JPH04243186A - Laminated board for printed circuit - Google Patents

Laminated board for printed circuit

Info

Publication number
JPH04243186A
JPH04243186A JP1836991A JP1836991A JPH04243186A JP H04243186 A JPH04243186 A JP H04243186A JP 1836991 A JP1836991 A JP 1836991A JP 1836991 A JP1836991 A JP 1836991A JP H04243186 A JPH04243186 A JP H04243186A
Authority
JP
Japan
Prior art keywords
resin
printed circuit
glass
laminate
nonwoven fabric
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
Application number
JP1836991A
Other languages
Japanese (ja)
Inventor
Kiyoyuki Minamimura
清之 南村
Keiji Imasho
今庄 啓二
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanegafuchi Chemical Industry Co Ltd
Original Assignee
Kanegafuchi Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kanegafuchi Chemical Industry Co Ltd filed Critical Kanegafuchi Chemical Industry Co Ltd
Priority to JP1836991A priority Critical patent/JPH04243186A/en
Publication of JPH04243186A publication Critical patent/JPH04243186A/en
Pending legal-status Critical Current

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  • Laminated Bodies (AREA)

Abstract

PURPOSE:To obtain a laminated board for a printed circuit having excellent heat resistance and workability. CONSTITUTION:In a laminated board for a printed circuit of a composite structure in which a glass cloth is arranged on a surface layer and nonwoven fabric is arranged on an intermediate layer, a base material of the surface layer and/or a core layer is impregnated with radical curable unsaturated resin mixed with boehmite type aluminum hydroxide, and then, thermally cured to manufacture the laminated board.

Description

【発明の詳細な説明】[Detailed description of the invention]

【0001】(産業上の利用分野)本発明は耐熱性が優
れた印刷回路用積層板に関するものである。
(Industrial Application Field) The present invention relates to a printed circuit laminate having excellent heat resistance.

【0002】(従来技術)近年印刷回路用銅張積層板と
してガラス不織布を中間層としてガラス織布を表面基材
とした積層板(以下コンポジット積層板と省略する)が
多量に使用されるようになった。コンポジット積層板は
ガラス織布基材の積層板より経済的に安価で且つ、打ち
抜き孔あけ加工が可能な点で優れている。しかし、ガラ
ス織布基材積層板に比べて寸法安定性やスルーホールメ
ッキの信頼性が低いと評価されてきた。この特性を向上
させるために、樹脂中にギブサイト型水酸化アルミニウ
ム(以下、ギブサイトという)を充填させるのが一般的
である。ギブサイトは、200℃から500℃の範囲で
水を放出する。この時の吸熱量が大きいので、これを利
用して一般の合成樹脂では難燃性を持たせるために充填
剤として用いられている。しかし積層板は印刷回路及び
組み立て工程において高熱状態にさらされる頻度が高く
、例えば半田工程では通常260℃の半田浴に浸るので
、ギブサイトを充填剤として用いたコンポジット積層板
は浸漬時間が長くなるとギブサイトからの水の放出でふ
くれによる不良が発生する。
(Prior Art) In recent years, laminates (hereinafter abbreviated as composite laminates) that have a glass nonwoven fabric as an intermediate layer and a glass woven fabric as a surface material have been widely used as copper-clad laminates for printed circuits. became. Composite laminates are superior to laminates based on woven glass fabric in that they are economically cheaper and can be punched and punched. However, it has been evaluated as having lower dimensional stability and reliability in through-hole plating than glass woven fabric base laminates. In order to improve this property, it is common to fill the resin with gibbsite-type aluminum hydroxide (hereinafter referred to as gibbsite). Gibbsite releases water at temperatures ranging from 200°C to 500°C. Since the amount of heat absorbed at this time is large, it is used as a filler in general synthetic resins to make them flame retardant. However, laminates are frequently exposed to high heat conditions during printed circuit and assembly processes, for example, during the soldering process they are typically immersed in a 260°C solder bath. Defects occur due to blistering due to the release of water.

【0003】特開昭60−59795には、エポキシ樹
脂ガラス印刷回路用積層板においてベーマイト型水酸化
アルミニウム(以下ベーマイトと呼ぶ)を充填させるこ
とが提案されている。しかし、エポキシ樹脂ガラス印刷
回路用積層板は本発明のような不飽和樹脂を使用した印
刷回路用積層板に比べ、電気特性、耐トラッキング性の
点で劣る。また、エポキシ樹脂ガラス印刷回路用積層板
はバッチプロセスで製造することが一般的であり、生産
性の点で問題がある。
JP-A-60-59795 proposes filling an epoxy resin glass printed circuit laminate with boehmite-type aluminum hydroxide (hereinafter referred to as boehmite). However, the epoxy resin glass printed circuit laminate is inferior to the printed circuit laminate using an unsaturated resin as in the present invention in terms of electrical properties and tracking resistance. Furthermore, epoxy resin glass printed circuit laminates are generally manufactured by a batch process, which poses a problem in terms of productivity.

【0004】(発明が解決しようとする課題)本発明者
らは従来の不飽和樹脂にギブサイトを充填した印刷回路
用積層板の耐熱性不良の問題を解消することを目的とし
て鋭意検討を行った結果、アルミナ水和物と半田耐熱性
の関係を見いだした。印刷回路用積層板において、表面
層及び/またはコア層にベーマイト型水酸化アルミニウ
ムを充填することにより半田耐熱性を著しく向上させる
ことに成功した。
(Problems to be Solved by the Invention) The present inventors conducted extensive studies with the aim of solving the problem of poor heat resistance of conventional printed circuit laminates made of unsaturated resin filled with gibbsite. As a result, we found a relationship between alumina hydrate and soldering heat resistance. In a printed circuit laminate, we succeeded in significantly improving the soldering heat resistance by filling the surface layer and/or core layer with boehmite-type aluminum hydroxide.

【0005】(課題を解決するための手段)本発明は、
常温で液状で硬化に際し副反応生成物を発生しない硬化
性不飽和樹脂を表層のガラス織布および中間層の不織布
に含浸し、連続的に積層し、ついで硬化させてなる印刷
回路用積層板において、表面層及び/またはコア層がベ
ーマイト型水酸化アルミニウムを含有することを特徴と
する印刷回路用積層板に関するものである。
(Means for Solving the Problems) The present invention has the following features:
A laminate for printed circuits in which a curable unsaturated resin that is liquid at room temperature and does not generate side reaction products upon curing is impregnated into a glass woven fabric for the surface layer and a nonwoven fabric for the intermediate layer, which are laminated continuously and then cured. The present invention relates to a printed circuit laminate characterized in that the surface layer and/or the core layer contain boehmite-type aluminum hydroxide.

【0006】ベーマイトは樹脂に対して10〜200%
(重量%以下同じ)、好ましくは20〜200%含まれ
る。10%以下では半田耐熱の効果が小さく、200%
以上ではベーマイト混合時の樹脂粘度が高くなりすぎて
ガラス基材への含浸が困難となる。20%以上の場合は
、半田耐熱性向上効果がより確実なものとなる。この時
、ベーマイトの一部をギブサイトに置換して併用しても
よい。また、水酸化アルミニウム以外の無機充填剤(例
えばシリカ、タルク、炭酸カルシウム、チタン酸化物、
水酸化マグネシウム)を同時に用いることもできる。ベ
ーマイト単独又はベーマイトを含む無機充填剤の樹脂に
対する割合は、20%〜200%が好ましい。20%以
下では寸法安定性やスルホールメッキの信頼性が低下し
て好ましくない。200%以上では無機充填剤を樹脂に
混合したとき粘度が高くなり過ぎてガラス基材への含浸
が困難となる。
[0006] Boehmite accounts for 10 to 200% of the resin.
(the same applies below weight%), preferably 20 to 200%. If it is less than 10%, the effect of soldering heat resistance is small, and if it is 200%
If the resin is mixed with boehmite, the viscosity of the resin becomes too high, making it difficult to impregnate the glass substrate. When it is 20% or more, the effect of improving soldering heat resistance becomes more reliable. At this time, part of boehmite may be replaced with gibbsite and used in combination. Inorganic fillers other than aluminum hydroxide (such as silica, talc, calcium carbonate, titanium oxide,
Magnesium hydroxide) can also be used at the same time. The ratio of boehmite alone or an inorganic filler containing boehmite to the resin is preferably 20% to 200%. If it is less than 20%, the dimensional stability and the reliability of through-hole plating decrease, which is not preferable. If it is 200% or more, the viscosity becomes too high when the inorganic filler is mixed with the resin, making it difficult to impregnate the glass substrate.

【0007】この様な充填剤が樹脂中でいわゆるままこ
にならないで均一に分散し、ガラス基材に含浸させたと
きにも均一に分布するためには、充填剤の平均粒径が1
〜40μmであることが好ましい。充填剤の平均粒径が
40μmよりも大きい場合には、含浸時の沈澱等により
充填剤の分布が不均一になり易い。一方無機充填剤の粒
子の多くが1μmよりも小さい場合には、無機充填剤の
微粉末がままこの状態になりやすくやはり無機充填剤の
分布が不均一になる。
[0007] In order for such a filler to be uniformly dispersed in the resin without clumping, and also to be uniformly distributed when impregnated into a glass substrate, the average particle size of the filler must be 1.
It is preferable that it is 40 micrometers. When the average particle size of the filler is larger than 40 μm, the distribution of the filler tends to become uneven due to precipitation during impregnation. On the other hand, if most of the particles of the inorganic filler are smaller than 1 μm, the fine powder of the inorganic filler tends to remain in this state, resulting in uneven distribution of the inorganic filler.

【0008】また、本発明の積層板は、さきに本出願人
が特開昭55−4838、同56−98136等におい
て提案した連続法によって製造することが好ましい。ま
た、積層や硬化の際に加圧を行っても良い。これらの連
続法では、常温で液状で、硬化に際し揮発性副生成物を
発生しない硬化性不飽和樹脂を用いる。この様な不飽和
樹脂とは、硬化前樹脂がラジカル重合可能な二重結合不
飽和基を含み、該不飽和基のラジカル重合反応によって
硬化するものをいう。不飽和ポリエステルはその典型的
なものであるが、その他にもエポキシアクリレート樹脂
、ウレタンアクリレート樹脂、ジアリルフタレート樹脂
等がその例である。これらの樹脂は単独で用いても二つ
以上を混合して用いてもよい。本出願人の特開昭60−
215998に開示されている樹脂構成は印刷回路用積
層板として優れた特性を有しており、本発明でのよい樹
脂の例である。
The laminate of the present invention is preferably manufactured by a continuous method previously proposed by the applicant in JP-A-55-4838 and JP-A-56-98136. Further, pressure may be applied during lamination and curing. These continuous methods use curable unsaturated resins that are liquid at room temperature and do not generate volatile byproducts during curing. Such an unsaturated resin refers to one in which the resin before curing contains a radically polymerizable double bond unsaturated group and is cured by a radical polymerization reaction of the unsaturated group. Unsaturated polyester is a typical example, but other examples include epoxy acrylate resin, urethane acrylate resin, and diallyl phthalate resin. These resins may be used alone or in combination of two or more. Applicant's Japanese Unexamined Patent Publication No. 1986-
The resin composition disclosed in No. 215,998 has excellent properties as a printed circuit laminate and is an example of a good resin for use in the present invention.

【0009】硬化性樹脂は、その骨格へ結合したハロゲ
ン原子、特に臭素を含有することによって難燃化するこ
とが出来る。難燃化はハロゲンを含有しない樹脂へ添加
型のハロゲン型難燃剤を添加することによっても達成す
ることが出来る。
Curable resins can be rendered flame retardant by containing halogen atoms, particularly bromine, bonded to their skeletons. Flame retardancy can also be achieved by adding an additive halogen-type flame retardant to a halogen-free resin.

【0010】基材は表層にガラスクロス、中間ないしコ
ア層に不織布を使用する。ガラスクロスとは、通常太さ
9μm程度のガラスフィラメントを50〜800本集束
したヤーンを、朱子織り、平織り、目抜き平織り、綾織
りなどの各種の織り方で、縦、横に織り込んだ布の総称
である。不織布としては、太さ1〜20μmのガラス繊
維を水中に分散し、バインダーにアクリル樹脂、ポリビ
ニルアルコール、エポキシ樹脂、メラミン樹脂等を用い
て湿式で抄造した長尺のシート状のガラス不織布(ガラ
スペーパーとも言う)や、紙とガラス繊維からなるガラ
ス混抄紙、ポリエステル等の合成繊維、レーヨン、石綿
、岩綿などからなる不織布もある。CEM1を目的とす
る場合には中間基材が紙である場合もある。中間基材の
基材層は板厚に応じて1層もしくは数層とすることがで
きる。以下に、本発明の実施例および比較例(従来例)
を示す。
[0010] As the base material, a glass cloth is used for the surface layer, and a nonwoven fabric is used for the middle or core layer. Glass cloth is a cloth made by weaving yarns made of 50 to 800 glass filaments, usually about 9 μm thick, woven vertically and horizontally in various weaving methods such as satin weave, plain weave, open plain weave, and twill weave. It is a generic term. The non-woven fabric is a long sheet-shaped glass non-woven fabric (glass paper) made by dispersing glass fibers with a thickness of 1 to 20 μm in water and wet-forming the binder using acrylic resin, polyvinyl alcohol, epoxy resin, melamine resin, etc. There are also glass-mixed papers made of paper and glass fibers, synthetic fibers such as polyester, and non-woven fabrics made of rayon, asbestos, rock wool, etc. When the purpose is CEM1, the intermediate base material may be paper. The base material layer of the intermediate base material can be one layer or several layers depending on the plate thickness. Examples and comparative examples (conventional examples) of the present invention are shown below.
shows.

【0011】(実施例)上下最外層にガラスクロス(日
東紡  WE−18K)を配し、中間にガラス不織布3
層を配した両面銅張コンポジット積層板を連続法によっ
て製造した。基材をロールから連続的に繰り出し、並行
して搬送しながら、これらの基材に市販の不飽和ポリエ
ステル(武田薬品、ポリマール6311)100重量部
、ベンゾイルパーオキシド1重量部、ベーマイト型水酸
化アルミニウム(Al2O3・2.4H2O)80重量
部よりなる樹脂液を含浸し、含浸した基材を積層合体し
、両表面に銅箔をラミネートした後、トンネル型硬化炉
を連続的に通過させて、100℃で15分間、150℃
で10分間熱硬化させ、厚さ1.6mmの両面銅張積層
板を製造した。
(Example) Glass cloth (Nittobo WE-18K) was placed on the upper and lower outermost layers, and a glass nonwoven fabric 3 was placed in the middle.
Double-sided copper-clad composite laminates with layers were manufactured by continuous method. While the base materials are continuously fed out from the rolls and conveyed in parallel, 100 parts by weight of commercially available unsaturated polyester (Takeda Pharmaceutical, Polymer 6311), 1 part by weight of benzoyl peroxide, and boehmite type aluminum hydroxide are added to these base materials. (Al2O3.2.4H2O) was impregnated with a resin liquid consisting of 80 parts by weight, the impregnated base materials were laminated and combined, copper foil was laminated on both surfaces, and then continuously passed through a tunnel type curing furnace. ℃ for 15 minutes at 150℃
This was heat-cured for 10 minutes to produce a double-sided copper-clad laminate with a thickness of 1.6 mm.

【0012】(比較例)含浸樹脂液として市販の不飽和
ポリエステル(武田薬品、ポリマール6311)100
重量部、ベンゾイルパーオキシド1重量部、ギブサイト
型水酸化アルミニウム(Al2O3・3H2O) 80
重量部を使用する以外は、実施例と同様にして厚さ1.
6mmの両面銅張積層板を製造した。
(Comparative example) Commercially available unsaturated polyester (Takeda Pharmaceutical, Polymer 6311) 100
Part by weight, 1 part by weight of benzoyl peroxide, gibbsite type aluminum hydroxide (Al2O3.3H2O) 80
Thickness 1.
A 6 mm double-sided copper-clad laminate was manufactured.

【0013】以上の実施例及び比較例において、半田耐
熱性の測定結果を表1に示す。なお、寸法安定性、スル
ホールメッキの信頼性、電気絶縁性等も測定したが、実
施例と比較例の間に差は見られなかった。
[0013] Table 1 shows the measurement results of solder heat resistance in the above Examples and Comparative Examples. In addition, dimensional stability, reliability of through-hole plating, electrical insulation properties, etc. were also measured, but no difference was found between the example and the comparative example.

【表1】[Table 1]

【0014】(発明の効果)以上のように本発明の印刷
回路用積層板は積層板の半田耐熱性を著しく向上させた
積層板である。
(Effects of the Invention) As described above, the printed circuit laminate of the present invention is a laminate in which the solder heat resistance of the laminate is significantly improved.

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】常温で液状で硬化に際し副反応生成物を発
生しない硬化性不飽和樹脂を表層のガラス織布および中
間層の不織布に含浸し、連続的に積層し、ついで硬化さ
せてなる印刷回路用積層板において、表面層及び/また
はコア層がベーマイト型水酸化アルミニウムを含有する
ことを特徴とする印刷回路用積層板。
[Claim 1] Printing made by impregnating a surface layer glass woven fabric and an intermediate layer nonwoven fabric with a curable unsaturated resin that is liquid at room temperature and does not generate side reaction products upon curing, and then laminating them continuously and then curing them. A laminate for printed circuits, wherein the surface layer and/or the core layer contain boehmite-type aluminum hydroxide.
【請求項2】硬化性不飽和樹脂が不飽和ポリエステル樹
脂、エポキシアクリレート樹脂、ウレタンアクリレート
樹脂またはジアリルフタレート樹脂単独か、またはそれ
らの混合物である請求項1記載の印刷回路用積層板。
2. The laminate for printed circuits according to claim 1, wherein the curable unsaturated resin is an unsaturated polyester resin, an epoxy acrylate resin, a urethane acrylate resin, or a diallyl phthalate resin, or a mixture thereof.
【請求項3】ベーマイト型水酸化アルミニウムが樹脂に
対して10〜200重量%含有されていることを特徴と
する請求項1または請求項2に記載の印刷回路用積層板
3. The printed circuit laminate according to claim 1, wherein the boehmite type aluminum hydroxide is contained in an amount of 10 to 200% by weight based on the resin.
【請求項4】中間層の不織布がガラス不織布であること
を特徴とする請求項1ないし請求項3のいずれかに記載
の印刷回路用積層板。
4. The printed circuit laminate according to claim 1, wherein the nonwoven fabric of the intermediate layer is a glass nonwoven fabric.
JP1836991A 1991-01-17 1991-01-17 Laminated board for printed circuit Pending JPH04243186A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1836991A JPH04243186A (en) 1991-01-17 1991-01-17 Laminated board for printed circuit

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1836991A JPH04243186A (en) 1991-01-17 1991-01-17 Laminated board for printed circuit

Publications (1)

Publication Number Publication Date
JPH04243186A true JPH04243186A (en) 1992-08-31

Family

ID=11969794

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1836991A Pending JPH04243186A (en) 1991-01-17 1991-01-17 Laminated board for printed circuit

Country Status (1)

Country Link
JP (1) JPH04243186A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009142192A1 (en) * 2008-05-19 2009-11-26 パナソニック電工株式会社 Laminate, metal-foil-clad laminate, circuit board, and circuit board for led mounting
JP2010000774A (en) * 2008-05-19 2010-01-07 Panasonic Electric Works Co Ltd Laminate, prepreg, metal foil-clad laminate, circuit board, and circuit board for mounting led
JP2010254807A (en) * 2009-04-24 2010-11-11 Panasonic Electric Works Co Ltd Thermosetting resin composition, prepreg, composite laminate, metal-foil-clad laminate, circuit board, and circuit board for led mounting

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009142192A1 (en) * 2008-05-19 2009-11-26 パナソニック電工株式会社 Laminate, metal-foil-clad laminate, circuit board, and circuit board for led mounting
JP2010000774A (en) * 2008-05-19 2010-01-07 Panasonic Electric Works Co Ltd Laminate, prepreg, metal foil-clad laminate, circuit board, and circuit board for mounting led
JP2010254807A (en) * 2009-04-24 2010-11-11 Panasonic Electric Works Co Ltd Thermosetting resin composition, prepreg, composite laminate, metal-foil-clad laminate, circuit board, and circuit board for led mounting

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