JP2679005B2 - Composite copper clad laminate - Google Patents
Composite copper clad laminateInfo
- Publication number
- JP2679005B2 JP2679005B2 JP7079739A JP7973995A JP2679005B2 JP 2679005 B2 JP2679005 B2 JP 2679005B2 JP 7079739 A JP7079739 A JP 7079739A JP 7973995 A JP7973995 A JP 7973995A JP 2679005 B2 JP2679005 B2 JP 2679005B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- bisphenol
- clad laminate
- composite copper
- type epoxy
- 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.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 19
- 239000010949 copper Substances 0.000 title description 13
- 229910052802 copper Inorganic materials 0.000 title description 13
- 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 description 54
- 239000003822 epoxy resin Substances 0.000 claims description 44
- 229920000647 polyepoxide Polymers 0.000 claims description 44
- 239000011256 inorganic filler Substances 0.000 claims description 18
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229920003986 novolac Polymers 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000035939 shock Effects 0.000 description 9
- 239000002966 varnish Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 239000002341 toxic gas Substances 0.000 description 4
- 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 3
- 229930003836 cresol Natural products 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 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 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 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 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002759 woven fabric Substances 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 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性、耐湿性、含浸
性、スルーホール信頼性、耐トラッキング性およびノン
ハロゲンのため有毒ガスの発生がなく難燃性に優れ、ま
たボイドの発生が少なく作業性のよいコンポジット銅張
積層板に関する。INDUSTRIAL APPLICABILITY The present invention has excellent heat resistance, moisture resistance, impregnation property, through-hole reliability, tracking resistance and non-halogen and is excellent in flame retardancy without generation of toxic gas, and has less generation of voids. A composite copper clad laminate having good workability.
【０００２】[0002]
【従来の技術】近年、ＩＣ、ＬＳＩ等の集積回路を使用
した電子機器の発達は目覚ましく、それらに使用される
銅張積層板も多種多用となり、また、一段と優れた特性
をもつものが要求されてきた。ガラス不織布を基材の一
部とするコンポジット銅張積層板は、ガラス織布を基材
とする銅張積層板と電気特性がほぼ同等であり、寸法安
定性、スルーホール信頼性も優れ、かつ打抜加工が容易
であること等からその需要は急激に伸びている。2. Description of the Related Art In recent years, the development of electronic devices using integrated circuits such as ICs and LSIs has been remarkable, and the copper clad laminates used for them have been used in various types, and those having more excellent characteristics have been required. Came. The composite copper-clad laminate that uses a glass non-woven fabric as a part of the substrate has almost the same electrical characteristics as the copper-clad laminate that uses a glass woven fabric as a substrate, and has excellent dimensional stability and through-hole reliability, and Demand is rapidly increasing due to easy punching.
【０００３】コンポジット銅張積層板に使用されるエポ
キシ樹脂は、優れた要求特性に対応すべく種々改良が加
えられている。即ち、硬化収縮や熱膨張係数の低減、耐
トラッキング性、あるいは電気的、機械的特性向上のた
め無機質充填剤等を配合することが行われているが、ま
だ十分満足すべきものが得られていない。コンポジット
銅張積層板の耐熱性、耐熱衝撃性向上のため、無機質充
填剤を大量に配合すると、基材に含浸するエポキシ樹脂
の粘度が上昇し、これを塗布含浸すると基材に塗布むら
が生じ、ボイドや板厚不良の原因となる欠点がある。粘
度を下げるために無機質充填剤を減らすと、耐熱性や耐
熱衝撃性等の特性が低下する欠点がある。Epoxy resins used in composite copper-clad laminates have undergone various improvements in order to meet excellent required properties. That is, it has been attempted to blend an inorganic filler or the like in order to reduce the curing shrinkage or the thermal expansion coefficient, the tracking resistance, or the electrical and mechanical properties, but the satisfactory results have not been obtained yet. . In order to improve the heat resistance and thermal shock resistance of the composite copper clad laminate, if a large amount of inorganic filler is added, the viscosity of the epoxy resin that impregnates the base material will increase, and if this is applied and impregnated, uneven coating will occur on the base material. However, there is a defect that causes voids and defective plate thickness. When the amount of the inorganic filler is reduced in order to reduce the viscosity, there is a drawback that properties such as heat resistance and thermal shock resistance are deteriorated.
【０００４】また、積層板用エポキシ樹脂の硬化剤に
は、従来よりアミン系のものとフェノール系のものとが
利用されているが、一般にフェノール系はアミン系に比
べて耐熱性、耐湿性、耐マイグレーション性に優れてい
るが、層間結合力、含浸性に劣る欠点がある。フェノー
ル系のフェノールノボラック樹脂で分子量が大きいもの
を使用すると耐熱性、耐湿性に優れているが、層間結合
力、含浸性が著しく低下する。一方、分子量が小さいも
のを使用すると層間結合力、含浸性が向上するものの、
耐熱性、耐湿性が著しく低下する。従って、硬化剤とし
て使用するフェノールノボラック樹脂の分子量の調整に
よって、この相反する特性を両立させることは大変困難
であった。また、積層板用エポキシ樹脂には難燃性を向
上させることを目的として、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とを予め反応さ
せて得られる臭素化エポキシ樹脂を主樹脂として使用し
ているが、燃焼の際に有毒ガスであるハロゲン化水素を
発生するという欠点があった。Further, amine-based and phenol-based curing agents have been conventionally used as curing agents for epoxy resin for laminated boards. Generally, phenol-based curing agents have higher heat resistance and moisture resistance than amine-based curing agents. It has excellent migration resistance, but has the disadvantage of poor interlayer bond strength and impregnation. When a phenol-based phenol novolac resin having a large molecular weight is used, the heat resistance and the moisture resistance are excellent, but the interlayer bond strength and the impregnating property are significantly reduced. On the other hand, if the one with a small molecular weight is used, the interlayer bond strength and impregnability are improved,
Heat resistance and moisture resistance are significantly reduced. Therefore, it has been very difficult to satisfy these contradictory properties by adjusting the molecular weight of the phenol novolac resin used as the curing agent. In addition, a brominated epoxy resin obtained by previously reacting a bisphenol A type epoxy resin with tetrabromobisphenol A is used as a main resin for the epoxy resin for laminated plates for the purpose of improving flame retardancy. However, there is a drawback that hydrogen halide which is a toxic gas is generated during combustion.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の事情
に鑑みてなされたもので、耐熱性、耐湿性、耐熱衝撃
性、層間結合力、スルーホール信頼性、耐トラッキング
性、難燃性等に優れ、樹脂の粘度が低く塗布・含浸が容
易で、ボイドの発生が少なく、かつハロゲンを使用しな
いため燃焼の際に有毒ガスを発生しないコンポジット銅
張積層板を提供しようとするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is heat resistance, moisture resistance, thermal shock resistance, interlayer bonding strength, through hole reliability, tracking resistance, flame retardancy. It is intended to provide a composite copper-clad laminate that has excellent properties such as low resin viscosity, is easy to apply and impregnate, has few voids, and does not generate toxic gas during combustion because it does not use halogen. .
【０００６】[0006]
【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すすめた結果、プリプレグ
製造時の樹脂粘度を低下させるとともに赤リンを配合し
無機充填剤を増加させた特定未反応段階の組成物を用
い、その組成物を基材に塗布・含浸・乾燥させる工程に
おいて反応させるというプリプレグを用いた構成のコン
ポジット銅張積層板によって、上記目的が達成できるこ
とを見いだし、本発明を完成したものである。Means for Solving the Problems As a result of intensive research aimed at achieving the above-mentioned object, the present inventors have reduced the resin viscosity at the time of prepreg production and added red phosphorus to increase the inorganic filler. By using a composition of the specific unreacted stage, by a composite copper clad laminate having a configuration using a prepreg that reacts in the step of coating, impregnating and drying the composition, it was found that the above object can be achieved. The present invention has been completed.
【０００７】即ち、本発明は、ガラス基材にエポキシ樹
脂組成物を含浸・乾燥させたプリプレグ複数枚をコンポ
ジット構成に積層し、その少なくとも片面に銅箔を重ね
合わせて一体に成形されたコンポジット銅張積層板であ
って、（Ａ）ビスフェノールＡ型エポキシ樹脂、（Ｂ）
ノボラック型エポキシ樹脂、（Ｃ）ビスフェノールＡ、
（Ｄ）フェノールノボラック樹脂、（Ｅ）赤リンおよび
（Ｆ）無機質充填剤を必須成分とし、樹脂成分全体
［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）］に対して、（Ｅ）
の赤リンおよび（Ｆ）の無機質充填剤を35〜150 重量％
の割合で含有するエポキシ樹脂組成物を基材に含浸・乾
燥させる工程において、（Ａ）ビスフェノールＡ型エポ
キシ樹脂及び（Ｂ）ノボラック型エポキシ樹脂と、
（Ｃ）ビスフェノールＡとを反応させたプリプレグを用
いてなることを特徴とするコンポジット銅張積層板であ
る。That is, according to the present invention, a plurality of prepregs obtained by impregnating and drying a glass substrate with an epoxy resin composition are laminated in a composite structure, and a copper foil is superposed on at least one surface of the prepreg to integrally mold the composite copper. A laminated laminate, (A) bisphenol A type epoxy resin, (B)
Novolac type epoxy resin, (C) bisphenol A,
(D) Phenol novolac resin, (E) Red phosphorus and (F) Inorganic filler as essential components, and (E) with respect to the whole resin component [(A) + (B) + (C) + (D)] )
35 to 150% by weight of red phosphorus and inorganic filler (F)
In the step of impregnating and drying the epoxy resin composition contained in the ratio of (A) bisphenol A type epoxy resin and (B) novolac type epoxy resin,
(C) A composite copper-clad laminate characterized by using a prepreg made to react with bisphenol A.
【０００８】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【０００９】本発明に用いるプリプレグは、エポキシ樹
脂組成物を、ガラス基材に含浸・乾燥させる工程におい
て反応させてなるものである。The prepreg used in the present invention is obtained by reacting an epoxy resin composition in the step of impregnating and drying a glass substrate.
【００１０】エポキシ樹脂組成物は（Ａ）ビスフェノー
ルＡ型エポキシ樹脂、（Ｂ）ノボラック型エポキシ樹
脂、（Ｃ）ビスフェノールＡ、（Ｄ）フェノールノボラ
ック樹脂、（Ｅ）赤リンおよび（Ｆ）無機充填剤を必須
成分とするものである。The epoxy resin composition is (A) bisphenol A type epoxy resin, (B) novolac type epoxy resin, (C) bisphenol A, (D) phenol novolac resin, (E) red phosphorus and (F) inorganic filler. Is an essential component.
【００１１】エポキシ樹脂組成物の成分である（Ａ）ビ
スフェノールＡ型エポキシ樹脂としては、エポキシ当量
が 170〜340 であればよく、特に制限はなく広く使用す
ることができる。そしてこれらのビスフェノールＡ型エ
ポキシ樹脂は、単独または 2種以上混合して使用するこ
とができる。ビスフェノールＡ型エポキシ樹脂は一般に
エポキシ当量が 170以上であり、また 340を超えると含
浸性が低下し好ましくない。The bisphenol A type epoxy resin (A), which is a component of the epoxy resin composition, has an epoxy equivalent of 170 to 340 and is not particularly limited and can be widely used. These bisphenol A type epoxy resins can be used alone or in combination of two or more. The bisphenol A type epoxy resin generally has an epoxy equivalent of 170 or more, and when it exceeds 340, impregnating property is deteriorated, which is not preferable.
【００１２】エポキシ樹脂組成物の成分である（Ｂ）ノ
ボラック型エポキシ樹脂としては、フェノール型、クレ
ゾール型、ビスフェノールＡ型等が挙げられ、これらは
単独または 2種以上混合して使用することができる。The novolak type epoxy resin (B) which is a component of the epoxy resin composition includes phenol type, cresol type, bisphenol A type, etc. These can be used alone or in combination of two or more kinds. .
【００１３】またエポキシ樹脂組成物の成分である
（Ｃ）ビスフェノールＡとしては、通常のビスフェノー
ルＡが使用でき、その配合量は樹脂成分全体［（Ａ）＋
（Ｂ）＋（Ｃ）＋（Ｄ）］に対して10〜50重量％の割合
で含有することが望ましい。ビスフェノールＡの配合割
合が10重量％未満では、十分な層間結合力が得られず、
また50重量％を超えると耐熱衝撃性、耐湿性が低下し好
ましくない。As the (C) bisphenol A which is a component of the epoxy resin composition, a usual bisphenol A can be used, and the compounding amount thereof is the whole resin component [(A) +
(B) + (C) + (D)] is preferably contained in a proportion of 10 to 50% by weight. If the blending ratio of bisphenol A is less than 10% by weight, a sufficient interlayer bond strength cannot be obtained,
Further, if it exceeds 50% by weight, the thermal shock resistance and the moisture resistance are deteriorated, which is not preferable.
【００１４】さらに、エポキシ樹脂組成物の成分である
（Ｄ）フェノールノボラック樹脂としては、フェノール
型、アルキル変性フェノール型、ビスフェノールＡ型等
が挙げられ、これらは単独または 2種以上混合して使用
することができる。Examples of the phenol novolac resin (D), which is a component of the epoxy resin composition, include phenol type, alkyl-modified phenol type, and bisphenol A type. These are used alone or in combination of two or more. be able to.
【００１５】エポキシ樹脂組成物の成分である（Ｅ）赤
リンとしては、通常難燃剤として使用される赤リンを使
用することができる。また、赤リンを水酸化アルミニウ
ム又は酸化チタン等でコーティングされたものが挙げら
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。また、（Ｅ）赤リンとしては、樹脂組成物全体
［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）］に対して1 〜20重
量％の割合で配合することが望ましい。1 重量％未満で
は難燃性が出ず、20重量％を超えては絶縁性が低下す
る。As the red phosphorus (E) which is a component of the epoxy resin composition, the red phosphorus usually used as a flame retardant can be used. Further, red phosphorus coated with aluminum hydroxide, titanium oxide or the like can be mentioned, and these can be used alone or in combination of two or more kinds. Further, (E) red phosphorus is preferably blended in a proportion of 1 to 20% by weight based on the whole resin composition [(A) + (B) + (C) + (D)]. If it is less than 1% by weight, flame retardancy does not occur, and if it exceeds 20% by weight, the insulating property is lowered.
【００１６】エポキシ樹脂組成物の成分である（Ｆ）無
機質充填剤しては、タルク、シリカ、アルミナ、水酸化
アルミニウム、三酸化アンチモン等が挙げられ、これら
は単独または 2種以上混合して使用することができる。
本発明では（Ｅ）赤リンと（Ｆ）無機質充填剤を併用す
ることが特徴である。無機質充填剤の配合割合は、樹脂
組成物全体［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）］に対し
て、（Ｅ）の赤リンを含めて35〜150 重量％の割合で、
配合することが望ましい。配合量が35重量％未満では、
耐熱性、耐熱衝撃性が悪く、また150 重量％を超えると
粘度が増加し、基材に塗布ムラが発生しボイドや板厚不
良となり好ましくない。これらの成分からなるものを溶
剤に溶解してワニス状にして基材に含浸させる。Examples of the inorganic filler (F) which is a component of the epoxy resin composition include talc, silica, alumina, aluminum hydroxide, antimony trioxide and the like, and these are used alone or in combination of two or more. can do.
The present invention is characterized in that (E) red phosphorus and (F) inorganic filler are used in combination. The blending ratio of the inorganic filler is 35 to 150% by weight including the red phosphorus (E) with respect to the entire resin composition [(A) + (B) + (C) + (D)]. ,
It is desirable to mix them. If the amount is less than 35% by weight,
The heat resistance and the thermal shock resistance are poor, and when it exceeds 150% by weight, the viscosity increases, and coating unevenness occurs on the base material, resulting in voids and poor plate thickness. A material consisting of these components is dissolved in a solvent to form a varnish, which is then impregnated into the substrate.
【００１７】本発明において用いるプリプレグは、以上
の各成分を予め反応させて樹脂組成物としたものをガラ
ス基材に塗布・含浸・乾燥させるものではなく、上述し
た各成分を必須成分とするエポキシ樹脂組成物を、ガラ
ス基材に含浸・乾燥させる工程で（Ａ）ビスフェノール
Ａ型エポキシ樹脂及び（Ｂ）ノボラック型エポキシ樹脂
と（Ｃ）ビスフェノールＡとを反応させてプリプレグを
つくるものである。The prepreg used in the present invention is not a resin composition obtained by previously reacting each of the above components into a glass substrate, coating, impregnating and drying the same, but an epoxy containing the above components as essential components. In a step of impregnating and drying a resin composition on a glass substrate, (A) bisphenol A type epoxy resin and (B) novolac type epoxy resin are reacted with (C) bisphenol A to form a prepreg.
【００１８】本発明に用いるガラス基材および銅箔は、
ともに通常ガラスエポキシ銅張積層板に使用されるもの
であれば特に制限はなく使用することができる。ガラス
基材としてガラス織布、ガラス不織布、ガラスマット等
が挙げられる。The glass substrate and copper foil used in the present invention are
Both can be used without particular limitation as long as they are usually used for glass epoxy copper clad laminates. Examples of the glass substrate include a glass woven fabric, a glass nonwoven fabric, and a glass mat.
【００１９】本発明の銅張積層板の製造工程は、上述の
ようにしてつくったプリプレグの複数枚をコンポジット
構成に積層し、銅箔を重ねて加熱加圧一体に成形してコ
ンポジット銅張積層板を製造することができる。The manufacturing process of the copper clad laminate according to the present invention is carried out by laminating a plurality of prepregs prepared as described above in a composite structure, stacking copper foils and molding them under heat and pressure to form a composite copper clad laminate. Plates can be manufactured.
【００２０】[0020]
【作用】本発明は、エポキシ樹脂組成物を、ガラス基材
に含浸・乾燥させる工程で（Ａ）ビスフェノールＡ型エ
ポキシ樹脂及び（Ｂ）ノボラック型エポキシ樹脂と、
（Ｃ）ビスフェノールＡとを反応させてプリプレグをつ
くることを特徴としている。従来、積層板用の樹脂組成
物は、エポキシ樹脂と 2価ビスフェノールＡとを反応釜
中で反応させ高分子化した後、ガラス基材に塗布・含浸
・乾燥させてプリプレグを製造していた。これに対し
て、本発明では反応前の低分子の各成分をそのまま塗布
してガラスクロス等への含浸性を改善し、塗布ムラの発
生を防止し、無機質充填剤を増加させ、かつノンハロゲ
ンの赤リンを配合して耐熱性、難燃性を向上させること
ができた。またプリプレグ製造時に各成分の反応を進め
ることにより、エポキシ樹脂とビスフェノールＡと硬化
剤間での競争反応をコントロールして、層間結合力、耐
熱衝撃性を改善し、従来の特徴である耐熱性、耐湿性、
スルーホール信頼性も維持させたコンポジット銅張積層
板を製造することができたものである。The present invention comprises (A) a bisphenol A type epoxy resin and (B) a novolac type epoxy resin in a step of impregnating and drying an epoxy resin composition on a glass substrate.
(C) A prepreg is produced by reacting with bisphenol A. Conventionally, a resin composition for a laminated board has been produced by reacting an epoxy resin and a divalent bisphenol A in a reaction vessel to polymerize, and then coating, impregnating and drying the glass base material to produce a prepreg. On the other hand, in the present invention, each low-molecular component before the reaction is applied as it is to improve the impregnating property to the glass cloth and the like, the occurrence of coating unevenness is prevented, the inorganic filler is increased, and the halogen-free It was possible to improve heat resistance and flame retardancy by adding red phosphorus. In addition, by advancing the reaction of each component during the production of prepreg, the competitive reaction between the epoxy resin, bisphenol A and the curing agent is controlled to improve the interlayer bond strength and thermal shock resistance. Moisture resistance,
It was possible to manufacture a composite copper-clad laminate that also maintained through-hole reliability.
【００２１】[0021]
【実施例】次に本発明を実施例によって説明する。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。
以下の実施例および比較例において、「部」とは「重量
部」を意味する。Next, the present invention will be described by way of examples. The present invention is not limited by these examples.
In the following Examples and Comparative Examples, “parts” means “parts by weight”.
【００２２】実施例１ ビスフェノールＡ型エポキシ樹脂（エポキシ当量 187）
173部、クレゾールノボラックエポキシ樹脂（エポキシ
当量210 、固形分70重量％）23部、ビスフェノール41
部、ビスフェノールＡ型ノボラック樹脂（水酸基価 11
8、固形分70重量％）108 部、赤リン10部、無機質充填
剤として水酸化アルミニウム306 部、2-エチル-4−メチ
ルイミダゾール 0.1部およびメチルセロソルブを加えて
樹脂固形分80重量％のエポキシ樹脂ワニスを調製した。
このエポキシ樹脂ワニスを用いてガラス不織布に連続的
に含浸させ、165 ℃に保持した乾燥器で 6分間乾燥させ
てプリプレグ（I)を得た。このプリプレグ（I)を 6枚重
ね合わせ、その両面に別に準備した無機質充填剤を含ま
ないワニスをガラス織布に含浸・乾燥させてプリプレグ
（II）を重ね合わせ、さらにその両面に厚さ18μm の銅
箔を重ね、温度170 ℃，圧力 4.9ＭＰa で90分間加熱加
圧一体に成形してコンポジット銅張積層板を製造した。Example 1 Bisphenol A type epoxy resin (epoxy equivalent 187)
173 parts, cresol novolac epoxy resin (epoxy equivalent 210, solid content 70% by weight) 23 parts, bisphenol 41
Part, bisphenol A type novolac resin (hydroxyl value 11
(8, solid content 70% by weight) 108 parts, red phosphorus 10 parts, 306 parts aluminum hydroxide as an inorganic filler, 0.1 parts 2-ethyl-4-methylimidazole and methylcellosolve are added to obtain an epoxy resin having a solid content of 80% by weight. A resin varnish was prepared.
A glass non-woven fabric was continuously impregnated with this epoxy resin varnish and dried for 6 minutes in a drier kept at 165 ° C to obtain a prepreg (I). Six pieces of this prepreg (I) were overlaid, and a varnish containing no inorganic filler prepared separately was impregnated and dried on both sides of the prepreg (II) and overlaid on both sides with a thickness of 18 μm. Copper foils were layered and heat-pressed integrally at a temperature of 170 ° C and a pressure of 4.9MPa for 90 minutes to form a composite copper-clad laminate.
【００２３】実施例２ 実施例１のワニスの配合において、無機質充填剤として
水酸化アルミニウム204 部、タルク102 部とした以外
は、すべて実施例１と同一にしてワニスを調製し、さら
に実施例１と同一にしてコンポジット銅張積層板を製造
した。Example 2 A varnish was prepared in the same manner as in Example 1 except that 204 parts of aluminum hydroxide and 102 parts of talc were used as the inorganic fillers in the formulation of the varnish of Example 1, and further, Example 1 A composite copper clad laminate was manufactured in the same manner as in.
【００２４】比較例１ エポキシ樹脂（エポキシ当量 420、固形分75重量％）24
0 部、クレゾールノボラックエポキシ樹脂（エポキシ当
量 210、固形分70重量％）26部、ビスフェノールＡ型ノ
ボラック樹脂（水酸基価 118、固形分70重量％）87部、
無機質充填剤としてタルク259 部、2-エチル-4−メチル
イミダゾール 0.1部およびメチルセロソルブを加えて、
樹脂固形分80重量％のエポキシ樹脂ワニスを調製した。
さらに実施例１と同様にしてコンポジット銅張積層板を
製造した。Comparative Example 1 Epoxy resin (epoxy equivalent 420, solid content 75% by weight) 24
0 parts, cresol novolac epoxy resin (epoxy equivalent 210, solid content 70% by weight) 26 parts, bisphenol A type novolac resin (hydroxyl value 118, solid content 70% by weight) 87 parts,
As an inorganic filler, 259 parts of talc, 0.1 part of 2-ethyl-4-methylimidazole and methyl cellosolve were added,
An epoxy resin varnish having a resin solid content of 80% by weight was prepared.
Further, a composite copper-clad laminate was produced in the same manner as in Example 1.
【００２５】比較例２ 比較例１のワニスの配合において、無機質充填剤として
タルクを水酸化アルミニウムに替えた以外は、すべて比
較例１と同一にしてワニスを調製し、さらに比較例１と
同一にしてコンポジット銅張積層板を製造した。Comparative Example 2 A varnish was prepared in the same manner as in Comparative Example 1 except that talc was replaced with aluminum hydroxide as the inorganic filler in the varnish formulation of Comparative Example 1, and further the same as in Comparative Example 1. To produce a composite copper clad laminate.
【００２６】実施例１〜２および比較例１〜２で製造し
たコンポジット銅張積層板を用いて、半田耐熱性、耐熱
衝撃性、スルーホール信頼性、耐トラッキング性、難燃
性、ボイドの発生の状況を試験したのでその結果を表１
に示した。本発明はいずれの特性においても優れてお
り、本発明の効果を確認することができた。Using the composite copper clad laminates produced in Examples 1-2 and Comparative Examples 1-2, solder heat resistance, thermal shock resistance, through-hole reliability, tracking resistance, flame retardancy, and generation of voids. Since the situation was tested, the results are shown in Table 1.
It was shown to. The present invention was excellent in any of the characteristics, and the effect of the present invention could be confirmed.
【００２７】半田耐熱性は、コンポジット銅張積層板 2
5 mm×25 mm の試験片を260 ℃および280 ℃の半田浴に
浮かべ、フクレの発生するまでの時間を試験した。耐熱
衝撃性は銅箔をエッチングした 50 mm×50 mm の試験片
10個を、122 ℃， 0.1ＭＰa，7 時間の条件で前処理し
た後、260 ℃の半田浴に30秒間ディップし、フクレの発
生の有無を試験した。スルーホール信頼性は、200 穴の
導通したスルーホール基板をつくり、260 ℃のオイルに
10秒間浸漬した後、20℃のオイルに10秒間浸漬すること
を 1サイクルとし、各サイクル毎に導通抵抗を測定し、
断線するまでのサイクル数を測定した。難燃性はＵＬ９
４試験法に基づき試験した。ボイドの発生状況は、コン
ポジット銅張積層板30枚中のボイドの発生した枚数を調
べた。耐トラッキング性はＩＥＣ電解液滴下法によって
試験した。Solder heat resistance is a composite copper clad laminate 2
A 5 mm × 25 mm test piece was floated in a solder bath at 260 ° C. and 280 ° C., and the time until blistering occurred was tested. Thermal shock resistance is a 50 mm × 50 mm test piece obtained by etching copper foil.
Ten pieces were pretreated under the conditions of 122 ° C., 0.1 MPa, 7 hours, and then dipped in a solder bath at 260 ° C. for 30 seconds, and the presence or absence of blistering was tested. Through-hole reliability is achieved by making a 200-hole conductive through-hole substrate and using it at 260 ° C oil.
After soaking for 10 seconds, soaking in oil at 20 ° C for 10 seconds is one cycle, and the conduction resistance is measured at each cycle.
The number of cycles until disconnection was measured. Flame retardant is UL9
It tested based on 4 test methods. For the occurrence of voids, the number of voids in 30 composite copper-clad laminates was examined. The tracking resistance was tested by the IEC electrolytic drop method.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【発明の効果】以上の説明および表１から明らかなよう
に、本発明のコンポジット銅張積層板は、耐熱性、耐湿
性、耐熱衝撃性、層間結合力、耐トラッキング性、難燃
性、スルーホール信頼性等に優れ、樹脂の粘度が低く塗
布・含浸が容易で、ノンハロゲンのため有毒ガス発生が
なく、ボイドの発生の少ないもので電子機器等に好適な
ものである。As is clear from the above description and Table 1, the composite copper-clad laminate of the present invention has heat resistance, moisture resistance, thermal shock resistance, interlayer bonding strength, tracking resistance, flame retardancy, and through. It is excellent in hole reliability, low in resin viscosity, easy to apply and impregnate, does not generate toxic gas because it is non-halogen, and generates few voids, which is suitable for electronic equipment.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｋ 3/02 ＮＫＵ Ｃ０８Ｋ 3/02 ＮＫＵ Ｃ０８Ｌ 63/00 ＮＪＷ Ｃ０８Ｌ 63/00 ＮＪＷ Ｈ０５Ｋ 1/03 ６３０ Ｈ０５Ｋ 1/03 ６３０Ｆ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08K 3/02 NKU C08K 3/02 NKU C08L 63/00 NJW C08L 63/00 NJW H05K 1/03 630 H05K 1/03 630F
Claims (1)
・乾燥させたプリプレグ複数枚をコンポジット構成に積
層し、その少なくとも片面に銅箔を重ね合わせて一体に
成形したコンポジット銅張積層板であって、（Ａ）ビス
フェノールＡ型エポキシ樹脂、（Ｂ）ノボラック型エポ
キシ樹脂、（Ｃ）ビスフェノールＡ、（Ｄ）フェノール
ノボラック樹脂、（Ｅ）赤リンおよび（Ｆ）無機質充填
剤を必須成分とし、樹脂成分全体［（Ａ）＋（Ｂ）＋
（Ｃ）＋（Ｄ）］に対して、（Ｅ）の赤リンおよび
（Ｆ）の無機質充填剤を35〜150 重量％の割合で含有す
るエポキシ樹脂組成物を基材に含浸・乾燥させる工程に
おいて、（Ａ）ビスフェノールＡ型エポキシ樹脂及び
（Ｂ）ノボラック型エポキシ樹脂と、（Ｃ）ビスフェノ
ールＡとを反応させたプリプレグを用いてなることを特
徴とするコンポジット銅張積層板。1. A composite copper-clad laminate in which a plurality of prepregs obtained by impregnating and drying a glass substrate with an epoxy resin composition are laminated in a composite structure, and copper foils are laminated on at least one surface of the prepregs and integrally molded. And (A) bisphenol A type epoxy resin, (B) novolac type epoxy resin, (C) bisphenol A, (D) phenol novolac resin, (E) red phosphorus and (F) inorganic filler as essential components, All components [(A) + (B) +
(C) + (D)], a step of impregnating a base material with an epoxy resin composition containing 35 to 150% by weight of red phosphorus of (E) and an inorganic filler of (F) and drying. 2. A composite copper-clad laminate, comprising: (A) a bisphenol A type epoxy resin and (B) a novolac type epoxy resin, and (C) a prepreg obtained by reacting with bisphenol A.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7079739A JP2679005B2 (en) | 1995-03-10 | 1995-03-10 | Composite copper clad laminate |
| EP96900435A EP0763566A4 (en) | 1995-03-10 | 1996-01-12 | Halogen-free flame-retardant epoxy resin composition |
| PCT/JP1996/000032 WO1996028511A1 (en) | 1995-03-10 | 1996-01-12 | Halogen-free flame-retardant epoxy resin composition |
| CN96190181A CN1073132C (en) | 1995-03-10 | 1996-01-12 | Halogen-free flame-retardant epoxy resin composition |
| US08/737,173 US5994429A (en) | 1995-03-10 | 1996-01-12 | Halogen-free flame-retardant epoxy resin composition |
| TW85102432A TW322507B (en) | 1995-03-10 | 1996-02-29 | |
| KR1019960706337A KR970702899A (en) | 1995-03-10 | 1996-11-08 | Halogen-free flame retardant epoxy resin composition (HALOGEN-FREE FLAME-RETRA DANT EPOXY RESIN COMPOSITION) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7079739A JP2679005B2 (en) | 1995-03-10 | 1995-03-10 | Composite copper clad laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08244166A JPH08244166A (en) | 1996-09-24 |
| JP2679005B2 true JP2679005B2 (en) | 1997-11-19 |
Family
ID=13698597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7079739A Expired - Fee Related JP2679005B2 (en) | 1995-03-10 | 1995-03-10 | Composite copper clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2679005B2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5394357A (en) * | 1977-01-28 | 1978-08-18 | Hitachi Ltd | Flame-retardant resin composition |
| JPS5493044A (en) * | 1977-12-29 | 1979-07-23 | Sanyurejin Kk | Flameeretarded epoxy resin composition for impregnation |
| JPS63346A (en) * | 1986-06-19 | 1988-01-05 | Rin Kagaku Kogyo Kk | Red phosphorus flame retarder and flame-retardant resin composition |
| JPH05286075A (en) * | 1992-04-10 | 1993-11-02 | Toshiba Chem Corp | Manufacture of copper-clad laminate |
-
1995
- 1995-03-10 JP JP7079739A patent/JP2679005B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08244166A (en) | 1996-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3412585B2 (en) | Epoxy resin composition for prepreg used for production of printed wiring board and multilayer printed wiring board, prepreg, multilayer printed wiring board | |
| KR101456769B1 (en) | Epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board | |
| JP3821728B2 (en) | Prepreg | |
| JP3721950B2 (en) | Epoxy resin composition, prepreg, multilayer printed wiring board | |
| JP2003073543A (en) | Resin composition, prepreg and printed circuit board using the same | |
| JP2679005B2 (en) | Composite copper clad laminate | |
| JP3323873B2 (en) | Composite copper-clad laminate | |
| JPH05309789A (en) | Production of composite copper clad laminated sheet | |
| JP3870811B2 (en) | Phosphorus-modified epoxy resin composition for printed wiring board and method for producing the same | |
| JPH07162114A (en) | Composite copper-clad laminated board | |
| JP2931262B2 (en) | Manufacturing method of glass epoxy copper clad laminate | |
| JPH10193516A (en) | Production of glass epoxy copper plated laminated sheet | |
| JP4000754B2 (en) | Flame retardant epoxy resin composition and prepreg, laminate and printed wiring board using the same | |
| JP3855474B2 (en) | Composite metal foil laminate | |
| JP3119578B2 (en) | Manufacturing method of printed circuit board | |
| JP2003096296A (en) | Resin composition, prepreg and printed circuit board using the same | |
| JPH07276565A (en) | Production of composite copper-clad laminate sheet | |
| JP3620286B2 (en) | Composite metal foil laminate | |
| KR101556657B1 (en) | Resine composition and prepreg and printed wiring board using the same | |
| JPH05138808A (en) | Copper clad laminated sheet | |
| JPH05105778A (en) | Laminated board manufacturing method | |
| JP4075300B2 (en) | Composite laminate and printed wiring board | |
| JP3741382B2 (en) | Manufacturing method of prepreg | |
| JPH08276532A (en) | Glass epoxy copper-clad laminate | |
| JPH03257890A (en) | Copper clad laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |