JPH07223294A - Copper clad laminated sheet - Google Patents
Copper clad laminated sheetInfo
- Publication number
- JPH07223294A JPH07223294A JP3909994A JP3909994A JPH07223294A JP H07223294 A JPH07223294 A JP H07223294A JP 3909994 A JP3909994 A JP 3909994A JP 3909994 A JP3909994 A JP 3909994A JP H07223294 A JPH07223294 A JP H07223294A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- prepreg
- copper
- time
- clad laminate
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 48
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 48
- 239000011521 glass Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 16
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 16
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000004080 punching Methods 0.000 abstract description 12
- 238000005553 drilling Methods 0.000 abstract description 9
- 238000005336 cracking Methods 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 229920000570 polyether Polymers 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 14
- 239000002966 varnish Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 229930003836 cresol Natural products 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 239000004843 novolac epoxy resin Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 4
- 239000011190 CEM-3 Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 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
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- -1 glycidyl ester Chemical class 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ドリル加工時の穴壁粗
れや、打抜加工時のクラックの発生のない、信頼性に優
れた銅張積層板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper clad laminate having excellent reliability, which is free from hole wall roughness during drilling and cracks during punching.
【０００２】[0002]
【従来の技術】近年、電子機器の発達は目覚ましく、銅
張積層板の使用も多種多様となり、一段と優れた特性の
ものが要求されるようになってきた。ガラス不織布を基
材とする銅張積層板は、ガラス織布を基材とするいわゆ
るガラスエポキシ銅張積層板と電気的特性が同等である
上に、打抜加工性に優れているため、その生産量は急速
に伸びている。この不織布基材の銅張積層板は、厚さ 1
00〜600 μm のガラス不織布にエポキシ樹脂を塗布・含
浸し、加熱乾燥したプリプレグを得て、これに銅箔を重
ね加熱加圧一体に成形して製造されている。ガラス不織
布を基材とする銅張積層板は、ガラス織布を基材とする
銅張積層板に比べ、ドリル加工や打抜加工に優れている
が、寸法特性やスルーホール信頼性に劣るという欠点が
あった。これを改良するためエポキシ樹脂に20〜70重量
％の水酸化アルミニウム粉末やＥガラス粉末のような無
機質充填剤を加えた銅張積層板が一般的に使用されてい
る。2. Description of the Related Art In recent years, the development of electronic equipment has been remarkable, and the use of copper-clad laminates has been diversified, and demands have been made for those with even more excellent characteristics. The copper-clad laminate based on a glass non-woven fabric has the same electrical characteristics as a so-called glass epoxy copper-clad laminate based on a glass woven fabric and is excellent in punching workability. Production is growing rapidly. This non-woven substrate copper clad laminate has a thickness of 1
It is manufactured by coating and impregnating a glass non-woven fabric of 00-600 μm with epoxy resin, obtaining a heat-dried prepreg, and stacking a copper foil on it and integrally molding it with heat and pressure. Copper clad laminates based on non-woven glass are superior to copper clad laminates based on woven glass cloth in drilling and punching, but are inferior in dimensional characteristics and through-hole reliability. There was a flaw. In order to improve this, a copper clad laminate obtained by adding 20 to 70% by weight of an inorganic filler such as aluminum hydroxide powder or E glass powder to an epoxy resin is generally used.
【０００３】しかしながら、こうしたタイプの銅張積層
板は、硬く剪断抵抗が大きくなりドリル加工時の穴壁粗
れや、打抜加工時のクラックが発生しやすいという欠点
があった。However, such a type of copper-clad laminate has the drawback that it is hard and has a large shear resistance, so that the wall of the hole is roughened during drilling and cracks are easily generated during punching.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記の欠点
を解消するためになされたもので、ドリル加工時の穴壁
粗れや、打抜加工時のクラックの発生を防止し、信頼性
に優れた銅張積層板を提供することを目的とするもので
ある。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks, and prevents the wall wall roughness during drilling and the occurrence of cracks during punching, which improves reliability. It is an object of the present invention to provide a copper clad laminate excellent in heat resistance.
【０００５】[0005]
【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進めた結果、ガラス不織布
を基材とするプリプレグにフェノキシ樹脂およびエポキ
シ樹脂を用いることによって、上記目的を達成できるこ
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 found that the use of a phenoxy resin and an epoxy resin in a prepreg based on a glass non-woven fabric makes it possible to achieve the above-mentioned object. The present invention has been completed by finding that the above can be achieved.
【０００６】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を複数枚積層
し、その少なくとも片面に銅箔を重ね合わせて一体に成
形する銅張積層板において、ガラス不織布に下記の成
分、（Ａ）次の一般式で示されるフェノキシ樹脂、That is, the present invention relates to a copper clad laminate obtained by laminating a plurality of prepregs obtained by impregnating and drying an epoxy resin composition on a glass substrate, and superimposing a copper foil on at least one surface of the prepreg to integrally form the prepreg. The following components in the glass nonwoven fabric, (A) phenoxy resin represented by the following general formula,
【０００７】[0007]
【化２】 （ただし、式中Ｘは水素原子、臭素原子、あるいは水素
原子と臭素原子とが混在したものを示し、n は1 以上の
整数の高分子分子種を表す）（Ｂ）エポキシ樹脂、
（Ｃ）硬化剤、（Ｄ）硬化促進剤および（Ｅ）無機充填
剤を必須成分とするエポキシ樹脂組成物を含浸・乾燥さ
せたプリプレグを用いてなることを特徴とする銅張積層
板である。[Chemical 2] (In the formula, X represents a hydrogen atom, a bromine atom, or a mixture of a hydrogen atom and a bromine atom, and n represents a polymer molecular species of an integer of 1 or more) (B) Epoxy resin,
A copper clad laminate characterized by using a prepreg impregnated and dried with an epoxy resin composition containing (C) a curing agent, (D) a curing accelerator and (E) an inorganic filler as essential components. .
【０００８】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００９】本発明に用いるエポキシ樹脂組成物の成分
である（Ａ）化２に示されるフェノキシ樹脂は、1 種の
ポリヒドロキシポリエーテルである。フェノキシ樹脂は
数平均分子量 10000〜50000 程度の高分子量であるため
極めて粘度が高い。このため積層板としての用途を考え
る場合、一般的にはガラス織布に含浸しにくく、また、
加熱加圧一体成形時にずれ出しの原因となり好ましくな
い。しかし、フェノキシ樹脂はガラス不織布に含浸し、
エポキシ樹脂、硬化剤、硬化促進剤、無機充填剤ととも
に硬化させると、その硬化物の耐衝撃性が向上し打抜き
加工時のクラックが発生しにくいということを見いだし
たものである。フェノキシ樹脂の配合割合は、エポキシ
樹脂組成物に対して 2〜10重量％含有するように配合す
ることが望ましい。その割合が 2重量％未満では耐衝撃
性が不十分であり、また、10重量％を超えると樹脂組成
物の粘度が高くなり好ましくない。The phenoxy resin represented by Chemical formula (A) 2, which is a component of the epoxy resin composition used in the present invention, is one kind of polyhydroxy polyether. The phenoxy resin has a high molecular weight of about 10000 to 50000 and has an extremely high viscosity. Therefore, when considering the use as a laminated plate, it is generally difficult to impregnate a glass woven cloth,
It is not preferable because it may cause slippage during heating and pressure integral molding. However, the phenoxy resin impregnates the glass non-woven fabric,
It has been found that when cured together with an epoxy resin, a curing agent, a curing accelerator, and an inorganic filler, the cured product has improved impact resistance and cracks are less likely to occur during punching. It is desirable to mix the phenoxy resin so as to be contained in an amount of 2 to 10% by weight based on the epoxy resin composition. If the proportion is less than 2% by weight, impact resistance is insufficient, and if it exceeds 10% by weight, the viscosity of the resin composition becomes high, which is not preferable.
【００１０】本発明に用いるエポキシ樹脂組成物の成分
である（Ｂ）エポキシ樹脂としては、 1分子中に 2個以
上のエポキシ基を有する化合物であればよく、特に制限
はなく広く使用することができる。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、ノボラックエポキシ樹脂またはこれらの臭素化合物
等のグリシジルエーテル型エポキシ樹脂、グリシジルエ
ステル型エポキシ樹脂、グリシジルアミン型エポキシ樹
脂、脂環式エポキシ樹脂、複素環型エポキシ樹脂等が挙
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 (B) epoxy resin which is a component of the epoxy resin composition used in the present invention may be a compound having two or more epoxy groups in one molecule and is not particularly limited and can be widely used. it can. For example, glycidyl ether type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin or bromine compounds thereof, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, heterocycle Type epoxy resin and the like, which may be used alone or in admixture of two or more.
【００１１】本発明に用いるエポキシ樹脂組成物の成分
である（Ｃ）硬化剤としては、ジシアンジアミド、イミ
ダゾール類、芳香族アミン等のアミン類、フェノールノ
ボラック、クレゾールノボラック、ビスフェノールＡ型
ノボラック等のノボラック類、無水フタル酸、無水クロ
レンディック酸等いずれも使用可能で、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。これらのな
かでもジシアンジアミドやノボラック類が好ましく使用
される。The (C) curing agent, which is a component of the epoxy resin composition used in the present invention, includes dicyandiamide, imidazoles, amines such as aromatic amines, novolaks such as phenol novolac, cresol novolac and bisphenol A type novolac. , Phthalic anhydride, chlorendic anhydride and the like can be used, and these can be used alone or in combination of two or more kinds. Among these, dicyandiamide and novolaks are preferably used.
【００１２】本発明に用いるエポキシ樹脂組成物の成分
である（Ｄ）硬化促進剤としては、2-エチル-4−メチル
イミダゾール、2-フェニル-4−メチルイミダゾール、2-
メチルイミダゾール等のイミダゾール誘導体やこれらの
シアノエチル化合物、アジン化合物等やベンジルジメチ
ルアミン、1,8-ジアザビシクロ（ 5,4,0）ウンデセン-7
［ＤＢＵ］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。As the curing accelerator (D) which is a component of the epoxy resin composition used in the present invention, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-
Imidazole derivatives such as methylimidazole, their cyanoethyl compounds, azine compounds, benzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene-7
[DBU] and the like can be mentioned, and these can be used alone or in combination of two or more kinds.
【００１３】本発明に用いるエポキシ樹脂組成物の成分
である（Ｅ）無機充填剤としては、水酸化アルミニウ
ム、水酸化マグネシウム、タルク、Ｅガラス粉末、アル
ミナ、酸化マグネシウム、二酸化チタン、チタン酸カリ
ウム、ケイ酸カルシウム、炭酸カルシウム、クレイ等が
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。As the inorganic filler (E) which is a component of the epoxy resin composition used in the present invention, aluminum hydroxide, magnesium hydroxide, talc, E glass powder, alumina, magnesium oxide, titanium dioxide, potassium titanate, Examples thereof include calcium silicate, calcium carbonate, clay and the like, and these can be used alone or in combination of two or more kinds.
【００１４】本発明に用いるエポキシ樹脂組成物は、上
述したフェノキシ樹脂、エポキシ樹脂、硬化剤、硬化促
進剤および無機充填剤を必須成分とするが、本発明の目
的に反しない範囲において他の成分を添加配合すること
ができる。The epoxy resin composition used in the present invention contains the above-mentioned phenoxy resin, epoxy resin, curing agent, curing accelerator and inorganic filler as essential components, but other components within the range not deviating from the object of the present invention. Can be added and compounded.
【００１５】本発明に用いるガラス基材としては、通常
使用されているものであればよく、特に限定されるもの
ではない。ＥガラスまたはＤガラスからなるガラス織布
またはガラス不織布が使用される。The glass substrate used in the present invention is not particularly limited as long as it is a commonly used one. A woven glass fabric or a non-woven glass fabric made of E glass or D glass is used.
【００１６】上述したフェノキシ樹脂、エポキシ樹脂、
硬化剤、硬化促進剤および無機充填剤その他の添加剤か
らなるエポキシ樹脂組成物のワニスを、ガラス不織布に
常法により塗布・含浸・乾燥させてプリプレグ（i)をつ
くる。この際含浸を良くするために希釈溶剤を適宜使用
することもできる。こうして得られたプリプレグ（i)複
数枚の表裏面に通常のエポキシガラスクロスプリプレグ
(ii)を積層し、積層した全体のプリプレグの少なくとも
片面に銅箔を重ね合わせて加熱加圧一体に成形して、銅
張積層板を容易に製造することができる。ここでは、プ
リプレグ（i)を中央にはさんでプリプレグ(ii)を用いる
ことを説明したが、必要によってはこの逆又はプリプレ
グ（i)のみを使用することもできる。銅張積層板の製造
方法については、特に制限はなくいずれの方法でもよ
い。The above-mentioned phenoxy resin, epoxy resin,
A varnish of an epoxy resin composition comprising a curing agent, a curing accelerator, an inorganic filler and other additives is applied, impregnated and dried onto a glass non-woven fabric by a conventional method to prepare a prepreg (i). At this time, a diluting solvent can be appropriately used to improve impregnation. The prepreg thus obtained (i) Ordinary epoxy glass cloth prepreg on the front and back of multiple sheets
The copper-clad laminate can be easily manufactured by laminating (ii) and laminating copper foil on at least one surface of the entire laminated prepreg and integrally molding under heating and pressing. Here, it is explained that the prepreg (i) is used with the prepreg (i) sandwiched in the center, but if necessary, the opposite or only the prepreg (i) can be used. The method for producing the copper-clad laminate is not particularly limited, and any method may be used.
【００１７】[0017]
【作用】本発明の銅張積層板は、フェノキシ樹脂、エポ
キシ樹脂、硬化剤、硬化促進剤及び無機充填剤を含有し
たエポキシ樹脂組成物のプリプレグを用いたことによっ
て、ドリル加工時の穴壁粗れや、打抜加工時のクラック
の発生を防止し、信頼性に優れた銅張積層板を得ること
ができた。即ち、フェノキシ樹脂、エポキシ樹脂を用い
ることによって、組成物の粘度上昇を抑制し含浸性を損
なわずに、架橋点間距離を広げ、耐熱性を下げることな
く耐衝撃性を向上させることに成功した。その結果、ド
リル加工時の穴壁粗れや、打抜加工時のクラックの発生
を防止し、信頼性の高い銅張積層板を得ることができた
ものである。The copper-clad laminate of the present invention uses the prepreg of the epoxy resin composition containing the phenoxy resin, the epoxy resin, the curing agent, the curing accelerator, and the inorganic filler, so that the hole wall roughness during drilling is improved. Moreover, it was possible to prevent the occurrence of cracks during punching and obtain a copper clad laminate with excellent reliability. That is, by using a phenoxy resin or an epoxy resin, it succeeded in suppressing the viscosity increase of the composition and expanding the distance between crosslinking points without impairing the impregnating property and improving the impact resistance without lowering the heat resistance. . As a result, it is possible to obtain a highly reliable copper-clad laminate by preventing hole wall roughness during drilling and cracks during punching.
【００１８】[0018]
【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。EXAMPLES The present invention will now be described with reference to examples. The invention is not limited by these examples.
In the following examples and comparative examples, "part" means "part by weight".
【００１９】実施例１ 臭素化エポキシ樹脂（エポキシ当量 480）87部と、クレ
ゾールノボラックエポキシ樹脂（エポキシ当量 210）10
部と、フェノキシ樹脂としてフェノトートＹＰ−５０
（東都化成社製商品名、数平均分子量 12000） 3部と
に、無機充填剤として水酸化アルミニウム（平均粒径 1
μm ）80部、ジシアンジアミド 3部、2-エチル-4−メチ
ルイミダゾール 0.1部、アセトン60部およびジメチルホ
ルムアミド20部を加えて攪拌溶解してエポキシ樹脂ワニ
スを調製した。これを厚さ 300μm のガラス不織布に塗
布含浸し、160 ℃の温度で乾燥してプリプレグ (I)をつ
くった。Example 1 87 parts of brominated epoxy resin (epoxy equivalent 480) and 10 parts of cresol novolac epoxy resin (epoxy equivalent 210) 10
And Phenothote YP-50 as a phenoxy resin
(Toto Kasei Co., Ltd., trade name, number average molecular weight 12000) 3 parts and aluminum hydroxide as an inorganic filler (average particle size 1
μm) 80 parts, dicyandiamide 3 parts, 2-ethyl-4-methylimidazole 0.1 part, acetone 60 parts and dimethylformamide 20 parts were added and dissolved by stirring to prepare an epoxy resin varnish. This was coated and impregnated with a glass non-woven fabric having a thickness of 300 μm, and dried at a temperature of 160 ° C. to prepare a prepreg (I).
【００２０】次に、臭素化エポキシ樹脂（エポキシ当量
480）90部と、クレゾールノボラックエポキシ樹脂（エ
ポキシ当量 210）10部とに、ジシアンジアミド 3部、2-
エチル-4−メチルイミダゾール 0.1部、アセトン60部お
よびジメチルホルムアミド20部を加えて攪拌溶解し調製
したエポキシ樹脂ワニスを、厚さ 180μm のガラスクロ
スに塗布・含浸・乾燥してプリプレグ（II）をつくっ
た。Next, a brominated epoxy resin (epoxy equivalent
480) 90 parts and cresol novolac epoxy resin (epoxy equivalent 210) 10 parts, dicyandiamide 3 parts, 2-
Epoxy resin varnish prepared by adding 0.1 part of ethyl-4-methylimidazole, 60 parts of acetone and 20 parts of dimethylformamide and stirring and dissolving was applied, impregnated and dried on a glass cloth having a thickness of 180 μm to prepare a prepreg (II). It was
【００２１】このプリプレグ(I) 6 枚を重ね合わせ、そ
の上下面に前記プリプレグ（II）をそれぞれ 1枚重ね合
わせ、さらにその上下に厚さ35μm の銅箔を重ねて 170
℃，40kg／cm2 で90分間、加熱加圧一体に成形して板厚
1.6mmのＣＥＭ−３の銅張積層板を製造した。Six pieces of this prepreg (I) were piled up, one piece of the prepreg (II) was piled up on each of the upper and lower surfaces thereof, and a copper foil having a thickness of 35 μm was piled on the upper and lower sides thereof.
℃, 40kg / cm 2 90 minutes, heat and pressure integrally molded into a sheet thickness
A 1.6 mm CEM-3 copper clad laminate was produced.
【００２２】実施例２ 臭素化エポキシ樹脂（エポキシ当量 480）84部と、クレ
ゾールノボラックエポキシ樹脂（エポキシ量 210）10部
と、フェノキシ樹脂としてフェノトートＹＰ−５０（東
都化成社製商品名、数平均分子量 12000） 6部とに、無
機充填剤として水酸化アルミニウム（平均粒径 1μm ）
80部、フェノールノボラック樹脂（水酸基当量 104）18
部、2-エチル-4−メチルイミダゾール 0.2部、アセトン
70部およびメチルセロソルブ30部を加え攪拌溶解してエ
ポキシ樹脂ワニスを調製した。これを厚さ 300μm のガ
ラス不織布に塗布含浸し、160 ℃の温度で乾燥してプリ
プレグ(III) をつくった。Example 2 84 parts of brominated epoxy resin (epoxy equivalent 480), 10 parts of cresol novolac epoxy resin (epoxy amount 210), and phenoxy resin Phenototo YP-50 (trade name, manufactured by Tohto Kasei Co., number average) Molecular weight 12000) 6 parts with aluminum hydroxide as an inorganic filler (average particle size 1 μm)
80 parts, phenol novolac resin (hydroxyl group equivalent 104) 18
Part, 2-ethyl-4-methylimidazole 0.2 part, acetone
70 parts and 30 parts of methyl cellosolve were added and dissolved by stirring to prepare an epoxy resin varnish. A 300 μm thick glass non-woven fabric was coated and impregnated with this, and dried at a temperature of 160 ° C. to prepare a prepreg (III).
【００２３】次に、臭素化エポキシ樹脂（エポキシ当量
480）90部と、クレゾールノボラックエポキシ樹脂（エ
ポキシ当量 210）10部とに、フェノールノボラック樹脂
（水酸基当量 104）18部、アセトン55部およびメチルセ
ロソルブ30部を加えて攪拌溶解し調製したエポキシ樹脂
ワニスを、厚さ 180μm のガラスクロスに塗布・含浸・
乾燥してプリプレグ（IV）をつくった。Next, a brominated epoxy resin (epoxy equivalent
480) 90 parts and 10 parts of cresol novolac epoxy resin (epoxy equivalent 210), 18 parts of phenol novolac resin (hydroxyl equivalent 104), 55 parts of acetone and 30 parts of methyl cellosolve were added and stirred to prepare an epoxy resin varnish. On a glass cloth with a thickness of 180 μm.
It was dried to prepare a prepreg (IV).
【００２４】このプリプレグ (III) 6枚を重ね合わせ、
その上下面に前記プリプレグ（lV）をそれぞれ 1枚重ね
合わせ、さらにその上下に厚さ35μm の銅箔を重ねて、
170℃，40kg／cm2 で90分間、加熱加圧一体に成形して
板厚 1.6mmのＣＥＭ−３の銅張積層板を製造した。6 pieces of this prepreg (III) are piled up,
One piece of the prepreg (lV) is overlaid on each of the upper and lower surfaces, and a copper foil with a thickness of 35 μm is overlaid on the upper and lower surfaces.
A CEM-3 copper clad laminate having a plate thickness of 1.6 mm was manufactured by integrally molding under heating and pressing at 170 ° C. and 40 kg / cm 2 for 90 minutes.
【００２５】比較例１ 実施例１のプリプレグ(I) に用いたエポキシ樹脂ワニス
において、フェノキシ樹脂を含まずに、臭素化エポキシ
樹脂（エポキシ当量 480）90部と、クレゾールノボラッ
クエポキシ樹脂（エポキシ当量 210）10部とを用いたエ
ポキシ樹脂ワニスを使用した以外は、実施例１と同様に
してＣＥＭ−３の銅張積層板を製造した。Comparative Example 1 In the epoxy resin varnish used in the prepreg (I) of Example 1, 90 parts of a brominated epoxy resin (epoxy equivalent 480) and cresol novolac epoxy resin (epoxy equivalent 210 ) A copper clad laminate of CEM-3 was produced in the same manner as in Example 1 except that 10 parts of epoxy resin varnish was used.
【００２６】比較例２ 実施例２のプリプレグ(III) に用いたエポキシ樹脂ワニ
スにおいて、フェノキシ樹脂を含まずに、臭素化エポキ
シ樹脂（エポキシ当量 480）90部と、クレゾールノボラ
ックエポキシ樹脂（エポキシ当量 210）10部とを用いた
エポキシ樹脂ワニスを使用した以外は、実施例２と同様
にしてＣＥＭ−３の銅張積層板を製造した。Comparative Example 2 In the epoxy resin varnish used in the prepreg (III) of Example 2, 90 parts of brominated epoxy resin (epoxy equivalent 480) and cresol novolac epoxy resin (epoxy equivalent 210 ) A copper clad laminate of CEM-3 was produced in the same manner as in Example 2 except that 10 parts of epoxy resin varnish was used.
【００２７】実施例１〜２および比較例１〜２で製造し
た銅張積層板について、諸特性を試験したのでその結果
を表１に示したが、本発明は穴壁粗れや、クラックの発
生がなく、その効果を確認することができた。Various properties of the copper clad laminates produced in Examples 1 and 2 and Comparative Examples 1 and 2 were tested. The results are shown in Table 1. In the present invention, the hole wall roughness and cracks are not generated. There was no occurrence and the effect could be confirmed.
【００２８】[0028]
【表１】 ＊1 ：東都化成社製商品名、数平均分子量 12000 ＊2 ：ストレートタイプのドリル（ドリル系 0.9mm）を
用いて、重ね枚数 4枚、ドリル回転数 6000 回転／分、
送り速度60μm ／分で 5000 穴の穴明けを行い、4 枚目
の板の穴内壁を観察し、最大内壁粗さの平均を測定し
た。 ＊3 ：90トンの打抜きプレスにより、穴径 1.0mm、穴間
1.0mmの穴明けを行い、穴の目白およびクラックの有無
を観察評価した。○印…目白クラックなし、△印…目白
発生、×印…目白、穴間クラック発生。 ＊4 ：260 ℃の半田浴にサンプルを浮かべ、フクレが発
生するまでの時間を測定した。 ＊5 ：ＪＩＳ−Ｃ−６４８１に従い測定した。[Table 1] * 1: Toto Kasei Co., Ltd. product name, number average molecular weight 12000 * 2: Using a straight type drill (drill system 0.9 mm), stacking 4 sheets, drill rotation speed 6000 rotations / minute,
5000 holes were drilled at a feed rate of 60 μm / min, the inner wall of the hole of the fourth plate was observed, and the average of the maximum inner wall roughness was measured. * 3: With a 90-ton punching press, the hole diameter is 1.0 mm and the hole spacing is
A 1.0 mm hole was drilled, and the white of the hole and the presence or absence of cracks were observed and evaluated. ○ mark: No whitening cracks, △ mark: Whitening occurred, × mark: Whitening, inter-hole cracking occurred. * 4: The sample was floated in a solder bath at 260 ° C and the time until blistering occurred was measured. * 5: Measured according to JIS-C-6481.
【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、本発明の銅張積層板はドリル加工時の穴壁粗れや、
打抜加工時のクラックの発生を防止し、信頼性に優れ、
かつ他の電気的、機械的特性を従来品と同様にバランス
よく保持したもので電子機器、通信機器用として好適な
ものである。As is clear from the above description and Table 1, the copper clad laminate of the present invention has a hole wall roughness during drilling,
Prevents the occurrence of cracks during punching, has excellent reliability,
In addition, other electrical and mechanical properties are maintained in a well-balanced manner as in the conventional product, which is suitable for electronic devices and communication devices.
Claims (1)
・乾燥させたプリプレグを複数枚積層し、その少なくと
も片面に銅箔を重ね合わせて一体に成形する銅張積層板
において、ガラス不織布に下記の成分、（Ａ）次の一般
式で示されるフェノキシ樹脂、 【化１】 （ただし、式中Ｘは水素原子、臭素原子、あるいは水素
原子と臭素原子とが混在したものを示し、n は1 以上の
整数の高分子分子種を表す）（Ｂ）エポキシ樹脂、
（Ｃ）硬化剤、（Ｄ）硬化促進剤および（Ｅ）無機充填
剤を必須成分とするエポキシ樹脂組成物を含浸・乾燥さ
せたプリプレグを用いてなることを特徴とする銅張積層
板。1. A copper-clad laminate in which a glass substrate is laminated with a plurality of prepregs impregnated with an epoxy resin composition and dried, and copper foil is laminated on at least one surface of the prepreg to integrally mold the glass nonwoven fabric, A component of (A) a phenoxy resin represented by the following general formula: (In the formula, X represents a hydrogen atom, a bromine atom, or a mixture of a hydrogen atom and a bromine atom, and n represents a polymer molecular species of an integer of 1 or more) (B) Epoxy resin,
A copper clad laminate comprising a prepreg impregnated and dried with an epoxy resin composition containing (C) a curing agent, (D) a curing accelerator, and (E) an inorganic filler as essential components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3909994A JPH07223294A (en) | 1994-02-14 | 1994-02-14 | Copper clad laminated sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3909994A JPH07223294A (en) | 1994-02-14 | 1994-02-14 | Copper clad laminated sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07223294A true JPH07223294A (en) | 1995-08-22 |
Family
ID=12543637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3909994A Pending JPH07223294A (en) | 1994-02-14 | 1994-02-14 | Copper clad laminated sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07223294A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018124215A1 (en) * | 2016-12-28 | 2018-07-05 | 新日鉄住金化学株式会社 | Metal/fiber-reinforced resin material composite body, method for producing same and bonding sheet |
-
1994
- 1994-02-14 JP JP3909994A patent/JPH07223294A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018124215A1 (en) * | 2016-12-28 | 2018-07-05 | 新日鉄住金化学株式会社 | Metal/fiber-reinforced resin material composite body, method for producing same and bonding sheet |
| JPWO2018124215A1 (en) * | 2016-12-28 | 2019-10-31 | 日鉄ケミカル＆マテリアル株式会社 | Metal-fiber reinforced resin material composite, its production method and adhesive sheet |
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