accounts for 5 to 95 parts by weight in 00 parts by weight.
【００１１】ここで、ビスフェノールＡ型エポキシ樹脂
をＣＴＢＮで変性した変性エポキシ樹脂としては、次の
「化１」で示す構造式のものを用いることができる。Here, as a modified epoxy resin obtained by modifying a bisphenol A type epoxy resin with CTBN, a modified epoxy resin represented by the following chemical formula 1 can be used.
【００１２】[0012]
【化１】 Embedded image
【００１３】上記の構造式において、ｎ＝０〜３、ｍ＝
１〜３である。またｘとｙは組成比でｘ＝０．６５〜
０．９５、ｙ＝０．０５〜０．３５（但しｘ＋ｙ＝
１）、ｚ＝５９〜７１である。上記のようなビスフェノ
ールＡ型エポキシ樹脂をＣＴＢＮで変性した変性エポキ
シ樹脂を用いるにあたって、このＣＴＢＮによる変性量
が、エポキシ樹脂総量１００重量部に対して３〜１５重
量部（より好ましくは５〜１０重量部）になるように、
すなわちエポキシ樹脂総量に対する変性率が３〜１５重
量％になるように設定するのが好ましい。ＣＴＢＮによ
る変性量がエポキシ樹脂総量１００重量部に対して３重
量部未満であると、ＣＴＢＮによる変性によって銅箔に
対する接着性を高める効果を十分に得ることは難しく、
逆に１５重量部を超えると、積層板に成形したときの誘
電正接が上昇し、電気的特性の面で好ましくない。In the above structural formula, n = 0 to 3, m =
1 to 3. X and y are composition ratios x = 0.65 to 0.65.
0.95, y = 0.05 to 0.35 (where x + y =
1), z = 59-71. In using the modified epoxy resin obtained by modifying the bisphenol A type epoxy resin with CTBN as described above, the amount of modification by CTBN is 3 to 15 parts by weight (more preferably 5 to 10 parts by weight) based on 100 parts by weight of the total amount of epoxy resin. Part),
That is, it is preferable to set the modification ratio to 3 to 15% by weight based on the total amount of the epoxy resin. If the amount of modification by CTBN is less than 3 parts by weight with respect to 100 parts by weight of the total amount of epoxy resin, it is difficult to sufficiently obtain the effect of improving adhesion to copper foil by modification with CTBN,
Conversely, if it exceeds 15 parts by weight, the dielectric loss tangent when formed into a laminate increases, which is not preferable in terms of electrical characteristics.
【００１４】また上記のＣＴＢＮによる変性エポキシ樹
脂以外のエポキシ樹脂としては、２官能以上のものであ
れば特に制限されることなく使用することができるもの
であり、例えば、ビスフェノールＡ型エポキシ樹脂、ビ
スフェノールＦ型エポキシ樹脂、フェノールノボラック
型エポキシ樹脂、ビス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、ジアミノ
ジフェニルメタン型エポキシ樹脂及び、これらのエポキ
シ樹脂中の水素原子の一部をハロゲン化することによっ
て難燃化したエポキシ樹脂などを用いることができ、こ
れらは１種単独で使用する他、２種以上を併用すること
もできる。Epoxy resins other than the above-described CTBN-modified epoxy resins can be used without any particular limitation as long as they have two or more functionalities. For example, bisphenol A type epoxy resin, bisphenol A F type epoxy resin, phenol novolak type epoxy resin, bisphenol novolak type epoxy resin, cresol novolak type epoxy resin, diaminodiphenylmethane type epoxy resin, and flame retardant by halogenating some of the hydrogen atoms in these epoxy resins Epoxy resins and the like can be used, and these can be used alone or in combination of two or more.
【００１５】また本発明にあって、硬化剤としては、銅
箔との接着強度を高く得るために、ジシアンジアミド
（ＤＩＣＹ）を用いるのが好ましい。硬化促進剤につい
ては特に制限されるものではないが、２−エチル−４−
メチルイミダゾール（２Ｅ４ＭＺ）などのイミダゾール
類を用いることができる。そして、ビスフェノールＡ型
エポキシ樹脂をＣＴＢＮで変性した変性エポキシ樹脂、
この変性エポキシ樹脂以外のエポキシ樹脂、硬化剤、硬
化促進剤を配合し、これらを溶剤に溶解することによっ
て、エポキシ樹脂ワニスとして使用されるエポキシ樹脂
組成物を調製することができるものである。溶剤として
は、メチルエチルケトン（ＭＥＫ）、ジメチルホルムア
ミド（ＤＭＦ）、メチルセロソルブなどを用いることが
できる。ここで、硬化剤の配合量は、全エポキシ樹脂に
対する当量比が０．２〜０．８（より好ましくは０．４
〜０．６）になるように調整するのが好ましく、硬化促
進剤の配合量は、０．０１〜０．３０ＰＨＲに調整する
のが好ましい。In the present invention, it is preferable to use dicyandiamide (DICY) as a curing agent in order to obtain a high adhesive strength to a copper foil. Although there is no particular limitation on the curing accelerator, 2-ethyl-4-
Imidazoles such as methylimidazole (2E4MZ) can be used. And a modified epoxy resin obtained by modifying bisphenol A type epoxy resin with CTBN,
An epoxy resin composition used as an epoxy resin varnish can be prepared by blending an epoxy resin other than the modified epoxy resin, a curing agent, and a curing accelerator and dissolving them in a solvent. As the solvent, methyl ethyl ketone (MEK), dimethylformamide (DMF), methyl cellosolve, or the like can be used. Here, the compounding amount of the curing agent is such that the equivalent ratio to the total epoxy resin is 0.2 to 0.8 (more preferably 0.4 to 0.8).
To 0.6), and the amount of the curing accelerator is preferably adjusted to 0.01 to 0.30 PHR.
【００１６】一方、本発明において基材としては、ガラ
スクロスやガラス不織布などを用いることができるもの
であり、この基材に上記のように調製されるエポキシ樹
脂組成物のワニスを例えば樹脂含有率３５〜８０重量％
になるように含浸させ、これを例えば温度１４０〜１８
０℃、時間１〜３０分の条件で加熱乾燥してエポキシ樹
脂をＢステージ状態に半硬化させることによって、プリ
プレグを作製することができるものある。On the other hand, in the present invention, a glass cloth, a glass nonwoven fabric, or the like can be used as the substrate, and a varnish of the epoxy resin composition prepared as described above is coated on the substrate, for example, with a resin content of 35-80% by weight
And impregnated at a temperature of 140 to 18 for example.
A prepreg can be prepared by heating and drying under the conditions of 0 ° C. and a time of 1 to 30 minutes to semi-cure the epoxy resin into a B-stage state.
【００１７】そしてこのプリプレグを所要枚数重ねると
共に、その片側あるいは両側に銅箔を重ね、これを例え
ば温度１５０〜２００℃、圧力１〜８ＭＰａ、時間９０
〜１５０分の条件で加熱加圧して積層成形することによ
って、図１に示すような、プリプレグのエポキシ樹脂が
完全硬化して形成される絶縁層２に銅箔１を積層一体化
した銅張り積層板Ａを得ることができるものである。こ
の銅張り積層板Ａは、表面の銅箔１をプリント加工して
回路を形成することによって、プリント配線板に加工し
て用いられるものである。A required number of the prepregs are stacked, and a copper foil is stacked on one or both sides of the prepreg, for example, at a temperature of 150 to 200 ° C., a pressure of 1 to 8 MPa, and a time of 90 hours.
A copper-clad laminate in which a copper foil 1 is laminated and integrated with an insulating layer 2 formed by completely curing an epoxy resin of a prepreg as shown in FIG. A plate A can be obtained. The copper-clad laminate A is used by processing a printed wiring board by printing a copper foil 1 on the surface to form a circuit.
【００１８】ここで、絶縁層２を形成するプリプレグの
エポキシ樹脂は、上記のようにビスフェノールＡ型エポ
キシ樹脂をＣＴＢＮで変性した変性エポキシ樹脂を含む
ものであり、この変性エポキシ樹脂によって絶縁層２と
銅箔１との接着強度を高く得ることができる。従って、
銅箔１をプリント加工して形成される回路の絶縁層２に
対する密着強度が高く、回路の信頼性を高めることがで
きると共に、電子部品を表面実装する際の実装信頼性を
高めることができるものである。Here, the epoxy resin of the prepreg forming the insulating layer 2 includes a modified epoxy resin obtained by modifying bisphenol A type epoxy resin with CTBN as described above. A high adhesive strength with the copper foil 1 can be obtained. Therefore,
A circuit formed by printing a copper foil 1 and having a high adhesion strength to the insulating layer 2, which can increase the reliability of the circuit and also enhance the mounting reliability when electronic components are surface-mounted. It is.
【００１９】また、上記のようにして得た銅張りの積層
板Ａの表面の銅箔１をプリント加工して内層回路３を形
成をすることによって内層用回路板４を作製することが
できる。そしてこの内層用回路板４の表面に上記のよう
に作製したプリプレグを介して銅箔１（あるいは外層用
回路板）を重ね、これを例えば温度１５０〜２００℃、
圧力１〜８ＭＰａ、時間９０〜１５０分の条件で加熱加
圧して二次積層成形することによって、図２に示すよう
な、内層用回路板４にプリプレグのエポキシ樹脂が完全
硬化して形成される絶縁層２によって銅箔１（あるいは
外層用回路板）を積層一体化した多層積層板Ｂを得るこ
とができるものである。この多層積層板Ｂは、表面の銅
箔１をプリント加工して外層回路を形成することによっ
て、多層プリント配線板に加工して用いられるものであ
る。尚、内層用回路板４としては、上記の銅張りの積層
板Ａを用いて形成する他に、一般のＦＲ−４材などを用
いて形成するようにしてもよい。Further, the inner layer circuit 3 can be formed by printing the copper foil 1 on the surface of the copper-clad laminate A obtained as described above to form the inner layer circuit 3. Then, the copper foil 1 (or the outer layer circuit board) is stacked on the surface of the inner layer circuit board 4 through the prepreg prepared as described above, and the copper foil 1 (for example, at a temperature of 150 to 200 ° C.).
By heating and pressing under the conditions of a pressure of 1 to 8 MPa and a time of 90 to 150 minutes to perform secondary lamination molding, the epoxy resin of the prepreg is completely cured and formed on the inner layer circuit board 4 as shown in FIG. The multilayer laminate B in which the copper foil 1 (or the outer layer circuit board) is laminated and integrated by the insulating layer 2 can be obtained. This multilayer laminated board B is used by processing the copper foil 1 on the surface to form an outer layer circuit and processing it into a multilayer printed wiring board. The circuit board 4 for the inner layer may be formed using a general FR-4 material or the like in addition to using the above-mentioned copper-clad laminate A.
【００２０】ここで、内層回路板４の表面に積層される
絶縁層２を形成するプリプレグのエポキシ樹脂は、上記
のようにビスフェノールＡ型エポキシ樹脂をＣＴＢＮで
変性した変性エポキシ樹脂を含むものであり、この変性
エポキシ樹脂によって絶縁層２と銅箔１で形成される内
層回路３との接着強度を高く得ることができる。従っ
て、内層回路３の表面を黒化処理して銅酸化物層を形成
したり、内層回路３を形成する銅箔１として表面を黒化
処理して銅酸化物層を形成したものを用いたりする必要
なく、ソフトエッチングなどの簡単な処理で銅箔１や内
層回路３の表面を粗面化することによって、対処するこ
とができるものである。Here, the epoxy resin of the prepreg forming the insulating layer 2 laminated on the surface of the inner circuit board 4 contains a modified epoxy resin obtained by modifying a bisphenol A type epoxy resin with CTBN as described above. With this modified epoxy resin, a high adhesive strength between the insulating layer 2 and the inner layer circuit 3 formed of the copper foil 1 can be obtained. Therefore, a copper oxide layer is formed by blackening the surface of the inner layer circuit 3, or a copper foil 1 forming a copper oxide layer by blackening the surface is used as the copper foil 1 for forming the inner layer circuit 3. This can be dealt with by roughening the surfaces of the copper foil 1 and the inner layer circuit 3 by a simple treatment such as soft etching.
【００２１】[0021]
【実施例】次に、本発明を実施例によって具体的に説明
する。 （実施例１〜５、比較例１〜３）ビスフェノールＡ型エ
ポキシ樹脂をＣＴＢＮで変性した変性エポキシ樹脂とし
て、ＣＴＢＮの含有率が１０重量％のもの（エポキシ当
量２１０）、ＣＴＢＮの含有率が３０重量％のもの（エ
ポキシ当量２８５）、ＣＴＢＮの含有率が５０重量％の
もの（エポキシ当量４３５）を用いた（いずれも大日本
インキ工業株式会社製）。また変性エポキシ樹脂以外の
エポキシ樹脂として、エポキシ当量５００のテトラブロ
モビスフェノールＡ型エポキシ樹脂（大日本インキ工業
株式会社製「ＥＰＩＣＬＯＮ １１２１」）、エポキシ
当量７６０のテトラブロモビスフェノールＡ型エポキシ
樹脂（同社製「ＥＰＩＣＬＯＮ １１２６」）、エポキ
シ当量２２５のクレゾールノボラック型エポキシ樹脂
（同社製「ＥＰＩＣＬＯＮ Ｎ−６９０」）を用いた。Next, the present invention will be described specifically with reference to examples. (Examples 1 to 5, Comparative Examples 1 to 3) As a modified epoxy resin obtained by modifying a bisphenol A type epoxy resin with CTBN, one having a CTBN content of 10% by weight (epoxy equivalent: 210) and a CTBN content of 30 % (Epoxy equivalent: 285) and those having a CTBN content of 50% by weight (epoxy equivalent: 435) (both manufactured by Dainippon Ink and Chemicals, Inc.). In addition, as epoxy resins other than the modified epoxy resin, a tetrabromobisphenol A type epoxy resin having an epoxy equivalent of 500 (“EPICLON 1121” manufactured by Dainippon Ink Industries, Ltd.) and a tetrabromobisphenol A type epoxy resin having an epoxy equivalent of 760 (manufactured by the company) EPICLON 1126 ") and a cresol novolac type epoxy resin having an epoxy equivalent of 225 (" EPICLON N-690 "manufactured by the company).
【００２２】そして表１に示す配合で変性エポキシ樹
脂、変性エポキシ樹脂以外のエポキシ樹脂、硬化剤、硬
化促進剤、溶剤を配合することによって、エポキシ樹脂
組成物のワニスを得た。次に、このエポキシ樹脂組成物
のワニスを７６２８タイプのガラスクロスに含浸し、１
６０℃、１５分の条件で加熱乾燥することによって、樹
脂含有率が６０重量％のプリプレグを得た。Then, a varnish of an epoxy resin composition was obtained by blending the modified epoxy resin, an epoxy resin other than the modified epoxy resin, a curing agent, a curing accelerator, and a solvent in the composition shown in Table 1. Next, the varnish of this epoxy resin composition was impregnated into a 7628 type glass cloth,
By heating and drying at 60 ° C. for 15 minutes, a prepreg having a resin content of 60% by weight was obtained.
【００２３】次に、このプリプレグを４枚重ね、その上
下にそれぞれ厚み３５μｍの銅箔を重ね、これを１７０
℃、３．９ＭＰａ、１２０分の条件で加熱加圧成形する
ことによって、図１のような厚み０．８ｍｍの両面銅張
り積層板を得た。また、両面に厚み３５μｍの銅箔を張
った厚み０．８ｍｍのＦＲ−４タイプの両面銅張り積層
板を内層用回路板として用い、この内層用回路板の両面
に上記のプリプレグを１枚ずつ重ねると共にさらにその
各外側に厚み３５μｍの銅箔を重ね、これを１７０℃、
３．９ＭＰａ、１２０分の条件で加熱加圧成形すること
によって、図２のような４層構成の厚み１．２ｍｍの多
層積層板を得た。Next, four prepregs were stacked, and a copper foil having a thickness of 35 μm was stacked on the upper and lower sides of the prepreg.
By performing the heating and press molding under the conditions of 3.9 MPa and 120 ° C. for 120 minutes, a double-sided copper-clad laminate having a thickness of 0.8 mm as shown in FIG. 1 was obtained. In addition, a 0.8 mm thick FR-4 type double-sided copper-clad laminate having 35 μm thick copper foil on both sides is used as an inner layer circuit board, and the above-mentioned prepregs are placed on both sides of the inner layer circuit board one by one. At the same time, a copper foil having a thickness of 35 μm was further layered on each outside thereof,
By heating and pressing under the conditions of 3.9 MPa and 120 minutes, a multilayer laminate having a four-layer structure and a thickness of 1.2 mm as shown in FIG. 2 was obtained.
【００２４】ここで、この内層用回路板において、実施
例１〜５及び比較例１，２では、銅箔の表面を硫酸、Ｈ
2 Ｏ2 、硫酸銅を主成分とするソフトエッチング液でソ
フトエッチング処理したものを用い、また比較例３で
は、銅箔の表面に黒化処理して銅酸化物層を形成したも
のを用いた。In the circuit board for the inner layer, in Examples 1 to 5 and Comparative Examples 1 and 2, the surface of the copper foil was sulfuric acid, H
A soft-etched solution mainly containing 2 O 2 and copper sulfate was used. In Comparative Example 3, a copper oxide layer was formed by blackening the surface of a copper foil. .
【００２５】[0025]
【表１】 [Table 1]
【００２６】上記のようにして得られた両面銅張り積層
板について、表面の銅箔の引き剥がし強度を測定した。
結果を表２の「銅箔ピール」の項目の欄に示す。また上
記のようにして得られた多層積層板について、内層の銅
箔と絶縁層との引き剥がし強度を測定した。結果を表２
の「内層ピール」の項目の欄に示す。さらに上記のよう
にして得られた両面銅張り積層板について比誘電率を測
定した。結果を表２に示す。The peel strength of the copper foil on the surface of the double-sided copper-clad laminate obtained as described above was measured.
The results are shown in the column of “Copper foil peel” in Table 2. The peel strength between the inner layer copper foil and the insulating layer was measured for the multilayer laminate obtained as described above. Table 2 shows the results
In the column of “Inner layer peel”. Further, the relative permittivity of the double-sided copper-clad laminate obtained as described above was measured. Table 2 shows the results.
【００２７】[0027]
【表２】 [Table 2]
【００２８】表２の「銅箔ピール」の項目の欄にみられ
るように、各実施例のものは各比較例のものよりも銅箔
の接着強度が高くなっていることが確認される。また表
２の「内層ピール」の項目の欄にみられるように、各実
施例のものは比較例１，２のものよりも銅箔の接着強度
が高くなっており、各実施例のものは黒化処理した比較
例３のものに匹敵する接着強度を有することが確認され
る。As can be seen from the column of "Copper foil peel" in Table 2, it is confirmed that the adhesive strength of the copper foil is higher in each of the examples than in the comparative examples. Further, as can be seen in the column of “Inner Peel” in Table 2, the adhesive strength of the copper foil of each of the examples was higher than those of Comparative Examples 1 and 2, and that of each of the examples was It is confirmed that it has an adhesive strength comparable to that of Comparative Example 3 subjected to the blackening treatment.
【００２９】[0029]
【発明の効果】上記のように本発明に係るエポキシ樹脂
組成物は、ビスフェノールＡ型エポキシ樹脂をカルボキ
シル末端アクリロニトリルブタジエン共重合体で変性し
た変性エポキシ樹脂、この変性エポキシ樹脂以外のエポ
キシ樹脂、硬化剤としてジシアンジアミド、硬化促進剤
を含有し、上記変性エポキシ樹脂としてカルボキシル末
端アクリロニトリルブタジエン共重合体による変性量が
エポキシ樹脂総量１００重量部に対して３〜１５重量部
のものを用いて調製するようにしたので、カルボキシル
末端アクリロニトリルブタジエン共重合体による変性に
よって、銅箔に対するエポキシ樹脂の接着強度を高く得
ることができるものであり、しかもジシアンジアミドに
よって銅箔に対するエポキシ樹脂の接着強度を一層高め
ることができるものであるまた本発明に係るプリプレグ
は、上記のエポキシ樹脂組成物が基材に含浸されている
と共に半硬化状態にあることを特徴とするものであり、
カルボキシル末端アクリロニトリルブタジエン共重合体
で変性したエポキシ樹脂を含有することによって、銅箔
に対する接着強度の高い絶縁層を形成することができる
ものである。As described above, the epoxy resin composition according to the present invention comprises a modified epoxy resin obtained by modifying a bisphenol A type epoxy resin with a carboxyl terminal acrylonitrile butadiene copolymer, an epoxy resin other than the modified epoxy resin, and a curing agent. Dicyandiamide and a curing accelerator, and the modified epoxy resin is prepared by using a carboxyl-terminated acrylonitrile butadiene copolymer having a modification amount of 3 to 15 parts by weight based on 100 parts by weight of the total epoxy resin. Therefore, by modification with a carboxyl-terminated acrylonitrile butadiene copolymer, the adhesive strength of the epoxy resin to the copper foil can be increased, and the adhesive strength of the epoxy resin to the copper foil can be further increased by dicyandiamide. The prepreg according to the present invention is is characterized in that the semi-cured state together with the above epoxy resin composition is impregnated into the substrate,
By containing an epoxy resin modified with a carboxyl-terminated acrylonitrile-butadiene copolymer, an insulating layer having high adhesive strength to a copper foil can be formed.
【００３０】本発明に係る銅張り積層板は、上記のプリ
プレグと銅箔とが積層一体化されていると共にエポキシ
樹脂組成物が完全硬化状態にあることを特徴とするもの
であり、プリプレグにはカルボキシル末端アクリロニト
リルブタジエン共重合体で変性したエポキシ樹脂を含有
することによって、銅箔を高い接着強度で積層すること
ができ、銅箔をプリント加工して形成される回路の信頼
性を高めることができると共に、電子部品を表面実装す
る際の実装信頼性を高めることができるものである。The copper-clad laminate according to the present invention is characterized in that the prepreg and the copper foil are laminated and integrated, and the epoxy resin composition is in a completely cured state. By containing an epoxy resin modified with a carboxyl-terminated acrylonitrile-butadiene copolymer, copper foil can be laminated with high adhesive strength, and the reliability of circuits formed by printing copper foil can be increased. At the same time, the mounting reliability when the electronic component is surface-mounted can be improved.
【００３１】本発明に係る多層積層板は、表面未処理の
銅箔で内層回路が形成された内層用回路板の表面に、上
記のプリプレグが完全硬化して形成される絶縁層が積層
一体化されていることを特徴とするものであり、プリプ
レグにはカルボキシル末端アクリロニトリルブタジエン
共重合体で変性したエポキシ樹脂を含有することによっ
て、銅箔で形成される内層回路に高い接着強度で積層す
ることができ、表面未処理の銅箔であっても使用が可能
になるものである。In the multilayer laminate according to the present invention, an insulating layer formed by completely hardening the prepreg is integrally formed on the surface of an inner layer circuit board having an inner layer circuit formed of untreated copper foil. The prepreg contains an epoxy resin modified with a carboxyl-terminal acrylonitrile-butadiene copolymer, so that it can be laminated with high adhesive strength to an inner layer circuit formed of copper foil. It is possible to use even a surface-untreated copper foil.
【００３２】また請求項５の発明は、上記の表面未処理
の銅箔が、表面に銅酸化物層を形成していない銅箔であ
ることを特徴とするものであり、プリプレグにはカルボ
キシル末端アクリロニトリルブタジエン共重合体で変性
したエポキシ樹脂を含有することによって、銅箔で形成
される内層回路に高い接着強度で積層することができ、
黒化処理で銅酸化物層を形成していない表面未処理の銅
箔であっても使用が可能になるものであり、手間を要す
る黒化処理を省くことができるものである。Further, the invention of claim 5 is characterized in that the untreated copper foil is a copper foil having no copper oxide layer formed on the surface, and the prepreg has a carboxyl terminal. By containing an epoxy resin modified with acrylonitrile butadiene copolymer, it can be laminated with high adhesive strength on the inner layer circuit formed of copper foil,
Even a copper foil having an untreated surface without a copper oxide layer formed by the blackening treatment can be used, and a troublesome blackening treatment can be omitted.
【図１】銅張り積層板の正面図である。FIG. 1 is a front view of a copper-clad laminate.
【図２】多層積層板の正面図である。FIG. 2 is a front view of the multilayer laminate.
１ 銅箔 ２ 絶縁層 ３ 内層回路 ４ 内層用回路板 DESCRIPTION OF SYMBOLS 1 Copper foil 2 Insulating layer 3 Inner layer circuit 4 Inner layer circuit board
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｇ 59/44 Ｃ０８Ｇ 59/44 Ｃ０８Ｊ 5/24 ＣＦＣ Ｃ０８Ｊ 5/24 ＣＦＣ Ｈ０５Ｋ 3/46 Ｈ０５Ｋ 3/46 Ｔ Ｇ // Ｃ０８Ｌ 63:00 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08G59 / 44 C08G59 / 44 C08J 5/24 CFC C08J 5/24 CFC H05K 3/46 H05K 3/46 TG // C08L 63 : 00
Claims (5)
ボキシル末端アクリロニトリルブタジエン共重合体で変
性した変性エポキシ樹脂、この変性エポキシ樹脂以外の
エポキシ樹脂、硬化剤としてジシアンジアミド、硬化促
進剤を含有し、上記変性エポキシ樹脂としてカルボキシ
ル末端アクリロニトリルブタジエン共重合体による変性
量がエポキシ樹脂総量１００重量部に対して３〜１５重
量部のものを用いることを特徴とするエポキシ樹脂組成
物。1. A modified epoxy resin comprising a modified epoxy resin obtained by modifying a bisphenol A type epoxy resin with a carboxyl terminal acrylonitrile butadiene copolymer, an epoxy resin other than the modified epoxy resin, dicyandiamide as a curing agent, and a curing accelerator. An epoxy resin composition characterized in that a carboxyl-terminated acrylonitrile-butadiene copolymer is used in an amount of 3 to 15 parts by weight based on 100 parts by weight of the total epoxy resin.
基材に含浸されていると共に半硬化状態にあることを特
徴とするプリプレグ。2. A prepreg, wherein the epoxy resin composition according to claim 1 is impregnated into a substrate and is in a semi-cured state.
積層一体化されていると共にエポキシ樹脂組成物が完全
硬化状態にあることを特徴とする銅張り積層板。3. A copper-clad laminate wherein the prepreg according to claim 2 and a copper foil are laminated and integrated, and the epoxy resin composition is in a completely cured state.
た内層用回路板の表面に、請求項２に記載のプリプレグ
が完全硬化して形成される絶縁層が積層一体化されてい
ることを特徴とする多層積層板。4. An insulating layer formed by completely hardening the prepreg according to claim 2 on the surface of an inner layer circuit board having an inner layer circuit formed of untreated copper foil. A multilayer laminate characterized by the above-mentioned.
化物層を形成していない銅箔であることを特徴とする請
求項４に記載の多層積層板。5. The multilayer laminate according to claim 4, wherein the untreated copper foil is a copper foil having no copper oxide layer formed on the surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3179298A JP3906547B2 (en) | 1998-02-13 | 1998-02-13 | Copper-clad laminate, multilayer laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3179298A JP3906547B2 (en) | 1998-02-13 | 1998-02-13 | Copper-clad laminate, multilayer laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11228669A true JPH11228669A (en) | 1999-08-24 |
| JP3906547B2 JP3906547B2 (en) | 2007-04-18 |
Family
ID=12340933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3179298A Expired - Lifetime JP3906547B2 (en) | 1998-02-13 | 1998-02-13 | Copper-clad laminate, multilayer laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3906547B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294035A (en) * | 2001-04-03 | 2002-10-09 | Nippon Kayaku Co Ltd | Epoxy resin composition and powder coating |
| JP2011504198A (en) * | 2007-11-21 | 2011-02-03 | シーカ・テクノロジー・アーゲー | Impact strength modifier for epoxy resin compositions |
| CN117925163A (en) * | 2024-01-05 | 2024-04-26 | 苏州纳可新材料有限公司 | Thermosetting resin composition, insulating film, preparation method and hot-press lamination method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390145B (en) * | 2011-08-05 | 2014-06-11 | 金安国纪科技（珠海）有限公司 | Environment-friendly copper clad laminate and preparation method thereof |
-
1998
- 1998-02-13 JP JP3179298A patent/JP3906547B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294035A (en) * | 2001-04-03 | 2002-10-09 | Nippon Kayaku Co Ltd | Epoxy resin composition and powder coating |
| JP2011504198A (en) * | 2007-11-21 | 2011-02-03 | シーカ・テクノロジー・アーゲー | Impact strength modifier for epoxy resin compositions |
| JP2014177645A (en) * | 2007-11-21 | 2014-09-25 | Sika Technology Ag | Impact strength improving agent for epoxy resin composition |
| US9796809B2 (en) | 2007-11-21 | 2017-10-24 | Sika Technology Ag | Impact strength improving agent for epoxy resin compositions |
| CN117925163A (en) * | 2024-01-05 | 2024-04-26 | 苏州纳可新材料有限公司 | Thermosetting resin composition, insulating film, preparation method and hot-press lamination method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3906547B2 (en) | 2007-04-18 |
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