JPH0381141A - Manufacture of metal foil clad laminated sheet - Google Patents
Manufacture of metal foil clad laminated sheetInfo
- Publication number
- JPH0381141A JPH0381141A JP21787489A JP21787489A JPH0381141A JP H0381141 A JPH0381141 A JP H0381141A JP 21787489 A JP21787489 A JP 21787489A JP 21787489 A JP21787489 A JP 21787489A JP H0381141 A JPH0381141 A JP H0381141A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- metal foil
- resin varnish
- dispersed
- aluminum hydroxide
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 12
- 239000002184 metal Substances 0.000 title claims abstract description 12
- 239000011888 foil Substances 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- 239000002966 varnish Substances 0.000 claims abstract description 43
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 26
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005011 phenolic resin Substances 0.000 claims abstract description 17
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 13
- 239000003063 flame retardant Substances 0.000 claims abstract description 12
- 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 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000000839 emulsion Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000004640 Melamine resin Substances 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000004080 punching Methods 0.000 abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002987 primer (paints) Substances 0.000 abstract 5
- 239000000123 paper Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002655 kraft paper Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 240000002834 Paulownia tomentosa Species 0.000 description 3
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000002023 wood 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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、紙基材のフェノール樹脂金属箔張り積Ｎ板の
製造法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing a paper-based phenolic resin metal foil laminated N board.
従来の技術
紙基材フェノール樹脂積層板に難燃性を付与させるため
には、フェノール樹脂にＢｒ系化合物、Ｐ系化合物、Ｎ
系化合物、二酸化アンチモン等を混合して使用していた
。Conventional technology In order to impart flame retardancy to paper-based phenolic resin laminates, it is necessary to add Br-based compounds, P-based compounds, and N to the phenolic resin.
A mixture of antimony-based compounds, antimony dioxide, etc. was used.
さらに、難燃性を向上させるため、プリプレグの製造段
階で、あらかじめ紙基材をフェノール樹脂初期縮合物、
メラミン樹脂初期縮合物（その単独あるいは混合物の水
／メタノール溶液で処理しく下塗り）、続いて上塗りで
前記のフェノール樹脂、Ｂｒ、 Ｐ、 Ｎ系化合物の混
合物を使用する方法もある。上塗りで使用するフェノー
ル樹脂としては、近年の積層板の打抜き温度の低下、打
抜き加工性の向上の要求から、多くは桐油変性フェノー
ル樹脂が用いられている。Furthermore, in order to improve flame retardancy, the paper base material is treated with a phenolic resin initial condensate in advance at the prepreg manufacturing stage.
There is also a method of using a melamine resin initial condensate (either alone or as a mixture thereof, treated with a water/methanol solution and undercoated), followed by a topcoat of a mixture of the above-mentioned phenolic resin, Br, P, N type compounds. As the phenolic resin used in the top coating, tung oil-modified phenolic resin is often used due to recent demands for lowering the punching temperature of laminates and improving punching workability.
従来の配合系においては、さらに打抜き温度を低下させ
るためには桐油変性フェノール樹脂の使用量を増加させ
る必要があるが難燃性は低下する。一方、難燃性を向上
させるために前記Ｂｒ系化合物、Ｐ系化合物等の使用量
を増加させると耐熱性、打抜き時の層間密着の低下を引
き起こすだけでなく、材料のコストアップにつながる。In the conventional compounding system, in order to further lower the punching temperature, it is necessary to increase the amount of tung oil-modified phenolic resin used, but the flame retardance decreases. On the other hand, increasing the amount of the Br-based compound, P-based compound, etc. used to improve flame retardance not only causes a decrease in heat resistance and interlayer adhesion during punching, but also leads to an increase in material cost.
また、二酸化アンチモンを含むと、印刷回路板製造工程
中で、めっき液を汚染するため使用できない。Furthermore, if it contains antimony dioxide, it cannot be used because it contaminates the plating solution during the printed circuit board manufacturing process.
発明が解決しようとする課題
従って、従来の配合系においては、打抜き性、耐熱性の
向上と難燃性の確保が矛盾する関係となり両立させる事
が非常に困難であった。Problems to be Solved by the Invention Therefore, in conventional compounding systems, improving punchability and heat resistance and ensuring flame retardancy are contradictory, and it has been extremely difficult to achieve both.
本発明の課題は、従来の配合系におけるこの様な問題点
を解決し、打抜き性耐熱性、難燃性を併せ備えた紙基材
フェノール樹脂金属箔張り積層板を提供することである
。The object of the present invention is to solve these problems in conventional compounding systems and to provide a paper-based phenolic resin metal foil-clad laminate that is punchable, heat resistant, and flame retardant.
課題を解決するための手段
本発明に係る方法は、丁塗りと上塗りの二段階で樹脂ワ
ニス塗工乾燥して得た紙基材のプリプレグを金属箔と共
に積層成形する方法において、次の点に特徴を有する。Means for Solving the Problems The method according to the present invention is a method of laminating and molding a prepreg of paper base material obtained by coating and drying a resin varnish in two stages of coating and top coating, together with metal foil, and has the following points. Has characteristics.
すなわち、下塗り樹脂ワニスとして、フェノール樹脂相
ＫＪＩ縮音物とメラミン樹脂初期縮合物の水／メタノー
ル溶液に水酸化アルミニウムを分散させたものを用いる
。また、上塗り樹脂ワニスとして、難燃剤を含む油変性
フェノール樹脂を用いる。That is, the undercoat resin varnish is prepared by dispersing aluminum hydroxide in a water/methanol solution of a phenolic resin phase KJI condensate and a melamine resin initial condensate. Furthermore, an oil-modified phenol resin containing a flame retardant is used as the top resin varnish.
上記下塗り樹脂ワニスは、水を分散媒とするエマルジョ
ンとしてもよい。The undercoat resin varnish may be an emulsion using water as a dispersion medium.
また、上記下塗り樹脂ワニスは、油変性フェノール樹脂
の水分散エマルジョンに水酸化アルミニウムを分散させ
たものでもよい。Further, the undercoat resin varnish may be one in which aluminum hydroxide is dispersed in a water-dispersed emulsion of an oil-modified phenol resin.
さらに、水酸化アルミニウムは粒径１μ以下が望ましい
。Furthermore, the particle size of aluminum hydroxide is preferably 1 μm or less.
作用
上塗り樹脂ワニスに配合して使用するＢｒ系、Ｐ系、Ｎ
系難燃剤は、油変性フェノール樹脂の持つ可撓性（打抜
き性）、層間密着性を阻害する方向に働らくため、打抜
き性向上のためには前記Ｕ燃剤の使用量を極力少なくし
なければならない。フェノール樹脂初′＃Ｊ４縮合物、
メラミン樹脂初期縮合物のいずれかあるいは混合物で紙
基材を下塗り処理することは、上塗りの油変性フェノー
ル樹脂に配合する難燃剤の使用量を減らしても難燃性を
保持する上で有効である。しかし、紙基材を下塗り処理
する段階で、さらに積極的な難燃効果を持つ水酸化アル
ミニウムを併用することで、上塗り樹脂に配合する従来
の難燃剤の量を減らして、打抜き性、耐熱性と難燃性を
併せ備えることが可能になる。Function: Br-based, P-based, N
Since flame retardants work in the direction of inhibiting the flexibility (punching properties) and interlayer adhesion of oil-modified phenolic resins, the amount of the U flame retardant used must be minimized in order to improve punching properties. No. Phenolic resin first'#J4 condensate,
Undercoating the paper base with one or a mixture of melamine resin initial condensates is effective in maintaining flame retardancy even if the amount of flame retardant used in the oil-modified phenolic resin topcoat is reduced. . However, by using aluminum hydroxide, which has a more aggressive flame retardant effect, in the stage of undercoating the paper base material, the amount of conventional flame retardant added to the top coat resin can be reduced, improving punchability and heat resistance. This makes it possible to have both flame retardancy and flame retardancy.
ここで、下塗り樹脂ワニスに水酸化アルミニウムを分散
させるのは、次の理由による。The reason why aluminum hydroxide is dispersed in the undercoat resin varnish is as follows.
すなわち、上塗り樹脂ワニスに水酸化アルニミウムを配
合して下塗り後の紙基材に塗工すると、水酸化アルミニ
ウムは基材中に入りこめない。従って、基材層と水酸化
アルミニウムの充填材層が分離し、また、上塗りで付着
させるべき樹脂分が水酸化アルミニウムの分だけ減るた
め、打抜き時の層間密着、表面に一体に接着した金属箔
のビール強度が低下してしまう。That is, when aluminum hydroxide is blended into the top resin varnish and applied to a paper base material after undercoating, the aluminum hydroxide cannot penetrate into the base material. Therefore, the base material layer and the aluminum hydroxide filler layer are separated, and the resin content to be attached in the top coat is reduced by the amount of aluminum hydroxide. The strength of the beer will decrease.
また、紙基材への１回の塗工でプリプレグを作る方法で
、その樹脂ワニスに水酸化アルミニウムを配合すること
も考えられるが、紙基材の樹脂ワニスによる処理が不十
分で積層板の電気特性が低下してしまう。In addition, it is possible to mix aluminum hydroxide into the resin varnish in a method of making prepreg with one coating on the paper base material, but the treatment of the paper base material with the resin varnish is insufficient and the laminate Electrical characteristics will deteriorate.
本発明に係る方法のように、下塗り樹脂ワニス中に水酸
化アルミニウムを配合することにより、初めて所期の目
的を達成てできるのである。The desired purpose can only be achieved by blending aluminum hydroxide into the undercoat resin varnish, as in the method of the present invention.
水酸化アル美ニウムの粒子径を１μ以下にすれば、樹脂
ワニスへの分散性が良好であり、粒子径が大きくなると
ワニス中で水酸化アルミニウムの沈降を生じやすくなる
。When the particle size of aluminum hydroxide is 1 μm or less, the dispersibility in the resin varnish is good, and when the particle size becomes large, aluminum hydroxide tends to settle in the varnish.
実施例
本発明に係る方法において、下塗り樹脂ワニスに配合す
る水酸化アルミニウムの量は、特に限定するものではな
いが、下塗り樹脂ワニスの樹脂固形分１００重部に対し
５〜２０重量部が実用上適当である。配合量が少ないと
十分な難燃効果が得られず、多過ぎるとワニス−・の分
散性が低下し製造上の支障をきたす惧れがある。Example In the method according to the present invention, the amount of aluminum hydroxide blended into the undercoat resin varnish is not particularly limited, but it is practically 5 to 20 parts by weight based on 100 parts by weight of resin solid content of the undercoat resin varnish. Appropriate. If the amount is too small, a sufficient flame retardant effect cannot be obtained, and if the amount is too large, the dispersibility of the varnish may decrease, causing problems in production.
実施例１
本発明に係る実施例で用いる樹脂組成物を次の様にして
得た。Example 1 A resin composition used in Examples according to the present invention was obtained as follows.
（１）桐油変性フェノール樹脂；三ツロフラスコに桐油
７２０ｇ、ｍ−クレゾール５８０ｇ、パラトルエンスル
ホン酸０．７４ ｇを投入し、８０°Ｃで１時間反応後
、フェノール５００ ｇ、８６％パラホルム４５０ｇ、
２５％アンモニア水３５ｇを投入し８０″Ｃで反応を続
け、反応生成物の１６０°Ｃ熱盤上での硬化時間が６分
になった時点で脱水濃縮し、後にメタノールを加え、樹
脂分５０重量％に調整した（Ａ樹脂）。(1) Tung oil-modified phenolic resin: Put 720 g of tung oil, 580 g of m-cresol, and 0.74 g of paratoluenesulfonic acid into a Mitsuro flask, and after reacting at 80°C for 1 hour, 500 g of phenol, 450 g of 86% paraform,
Add 35g of 25% ammonia water and continue the reaction at 80"C. When the reaction product hardens on a 160°C hot plate for 6 minutes, it is dehydrated and concentrated. Later, methanol is added to reduce the resin content to 50". It was adjusted to % by weight (Resin A).
（２）フェノール樹脂初期縮合物；三ツロフラスコにフ
ェノール７００ｇ、８６％パラホルム５０８ｇ、トリメ
チルアミン７２ｇを投入し、８０’Ｃで後
５時間反応、メタノールを加え、樹脂分を５０、／＼。(2) Phenol resin initial condensate; 700 g of phenol, 508 g of 86% paraform, and 72 g of trimethylamine were put into a Mitsuro flask, and the mixture was reacted at 80'C for another 5 hours. Methanol was added, and the resin content was reduced to 50/\.
重量％に調整した（Ｂ樹脂）。It was adjusted to % by weight (B resin).
Ｂ樹脂、Ｉ・リメチロールメラミン、粒子径０．５μの
水酸化アルミニウムを固形分重量比率で６０／３０／１
０となる様に混合し、これを水／メタノール−４０／６
０ （重量比）の比率の溶媒で濃度１５重量％に希釈し
て、下塗り樹脂ワニスを調整した。B resin, I-limethylol melamine, aluminum hydroxide with a particle size of 0.5μ in a solid weight ratio of 60/30/1
0, and mix this with water/methanol-40/6
An undercoat resin varnish was prepared by diluting it to a concentration of 15% by weight with a solvent having a ratio of 0 (weight ratio).
１１ミルスのクラフト紙を前記下塗り樹脂ワニスに浸漬
し、１６０°Ｃで１０分間乾燥後、Ａ樹脂、エポキシ当
ｌ ４００でＢｒ含有率４８％のＢｒ化エポキシ樹脂、
トリフェニルホス牛フェートを固形分重量比率で７０／
２０／１０となる径調整した上塗り樹脂ワニスを含浸、
乾燥させ、総樹脂滑５０重四％のプリプレグを得た。A kraft paper of 11 mils was immersed in the undercoat resin varnish, and after drying at 160°C for 10 minutes, A resin, a Br-containing epoxy resin with a Br content of 48% at an epoxy weight of 400,
Triphenylphosoxphate in a solid weight ratio of 70/
Impregnated with top coat resin varnish with diameter adjusted to 20/10,
It was dried to obtain a prepreg with a total resin content of 50% by weight.
３５μ厚９Ｍ Ｍ及び前記プリプレグ８枚を重ね、加熱
、加圧して１ 、６ ｍｍ厚の片面銅張り積層板を得た
。Eight sheets of the 35 μm thick 9M M prepreg and the above prepreg were stacked, heated and pressed to obtain a single-sided copper-clad laminate with a thickness of 1.6 mm.
実施例２
水１ｋｇにＨＬＢ＝１．６のノニオン性界面活性剤を５
ｇ、ヒドロキシエチルセルロースを２．５ｇ添加し、ホ
モミキサーで高速撹拌しながら、Ｂ樹脂１２０ｇ、
ｆ・リメチロールメラミン３５ｇを投入し、１時間撹拌
を続けて、水分Ｍ型のエマルジョンを得た。Example 2 5 nonionic surfactants with HLB=1.6 were added to 1 kg of water.
g, 2.5g of hydroxyethylcellulose was added, and while stirring at high speed with a homomixer, 120g of B resin,
35 g of f.limethylolmelamine was added, and stirring was continued for 1 hour to obtain an emulsion with moisture M type.
さらに、粒子径１μの水酸化アルミニウム１５ｇを分散
させ、下塗り樹脂ワニスを調整した。Furthermore, 15 g of aluminum hydroxide having a particle size of 1 μm was dispersed to prepare an undercoat resin varnish.
この下塗り樹脂ワニスを１■ミルスのクラフト紙に含浸
、乾燥し、以下、実施例１と同様にして１．６ｍｍ厚の
片面銅張り積層板を得た。This undercoat resin varnish was impregnated into 1 mils kraft paper and dried, followed by the same procedure as in Example 1 to obtain a single-sided copper-clad laminate having a thickness of 1.6 mm.
実施例３
水１ ｋｇにＨＬＢ＝１．０のノニオン性界面活性剤を
５ｇ、ヒドロキシエチルセルロースを２．５ｇ添加し、
ホモミキサーで高速撹拌しながら、Ａ樹脂４００ ｇを
投入し、１時間撹拌を続けて水分散型のエマルジョンを
得た。さらに、粒子径１μの水酸化アルミニウム１００
ｇを分散させ、下塗り樹脂ワニスを調整した。Example 3 5 g of nonionic surfactant with HLB = 1.0 and 2.5 g of hydroxyethyl cellulose were added to 1 kg of water,
While stirring at high speed with a homomixer, 400 g of resin A was added, and stirring was continued for 1 hour to obtain a water-dispersed emulsion. Furthermore, 100% aluminum hydroxide with a particle size of 1μ
g was dispersed to prepare an undercoat resin varnish.
この下塗り樹脂ワニスを１１ξルスのクラフト紙に含浸
、乾燥し、以下、実施例１と同様にして、１．６胴厚の
片面銅張り積層板を得た。This undercoat resin varnish was impregnated into 11ξ lus kraft paper and dried, followed by the same procedure as in Example 1 to obtain a single-sided copper-clad laminate having a body thickness of 1.6 mm.
実施例４
粒子径２μの水酸化アルミニウムを用いて実施例１と同
様にして１．６ｍｍ厚い片面銅張り積層板を得た。Example 4 A 1.6 mm thick single-sided copper-clad laminate was obtained in the same manner as in Example 1 using aluminum hydroxide having a particle size of 2 μm.
比較例１
Ｂ樹脂、トリメチロールメラミンを固形分重量比率で７
０／３０となる様に混合し、これを水／メタノールー４
０／６０重量比）の比率の溶媒で濃度１５重量％に希釈
して、下塗り樹脂ワニスを調整した。Comparative Example 1 B resin, trimethylol melamine at a solid content weight ratio of 7
Mix so that the ratio is 0/30, and mix this with water/methanol-4
An undercoat resin varnish was prepared by diluting it to a concentration of 15% by weight with a solvent having a ratio of 0/60 (weight ratio).
この下塗り樹脂ワニスを１１ミルスのクラフト紙に含浸
、乾燥し、以下、実施例１と同様にして１ 、６ ｍｍ
厚の片面銅張り積層板を得た。This undercoat resin varnish was impregnated into 11 mils kraft paper, dried, and then processed in the same manner as in Example 1 to form a 1.6 mm thick paper.
A thick single-sided copper-clad laminate was obtained.
比較例２
比較例１と同様に下塗り樹脂ワニスでクラフト紙を処理
した後、Ａ樹脂、エポキシ当量４００でＢｒ含有率４８
％のＢｒ化エポキシ樹脂、トリフェニルホスフェートを
固形分重量比率で５０／４０／１０となる様に調整した
上塗り樹脂ワニスを含浸、乾燥し、以下実施例１と同様
にして１．６閣厚の片面銅張り積層板を得た。Comparative Example 2 After treating kraft paper with an undercoat resin varnish in the same manner as Comparative Example 1, A resin was used, the epoxy equivalent was 400, and the Br content was 48.
% of Br-based epoxy resin and triphenyl phosphate in a solid content weight ratio of 50/40/10 was impregnated with a top coat resin varnish, dried, and then treated in the same manner as in Example 1 with a thickness of 1.6 mm. A single-sided copper-clad laminate was obtained.
比較例３
比較例１と同様に下塗りを行った後、Ａ樹脂、エポキシ
当量４００で１３ｒ含有率４８％のＢｒ化エポキシ樹脂
、トリフェニルホスフェート、粒子径１μの水酸化アル
ミニウムを固形分重量比率で６０／２０／１０／１０と
なる様調整した上塗り樹脂ワニスを含浸、乾燥し、総樹
脂量５０重量％のプリプレグを得た。Comparative Example 3 After undercoating in the same manner as in Comparative Example 1, A resin, a Brized epoxy resin with an epoxy equivalent of 400 and a 13r content of 48%, triphenyl phosphate, and aluminum hydroxide with a particle size of 1 μm were added in solid weight ratio. A top coat resin varnish adjusted to have a ratio of 60/20/10/10 was impregnated and dried to obtain a prepreg with a total resin content of 50% by weight.
以下、実施例１と同様にして１．６＋＋ｎｎ厚の片面銅
張り積層板を得た。Thereafter, in the same manner as in Example 1, a single-sided copper-clad laminate having a thickness of 1.6++ nn was obtained.
比較例４
Ａ樹脂、・エポキシ当量４００でＢｒ含有率４８％のＢ
ｒ化エポキシ樹脂、トリフェニルホスフェート、粒子径
１μの水酸化アルミニウムを固形分重量比率で５０／２
０／１０／２０となる様調整した樹脂ワニスを１１ξル
スのクラフト紙に含浸、乾燥し、総樹脂量５０重量％の
プリプレグを得た。Comparative Example 4 A resin, B with an epoxy equivalent of 400 and a Br content of 48%
R-treated epoxy resin, triphenyl phosphate, and aluminum hydroxide with a particle size of 1μ in a solid weight ratio of 50/2.
A resin varnish adjusted to have a ratio of 0/10/20 was impregnated into 11ξ lus kraft paper and dried to obtain a prepreg with a total resin content of 50% by weight.
以下、実施例１と同様にして１．６ｍｍ厚の片面銅張り
積層板を得た。Thereafter, in the same manner as in Example 1, a single-sided copper-clad laminate having a thickness of 1.6 mm was obtained.
実施例、比較例における各銅張り積層板の特性試験結果
を第１表に示す。また、下塗り樹脂ワニスに分散させた
水酸化アルミニウムの安定性についても、第１表に併せ
て示す。Table 1 shows the characteristics test results of each copper-clad laminate in Examples and Comparative Examples. Table 1 also shows the stability of aluminum hydroxide dispersed in the undercoat resin varnish.
発明の効果
第１表から明らかなように、本発明に係る方法では、難
燃剤の使用量を減らしながら（実施例は比較例に比べて
Ｂｒ化エポキシ樹脂の使用量が半分）、優れた難燃を確
保できる。Effects of the Invention As is clear from Table 1, the method according to the present invention achieves excellent flame retardancy while reducing the amount of flame retardant used (the amount of Brized epoxy resin used in the example is half compared to the comparative example). You can secure fuel.
そして、難燃剤の減少分だけ油変性フェノール樹脂の量
を増加でき、打抜き性を向上させることができる。Then, the amount of oil-modified phenol resin can be increased by the amount of decrease in flame retardant, and punching performance can be improved.
特に、下塗り樹脂ワニスをエマルジョンとすることによ
り（実施例２．３）絶縁特性がさらに良くなり、また、
下塗り樹脂ワニスを油変性フェノール樹脂のエマルジョ
ンとすれば、
広い打抜きの温度範囲で、
優れた打抜き
性を保持させることができる。In particular, by using an emulsion as the undercoat resin varnish (Example 2.3), the insulation properties are further improved, and
If the undercoat resin varnish is an emulsion of oil-modified phenolic resin, excellent punching properties can be maintained over a wide punching temperature range.
特許出廓人 新神戸電機株式会社 代表取締役 刀ηズ 木 七夕patent distributor Shin-Kobe Electric Co., Ltd. CEO Katana η's wood Tanabata
Claims (1)
て得た紙基材のプリプレグを金属箔と共に積層成形する
方法において、 下塗り樹脂ワニスがフェノール樹脂初期縮合物とメラミ
ン樹脂初期縮合物の水／メタノール溶液に水酸化アルミ
ニウムを分散させたものであり、 上塗り樹脂ワニスが難燃剤を含む油変性フェノール樹脂
ワニスであることを特徴とする金属箔張り積層板の製造
法。 ２、水酸化アルミニウムを分散させる下塗り樹脂ワニス
がフェノール樹脂初期縮合物とメラミン樹脂初期縮合物
を混合した水分散エマルジョンである請求項１記載の金
属箔張り積層板の製造法。 ３、水酸化アルミニウムを分散させる下塗り樹脂ワニス
が油変性フェノール樹脂の水分散エマルジョンである。 請求項１記載の金属箔張り積層板の製造法。 ４、水酸化アルミニウムの粒径が１μ以下である請求項
１〜３のいずれか１項記載の金属箔張り積層板の製造法
。[Claims] 1. In a method of laminating and molding a prepreg of a paper base material obtained by coating and drying a resin varnish in two stages of undercoating and topcoating, together with metal foil, the undercoat resin varnish is an initial condensate of a phenolic resin. A method for producing a metal foil-clad laminate, characterized in that aluminum hydroxide is dispersed in a water/methanol solution of a melamine resin initial condensate, and the top resin varnish is an oil-modified phenolic resin varnish containing a flame retardant. . 2. The method for producing a metal foil-clad laminate according to claim 1, wherein the undercoat resin varnish in which aluminum hydroxide is dispersed is a water-dispersed emulsion containing a mixture of a phenolic resin initial condensate and a melamine resin initial condensate. 3. The undercoat resin varnish in which aluminum hydroxide is dispersed is a water-dispersed emulsion of oil-modified phenolic resin. A method for producing a metal foil-clad laminate according to claim 1. 4. The method for producing a metal foil-clad laminate according to any one of claims 1 to 3, wherein the particle size of the aluminum hydroxide is 1 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21787489A JPH0381141A (en) | 1989-08-24 | 1989-08-24 | Manufacture of metal foil clad laminated sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21787489A JPH0381141A (en) | 1989-08-24 | 1989-08-24 | Manufacture of metal foil clad laminated sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0381141A true JPH0381141A (en) | 1991-04-05 |
Family
ID=16711125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21787489A Pending JPH0381141A (en) | 1989-08-24 | 1989-08-24 | Manufacture of metal foil clad laminated sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0381141A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8048486B2 (en) * | 2005-09-15 | 2011-11-01 | Rutgers, The State University Of New Jersey | Flame-retardant coating |
-
1989
- 1989-08-24 JP JP21787489A patent/JPH0381141A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8048486B2 (en) * | 2005-09-15 | 2011-11-01 | Rutgers, The State University Of New Jersey | Flame-retardant coating |
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