JP2001113627A - Production method for metal-clad laminated sheet - Google Patents
Production method for metal-clad laminated sheetInfo
- Publication number
- JP2001113627A JP2001113627A JP29371399A JP29371399A JP2001113627A JP 2001113627 A JP2001113627 A JP 2001113627A JP 29371399 A JP29371399 A JP 29371399A JP 29371399 A JP29371399 A JP 29371399A JP 2001113627 A JP2001113627 A JP 2001113627A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- aluminum hydroxide
- parts
- metal
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000011888 foil Substances 0.000 claims abstract description 3
- 239000003365 glass fiber Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000011342 resin composition Substances 0.000 claims abstract description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000011190 CEM-3 Substances 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 1
- 229920003986 novolac Polymers 0.000 description 16
- 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 12
- 239000011521 glass Substances 0.000 description 9
- 239000004745 nonwoven fabric Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 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 4
- 229930003836 cresol Natural products 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 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
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229910000679 solder Inorganic materials 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
- 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 101100407151 Arabidopsis thaliana PBL6 gene Proteins 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101001024616 Homo sapiens Neuroblastoma breakpoint family member 9 Proteins 0.000 description 1
- 102100037013 Neuroblastoma breakpoint family member 9 Human genes 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
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 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
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- -1 imidazole compound Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気・電子機器等
に用いられるプリント配線板用金属張り積層板に関し、
耐熱性に優れた金属張り積層板の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-clad laminate for a printed wiring board used for electric and electronic equipment, etc.
The present invention relates to a method for producing a metal-clad laminate excellent in heat resistance.
【０００２】[0002]
【従来の技術】民生用電子機器、産業用電子機器の小型
化、高性能化に伴い計測機器やコンピューター、テレ
ビ、エアコン等にはＦＲ−４積層板が多く使われていお
り、最近では表層以外にガラス不織布を用いたＣＥＭ−
３積層板も低コストで加工性に優れていることで生産量
は急増している。また、ＰＬ法の施行などにより耐トラ
ッキング特性や難燃性などの安全性に対する要求や材料
のノンハロゲン化の要求が多くなっている。これらに対
応するため耐トラッキング積層板やノンハロゲン積層板
が多く上市されており、耐トラッキング特性の向上やノ
ンハロゲン化を図るために充填剤の添加による方法が主
流となりつつあり、主に難燃効果のある水酸化アルミニ
ウムが多く使用されている。一方では環境問題による法
規制により鉛を使用しない高融点はんだに対応した高耐
熱性基板の要求が多くなっており、従来の水酸化アルミ
ニウムを多く含有している耐トラッキング積層板やノン
ハロゲン積層板では対応できなくなってきている。2. Description of the Related Art With the miniaturization and high performance of consumer electronic equipment and industrial electronic equipment, FR-4 laminates have been widely used for measuring instruments, computers, televisions, air conditioners, and the like. CEM using glass nonwoven fabric
The production volume of the three-layer laminate is also rapidly increasing due to its low cost and excellent workability. Further, due to the enforcement of the PL method and the like, there are increasing demands for safety such as tracking resistance and flame retardancy, and for non-halogenation of materials. In order to cope with these, tracking-resistant laminates and non-halogen laminates are on the market in many cases, and a method of adding a filler is becoming mainstream in order to improve tracking resistance characteristics and achieve halogen-free. Certain aluminum hydroxides are often used. On the other hand, due to environmental laws and regulations, there is a growing demand for high heat-resistant substrates that are compatible with high-melting-point solders that do not use lead, and in conventional tracking-resistant laminates and non-halogen laminates that contain a large amount of aluminum hydroxide. It can no longer be handled.
【０００３】[0003]
【発明が解決しようとする課題】本発明はかかる状況に
鑑みなされたもので、ＦＲ−４積層板やＣＥＭ−３積層
板の難燃性および耐トラッキング特性を低下させること
なく耐熱性を向上させた金属張り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 such circumstances, and has been made to improve the heat resistance without deteriorating the flame retardancy and tracking resistance of FR-4 laminates and CEM-3 laminates. To provide a metal-clad laminate.
【０００４】[0004]
【課題を解決するための手段】すなわち本発明は、
（ａ）エポキシ樹脂、（ｂ）硬化剤、(ｃ)促進剤、及び
(ｄ)Ａｌ2Ｏ3・ｎＨ2Ｏのｎの値が２.６〜２.９である
水酸化アルミニウムを必須成分とする熱硬化性樹脂組成
物をガラス繊維基材に含浸して得られたプリプレグを金
属箔と積層し加熱加圧成形することを特徴とする金属張
り積層板に関する。That is, the present invention provides:
(A) an epoxy resin, (b) a curing agent, (c) an accelerator, and
The (d) Al 2 O 3 · nH value of 2 O n is a thermosetting resin composition as an essential component of aluminum hydroxide is 2.6 to 2.9 obtained by impregnating a glass fiber base material The present invention relates to a metal-clad laminate characterized by laminating a prepreg with a metal foil and subjecting the prepreg to heat and pressure molding.
【０００５】[0005]
【発明の実施の形態】以下、本発明について詳細に説明
する。（ａ）のエポキシ樹脂ついては、分子内に２個以
上のエポキシ基を有するものであればよく、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、ビスフェノールＳ型エポキシ樹脂、ビスフ
ェノール型エポキシ樹脂、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、脂環
式エポキシ樹脂、グリシジルアミン型エポキシ樹脂、あ
るいはこれらを臭素化したものがある。なお、臭素化し
たエポキシ樹脂を用いない場合にはテトラブロモビスフ
ェノールＡやテトラフェニルホスフィン等を難燃剤とし
て添加することも可能である。また、これらのエポキシ
樹脂の分子量は特に制限はなく、何種類かを併用するこ
ともできる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The epoxy resin (a) may be any resin having two or more epoxy groups in the molecule. Examples thereof include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a bisphenol epoxy resin, There are phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, and brominated products thereof. When a brominated epoxy resin is not used, tetrabromobisphenol A, tetraphenylphosphine, or the like can be added as a flame retardant. Further, the molecular weight of these epoxy resins is not particularly limited, and several types can be used in combination.
【０００６】本発明で用いる（ｂ）の硬化剤については
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ノボラック等のノボラック類、無
水フタル酸などの酸無水物等いずれも使用可能で何種類
かを併用することもできる。これらのなかでもジシアン
ジアミドやフェノールノボラック類が好ましく使用され
る。エポキシ樹脂として、ノボラック型エポキシ樹脂、
例えば、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、ビスフェノールＡノボ
ラック型エポキシ樹脂などと、硬化剤として、ノボラッ
ク型フェノール樹脂、例えば、フェノールノボラック樹
脂、クレゾールノボラック樹脂、ビスフェノールＡノボ
ラック樹脂などとを組み合わせるのが硬化物の耐熱性が
優れることから好ましい。As the curing agent (b) used in the present invention, amines such as dicyandiamide, imidazoles and aromatic amines, novolaks such as phenol novolak, cresol novolak and bisphenol A novolak, and acid anhydrides such as phthalic anhydride Any of these can be used, and several types can be used in combination. Of these, dicyandiamide and phenol novolaks are preferably used. Novolak type epoxy resin as epoxy resin,
For example, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak type epoxy resin and the like are combined with a novolak type phenol resin as a curing agent, for example, a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin and the like. Is preferred because the heat resistance of the cured product is excellent.
【０００７】硬化剤は、エポキシ樹脂のエポキシ基１当
量に対して、硬化剤の官能基が０．８〜１．４当量の範
囲となるように配合するのが好ましく、０．８５〜１．
２当量の範囲となるように配合するのがより好ましい。
硬化剤の官能基が０．８当量未満の場合、及び１．４当
量を超えるいずれの場合も、ガラス転移点が低くなり、
吸湿しやすくなるため、はんだ耐熱性が低下する傾向に
ある。本発明に用いられる(ｃ)の促進剤についてはイミ
ダゾール化合物やアミン類等があるが特に制限はない。
促進剤はエポキシ樹脂エポキシ樹脂１００重量部に対し
て、０．０１〜３重量部が好ましく、０．１〜２重量部
を配合するのがより好ましい。The curing agent is preferably blended so that the functional group of the curing agent is in the range of 0.8 to 1.4 equivalents per equivalent of epoxy group of the epoxy resin.
It is more preferable to mix them in the range of 2 equivalents.
When the functional group of the curing agent is less than 0.8 equivalent, and in any case more than 1.4 equivalent, the glass transition point becomes low,
Since it becomes easy to absorb moisture, the solder heat resistance tends to decrease. The accelerator (c) used in the present invention includes an imidazole compound and an amine, but is not particularly limited.
The accelerator is preferably used in an amount of 0.01 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the epoxy resin.
【０００８】本発明に用いられる(ｄ)水酸化アルミニウ
ムについては、Ａｌ2Ｏ3・ｎＨ2Ｏのｎの値が２.６〜
２.９であり、形状・粒子径については特に制限はな
い。ｎの値が３.０である従来の水酸化アルミニウムで
はＤＳＣによる熱分解開始温度が約２２５℃であり高温
での耐熱性が劣る。また、２.６より小さい場合は難燃
性が低下する傾向がある。このような水酸化アルミニウ
ムは、独逸国のMARTINSWERK社からMARTINALという商品
名で入手可能である。ｎ数については試料を５００℃で
加熱してその灰分測定により求めることができる。上記
水酸化アルミニウムの配合量は、ガラス織布基材に含浸
する場合では、エポキシ樹脂及び硬化剤１００重量部に
対し７０重量部〜２００重量部、より好ましくは８０〜
１８０重量部配合するのが好ましい。７０重量部未満で
は耐トラッキング指数６００Ｖを満足することができ
ず、２００重量部を超えると塗工作業性の低下や成形性
が悪化する。また、従来の水酸化アルミニウムとの併用
も可能であり、耐熱性の要求レベルやコストに応じて配
合比率を変更することができる。ガラス不織布基材に含
浸させる場合では、エポキシ樹脂及び硬化剤１００重量
部に対し５０〜２２０重量部、より好ましくは８０〜２
００重量部配合することができ、必要に応じて他の充填
材(タルク、マイカ、クレーなど)との併用が可能であ
る。ガラス織布、ガラス不織布については通常使用され
ているものでよく特に限定されない。これらのエポキシ
樹脂、硬化剤、促進剤、水酸化アルミニウム(ｎ=２.６
〜２.９)の値を必須成分として含有するワニスをガラス
織布、不織布に含浸、乾燥しプリプレグを作製する。こ
のプリプレグを複数枚構成し、銅はくを上下に配し、加
熱・加圧しＦＲ−４積層板を製造することができる。ま
た上記のプリプレグとガラス不織布プリプレグの複数枚
の上下に構成したＣＥＭ−３積層板を製造することがで
きる。[0008] With regard to the aluminum hydroxide (d) used in the present invention, the value of n of Al 2 O 3 .nH 2 O is from 2.6 to 2.5.
2.9, and there is no particular limitation on the shape and particle diameter. In the case of conventional aluminum hydroxide having a value of n of 3.0, the thermal decomposition onset temperature by DSC is about 225 ° C., and the heat resistance at high temperatures is inferior. If it is smaller than 2.6, the flame retardancy tends to decrease. Such an aluminum hydroxide is available from MARTINSWERK, Germany, under the trade name MARTINAL. The number n can be determined by heating the sample at 500 ° C. and measuring its ash content. In the case of impregnating the glass woven fabric base material, the amount of the aluminum hydroxide is 70 parts by weight to 200 parts by weight, more preferably 80 parts by weight, based on 100 parts by weight of the epoxy resin and the curing agent.
It is preferable to mix 180 parts by weight. If the amount is less than 70 parts by weight, the tracking resistance index of 600 V cannot be satisfied, and if it exceeds 200 parts by weight, the coating workability decreases and the moldability deteriorates. Further, it can be used in combination with conventional aluminum hydroxide, and the mixing ratio can be changed according to the required level of heat resistance and cost. In the case of impregnating the glass nonwoven fabric base material, 50 to 220 parts by weight, more preferably 80 to 2 parts by weight, per 100 parts by weight of the epoxy resin and the curing agent.
It can be added in an amount of 00 parts by weight, and can be used in combination with other fillers (talc, mica, clay, etc.) as necessary. The glass woven fabric and the glass nonwoven fabric are commonly used and are not particularly limited. These epoxy resins, curing agents, accelerators, aluminum hydroxide (n = 2.6
A varnish containing the value of ~ 2.9) as an essential component is impregnated into a glass woven fabric or nonwoven fabric and dried to prepare a prepreg. A plurality of the prepregs are arranged, copper foils are arranged vertically and heated and pressed to produce an FR-4 laminate. In addition, a CEM-3 laminate composed of a plurality of the above prepregs and a glass nonwoven fabric prepreg can be manufactured.
【０００９】本発明は（ａ）エポキシ樹脂、（ｂ）硬化
剤、(ｃ)促進剤、及び(ｄ)Ａｌ2Ｏ3・ｎＨ2Ｏのｎの値
が２.６〜２.９である水酸化アルミニウムを必須成分と
することにより、ＦＲ−４積層板やＣＥＭ−３積層板の
難燃性および耐トラッキング特性を低下させることなく
耐熱性を向上させることができたものである。通常使用
されている水酸化アルミニウムのｎの値は３.０であ
り、熱分解開始温度が約２２５℃である。これにより、
この水酸化アルミニウムを多く使用した積層板の耐熱性
も低下する。そこで、水酸化アルミニウム(Ａｌ2Ｏ3・
ｎＨ2Ｏ)のｎの値を２.９以下にすることで熱分解開始
温度が２５７℃付近となり耐熱性が向上する。しかし、
ｎの値が２.６より低い場合は水分子が減少することに
より、難燃性や耐トラッキング性が低下する。したがっ
てｎの値が２.６〜２.９である水酸化アルミを配合する
ことで、難燃性、耐トラッキング性を低下させることな
く耐熱性に優れた金属張り積層板を提供することが可能
となった。In the present invention, the value of n of (a) epoxy resin, (b) curing agent, (c) accelerator, and (d) Al 2 O 3 .nH 2 O is 2.6 to 2.9. By using aluminum hydroxide as an essential component, the heat resistance of the FR-4 laminate and the CEM-3 laminate can be improved without lowering the flame retardancy and the tracking resistance. The value of n of commonly used aluminum hydroxide is 3.0, and the thermal decomposition onset temperature is about 225 ° C. This allows
The heat resistance of the laminate using a large amount of this aluminum hydroxide also decreases. Therefore, aluminum hydroxide (Al 2 O 3.
By setting the value of n in (nH 2 O) to 2.9 or less, the thermal decomposition starting temperature becomes about 257 ° C., and the heat resistance is improved. But,
When the value of n is lower than 2.6, the flame retardancy and the tracking resistance decrease due to a decrease in water molecules. Therefore, it is possible to provide a metal-clad laminate excellent in heat resistance without deteriorating flame retardancy and tracking resistance by blending aluminum hydroxide having a value of n of 2.6 to 2.9. It became.
【００１０】[0010]
【実施例】以下に本発明における実施例を示すが、本発
明はこれに限定されるものではない。なお、部は重量部
を示す。 (実施例１) 臭素化ビスフェノールＡ型エポキシ樹脂 ６０部 (エポキシ当量４８０、臭素含有量２１５％) ビスフェノールＡ型エポキシ樹脂 ４０部 (エポキシ当量４５０) ビスフェノールＡ型ノボラック樹脂 ２４.５部 (水酸基当量１１８) ２−エチル−４−メチルイミダゾール ０．２部 水酸化アルミニウム （MARTINSWERK社製） １５０部 （Ａｌ2Ｏ3・ｎＨ2Ｏのｎの値は２.７) 上記材料をメチルエチルケトンに溶解・混合し、不揮発
分７５％のワニスを作製した。このワニスをガラス織布
(厚み０．２ｍｍ、坪量２１０ｇ／ｍ2)に樹脂分が４６
％になるように含浸、乾燥し織布プリプレグＡを得た。
このプリプレグＡを８枚構成し、その両面に１８μｍの
銅はくを配し、１７０℃、９０分、４ＭＰａでプレス成
形し厚さ１.６ｍｍのＦＲ−４積層板を得た。 (実施例２)実施例１のワニスをガラス不織布(日本バイ
リーン製ＥＰＭ−４０７５)に樹脂分が９０％になるよ
うに含浸、乾燥し不織布プリプレグＢを得た。この不織
布プリプレグ３枚を中間層とし、上下に実施例１のプリ
プレグＡを配し、さらにその両面に１８μｍの銅はくを
重畳し、１７０℃、９０分、４ＭＰａでプレス成形し厚
さ１.６ｍｍのＣＥＭ−３積層板を得た。EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. Parts indicate parts by weight. (Example 1) Brominated bisphenol A type epoxy resin 60 parts (epoxy equivalent 480, bromine content 215%) bisphenol A type epoxy resin 40 parts (epoxy equivalent 450) bisphenol A type novolak resin 24.5 parts (hydroxyl equivalent 118 ) 2-Ethyl-4-methylimidazole 0.2 parts Aluminum hydroxide (MARTINSWERK) 150 parts (The value of n of Al 2 O 3 .nH 2 O is 2.7) The above materials are dissolved and mixed in methyl ethyl ketone. And a varnish having a nonvolatile content of 75%. This varnish is woven glass
(Thickness 0.2 mm, basis weight 210 g / m 2 )
% To obtain woven prepreg A.
Eight prepregs A were formed, copper foil of 18 μm was arranged on both surfaces thereof, and pressed at 170 ° C. for 90 minutes at 4 MPa to obtain a 1.6 mm-thick FR-4 laminate. (Example 2) The varnish of Example 1 was impregnated into a glass nonwoven fabric (EPM-4075 manufactured by Japan Vilene) so that the resin content was 90%, and dried to obtain a nonwoven fabric prepreg B. The three nonwoven fabric prepregs were used as an intermediate layer, the prepregs A of Example 1 were arranged on the upper and lower sides, and copper foil of 18 μm was further superimposed on both surfaces thereof. A 6 mm CEM-3 laminate was obtained.
【００１１】(比較例１)水酸化アルミニウムのｎ値が
３.０である標準水酸化アルミニウムを配合し、その他
は実施例１と同様にしてＦＲ−４積層板を得た。 (比較例２)水酸化アルミニウムのｎ値が２．４である水
酸化アルミニウムを配合し、その他は実施例１と同様に
してＦＲ−４積層板を得た。 (比較例３)水酸化アルミニウムのｎ値が３.０である標
準水酸化アルミニウムを配合し、その他は実施例２と同
様にしてＣＥＭ−３積層板を得た。 (比較例４)水酸化アルミニウムのｎ値が２．４である水
酸化アルミニウムを配合し、その他は実施例２と同様に
してＣＥＭ−３積層板を得た。試験結果を表１に示す。
なお、表１において耐トラッキング性はＩＥＣ．Ｐｕ
ｂ．１１２に準じ、難燃性はＵＬ−９４Ｖに準じて測定
した。Comparative Example 1 An FR-4 laminate was obtained in the same manner as in Example 1 except that a standard aluminum hydroxide having an aluminum hydroxide n value of 3.0 was blended. (Comparative Example 2) An FR-4 laminate was obtained in the same manner as in Example 1 except that aluminum hydroxide having an aluminum hydroxide n value of 2.4 was blended. (Comparative Example 3) A CEM-3 laminate was obtained in the same manner as in Example 2 except that a standard aluminum hydroxide having an aluminum hydroxide n value of 3.0 was blended. (Comparative Example 4) A CEM-3 laminate was obtained in the same manner as in Example 2 except that aluminum hydroxide in which the n value of aluminum hydroxide was 2.4 was blended. Table 1 shows the test results.
Incidentally, in Table 1, the tracking resistance was determined by IEC. Pu
b. According to 112, the flame retardancy was measured according to UL-94V.
【００１２】[0012]
【表１】 [Table 1]
【００１３】以上の結果より明らかなように、水酸化ア
ルミニウムのｎの値が３未満のものを用いることにより
耐トラッキング性、難燃性を低下させることなくＦＲ−
４積層板の耐熱性が向上している(実施例１、比較例
１、２)。また、ＣＥＭ−３積層板についても同様にｎ
の値を２.６〜２.９にした水酸化アルミニウムを配合す
ることにより、難燃性、耐トラッキング性を低下させる
ことなく耐熱性が向上している(実施例２、比較例３、
４)。As is evident from the above results, the use of aluminum hydroxide having an n value of less than 3 does not reduce the FR-resistance without lowering the tracking resistance and flame retardancy.
The heat resistance of the four laminates is improved (Example 1, Comparative Examples 1 and 2). Similarly, for the CEM-3 laminate, n
The heat resistance is improved without lowering the flame retardancy and tracking resistance by blending the aluminum hydroxide having the value of 2.6 to 2.9 (Example 2, Comparative Example 3,
4).
【００１４】[0014]
【発明の効果】本発明によれば、特定の水酸化アルミニ
ウムを用いることにより、ＦＲ−４積層板やＣＥＭ−３
積層板の難燃性および耐トラッキング特性を低下させる
ことなく耐熱性を向上させることが可能となった。According to the present invention, by using a specific aluminum hydroxide, an FR-4 laminate or a CEM-3 can be obtained.
The heat resistance can be improved without lowering the flame retardancy and tracking resistance of the laminate.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０５Ｋ 1/03 ６１０ Ｈ０５Ｋ 1/03 ６１０Ｌ (72)発明者 成沢 浩 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館事業所内 Ｆターム(参考） 4F072 AB09 AD23 AE01 AE02 AK14 AL13 4F100 AA19A AA19H AB01B AB33B AG00A AK53A AL05A BA02 BA10A BA10B CA02A DG01A DG15A DH01A EA061 EC051 EJ202 EJ422 EJ82A GB43 JJ03 4J002 CD001 DE148 DL009 FA049 FD146 FD157 GF00 GQ00──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H05K 1/03 610 H05K 1/03 610L (72) Inventor Hiroshi Narusawa 1500 Ogawa Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical 4F072 AB09 AD23 AE01 AE02 AK14 AL13 4F100 AA19A AA19H AB01B AB33B AG00A AK53A AL05A BA02 BA10A BA10B CA02A DG01A DG15A DH01A EA06J04 EJ202A EJ202A EJ202A EJ202A EJ422A EJ202A
Claims (1)
促進剤、及び(ｄ)Ａｌ2Ｏ3・ｎＨ2Ｏのｎの値が２．６
〜２．９である水酸化アルミニウムを必須成分とする熱
硬化性樹脂組成物をガラス繊維基材に含浸して得られた
プリプレグを金属箔と積層し加熱加圧成形することを特
徴とする金属張り積層板の製造方法。1. An epoxy resin, (b) a curing agent, and (c) an epoxy resin.
The value of n of the accelerator and (d) Al 2 O 3 .nH 2 O is 2.6.
A prepreg obtained by impregnating a glass fiber base material with a thermosetting resin composition containing aluminum hydroxide as an essential component of 2.9 to 2.9, and laminating with a metal foil, followed by heat and pressure molding. A method for manufacturing a laminated laminate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29371399A JP2001113627A (en) | 1999-10-15 | 1999-10-15 | Production method for metal-clad laminated sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29371399A JP2001113627A (en) | 1999-10-15 | 1999-10-15 | Production method for metal-clad laminated sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001113627A true JP2001113627A (en) | 2001-04-24 |
Family
ID=17798285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29371399A Pending JP2001113627A (en) | 1999-10-15 | 1999-10-15 | Production method for metal-clad laminated sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001113627A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005209692A (en) * | 2004-01-20 | 2005-08-04 | Hitachi Chem Co Ltd | Thermosetting resin composition, prepreg for printed-wiring board and metal-clad laminate |
-
1999
- 1999-10-15 JP JP29371399A patent/JP2001113627A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005209692A (en) * | 2004-01-20 | 2005-08-04 | Hitachi Chem Co Ltd | Thermosetting resin composition, prepreg for printed-wiring board and metal-clad laminate |
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