JP3317575B2 - Manufacturing method of laminated board - Google Patents
Manufacturing method of laminated boardInfo
- Publication number
- JP3317575B2 JP3317575B2 JP08517394A JP8517394A JP3317575B2 JP 3317575 B2 JP3317575 B2 JP 3317575B2 JP 08517394 A JP08517394 A JP 08517394A JP 8517394 A JP8517394 A JP 8517394A JP 3317575 B2 JP3317575 B2 JP 3317575B2
- Authority
- JP
- Japan
- Prior art keywords
- phenol resin
- resin
- parts
- melamine
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気用積層板の製造方
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing an electric laminate.
【０００２】[0002]
【従来の技術】民生用プリント配線板の高密度化、表面
実装化に伴い、積層板はリフロー工程はんだディップ工
程での耐熱性、高温での引きはがし強さの改良要求があ
る。また、電子機器の多機能化及び高信頼性化等によ
り、紙基材を用いた金属張積層板の銀ペーストスルーホ
ール化、銅ペーストスルーホール化等が進み、高信頼性
が要求されている。また、安全の面から、積層板の難燃
性の要求が一段と厳しくなっており、規格も整備され、
その規制は強化されている。2. Description of the Related Art As densities and surface mounting of printed wiring boards for consumer use have increased, there has been a demand for improved heat resistance of a laminated board in a reflow soldering step and peeling strength at a high temperature. In addition, due to the multifunctionality and high reliability of electronic devices, metal paste laminates using paper base materials are being made into silver paste through holes, copper paste through holes, etc., and high reliability is required. . In addition, from the viewpoint of safety, the demand for flame retardancy of laminated boards has become more severe, standards have been established,
Its regulations have been tightened.
【０００３】金属張積層板は、基材としてクラフト紙、
リンター紙などの紙を、また、樹脂としてフェノール樹
脂、メラミン樹脂、不飽和ポリエステル樹脂などを用い
ている。銅はくは、通常接着剤付き銅はくが用いられて
いる。樹脂としては、特に、打抜加工性を良好とするた
め、乾性油変性フェノール樹脂を用いることが多い。フ
ェノール樹脂用フェノールとしては、フェノール、メタ
クレゾール、パラクレゾール、オルソクレゾール、イソ
プロピルフェノール、パラターシャリブチルフェノー
ル、パライソプロペニルフェノールオリゴマー、ノニル
フェノール、ビスフェノールＡなど、乾性油としては、
桐油、脱水ヒマシ油、オイチシカ油などを用いている。[0003] Metal-clad laminates are made of kraft paper,
Paper such as linter paper is used, and phenol resin, melamine resin, unsaturated polyester resin and the like are used as the resin. As the copper foil, a copper foil with an adhesive is usually used. In particular, a dry oil-modified phenol resin is often used as the resin in order to improve the punching workability. Phenols for phenolic resins include phenol, meta-cresol, para-cresol, ortho-cresol, isopropylphenol, para-tert-butylphenol, para-isopropenylphenol oligomer, nonylphenol, bisphenol A, etc.
It uses tung oil, dehydrated castor oil, and deer oil.
【０００４】また、リン酸エステルのようなリン系化合
物、ブロム化フェノールやブロム化エポキシ化合物のよ
うなブロム系化合物、メラミン化合物やトリアジン化合
物のような窒素系化合物又はび三酸化アンチモンのよう
な無機化合物を単独又は混合して熱硬化性樹脂に添加し
て難燃化している。紙基材に水溶性メラミン樹脂を含浸
したあと、疎水性樹脂を含浸することは、古くから知ら
れている（特公昭３８−１３７８１号公報参照）。紙基
材に水溶性フェノール樹脂を含浸したあと、難燃性フェ
ノール樹脂を含浸して耐金属マイグレーション性をよく
することも知られている（特公平２−１９７８０号公報
参照）。Further, phosphorus compounds such as phosphate esters, bromo compounds such as brominated phenol and brominated epoxy compounds, nitrogen compounds such as melamine compounds and triazine compounds, and inorganic compounds such as antimony trioxide. The compounds are used alone or as a mixture and added to a thermosetting resin to make it flame-retardant. It has long been known to impregnate a paper base with a water-soluble melamine resin and then impregnate a hydrophobic resin (see Japanese Patent Publication No. 38-137981). It is also known that a paper base material is impregnated with a water-soluble phenol resin and then impregnated with a flame-retardant phenol resin to improve the metal migration resistance (see Japanese Patent Publication No. 21980/1990).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、紙基材
を水溶性メラミン樹脂で処理すると耐熱性、打抜加工性
は向上するが、耐金属マイグレーション性引きはがし強
さが悪くなる。紙基材に水溶性フェノール樹脂を含浸し
たあと、難燃性フェノール樹脂を含浸する方法では、耐
金属マイグレーション性は向上するが、難燃性や耐熱性
が向上しない。このように、耐金属マイグレーション
性、耐燃性、耐熱性、引きはがし強さ及び打抜加工性を
同じに満足する方法は見出されていない。本発明は、耐
燃性、耐銀マイグレーション性、耐熱性、引きはがし強
さ及び打抜加工性に優れる金属張積層板を得ることがで
きる製造方法を提供することを目的とする。However, when a paper substrate is treated with a water-soluble melamine resin, heat resistance and punching workability are improved, but the metal migration resistance peeling strength is deteriorated. In a method of impregnating a paper base material with a water-soluble phenol resin and then impregnating a flame-retardant phenol resin, the metal migration resistance is improved, but the flame retardancy and heat resistance are not improved. As described above, no method has been found which equally satisfies the metal migration resistance, the flame resistance, the heat resistance, the peeling strength and the punching workability. An object of the present invention is to provide a manufacturing method capable of obtaining a metal-clad laminate excellent in flame resistance, silver migration resistance, heat resistance, peeling strength and punching workability.
【０００６】[0006]
【課題を解決するための手段】本発明は、紙基材にメラ
ミン樹脂で変性した水溶性フェノール樹脂ワニスを含浸
乾燥し、次に、乾性油で変性したフェノール樹脂にメラ
ミン樹脂で変性した水溶性フェノール樹脂を配合したワ
ニスを含浸乾燥して得られたプリプレグを所定枚数重ね
て加熱加圧することを特徴とする積層板の製造方法であ
る。According to the present invention, a paper base material is impregnated with a water-soluble phenol resin varnish modified with a melamine resin and dried, and then a phenol resin modified with a drying oil is added to a water-soluble phenol resin modified with a melamine resin. A method for producing a laminated board, characterized in that a predetermined number of prepregs obtained by impregnating and drying a varnish containing a phenol resin are stacked and heated and pressed.
【０００７】本発明において、メラミン樹脂変性フェノ
ール樹脂は、メラミン樹脂をフェノール樹脂に反応させ
たもののほか、メラミン樹脂をフェノール樹脂に混合し
たものも含む。乾性油変性フェノール樹脂１００重量部
に対し、前記メラミン変性フェノール樹脂は３〜２０重
量部が好ましい。３重量部未満であると効果が少なく、
２０重量部以上では、ワニスの相溶性、打抜加工性が低
下する問題がある。In the present invention, the melamine resin-modified phenol resin includes not only a melamine resin reacted with a phenol resin but also a melamine resin mixed with a phenol resin. The melamine-modified phenol resin is preferably 3 to 20 parts by weight based on 100 parts by weight of the drying oil-modified phenol resin. Less than 3 parts by weight has little effect,
If the content is more than 20 parts by weight, there is a problem that the compatibility of the varnish and the punching workability decrease.
【０００８】[0008]
【作用】乾性油変性フェノール樹脂にメラミン樹脂で変
性した水溶性フェノール樹脂を配合することで、紙基材
に対する親和性が改善され、樹脂と基材との密着性が向
上し、耐金属マイグレーション性、打抜加工性が改良さ
れる。また、メラミン変性フェノール樹脂は難燃効果が
あり、かつ、乾性油変性フェノール樹脂や接着剤付銅は
くに用い樹脂との相溶性が良いため、難燃性、耐熱性、
引きはがし強さが改良される。[Function] By blending a water-soluble phenol resin modified with a melamine resin with a dry oil-modified phenol resin, the affinity for the paper substrate is improved, the adhesion between the resin and the substrate is improved, and the metal migration resistance is improved. In addition, the punching processability is improved. In addition, melamine-modified phenolic resin has a flame-retardant effect, and because it has good compatibility with resin used for drying oil-modified phenolic resin and copper foil with adhesive, flame retardancy, heat resistance,
Peeling strength is improved.
【０００９】[0009]
実施例１ メラミン量１８重量％のメラミン樹脂変性フェノール樹
脂を、クラフト紙に付着量１７〜２０％になるように含
浸乾燥し、さらに、桐油量３５重量％の桐油変性フェノ
ール樹脂１００部（重量部、以下同じ）に、メラミン量
１８重量％のメラミン樹脂変性フェノール樹脂５部、ト
リフェニルホスフェイト３０部、テトラブロモビスフェ
ノールＡジグリシジルエーテル２０部を配合したワニス
を、樹脂付着量が５０〜５４％になるように含浸乾燥し
プリプレグを得た。このプリプレグ８枚を重ね、その両
面に接着剤付き銅はく２枚を重ね、加熱加圧して厚さ
１．６ｍｍの両面銅張積層板を得た。Example 1 A melamine resin-modified phenol resin having a melamine content of 18% by weight was impregnated and dried on kraft paper so as to have an adhesion amount of 17 to 20%, and 100 parts of a tung oil-modified phenol resin having a tung oil amount of 35% by weight (parts by weight) A varnish prepared by mixing 5 parts of a melamine resin-modified phenol resin having 18% by weight of melamine, 30 parts of triphenyl phosphate, and 20 parts of tetrabromobisphenol A diglycidyl ether was used. And dried to obtain a prepreg. Eight sheets of this prepreg were stacked, and two sheets of copper foil with an adhesive were stacked on both sides thereof, and heated and pressed to obtain a double-sided copper-clad laminate having a thickness of 1.6 mm.
【００１０】実施例２ メラミン量１８重量％のメラミン樹脂変性フェノール樹
脂を、クラフト紙に付着量１７〜２０％になるように含
浸乾燥し、さらに、桐油量３５重量％の桐油変性フェノ
ール樹脂１００部（重量部、以下同じ）に、メラミン量
１８重量％のメラミン樹脂変性フェノール樹脂１２部、
トリフェニルホスフェイト３０部、テトラブロモビスフ
ェノールＡジグリシジルエーテル２０部を配合したワニ
スを、樹脂付着量が５０〜５４％になるように含浸乾燥
しプリプレグを得た。このプリプレグ８枚を重ね、その
両面に接着剤付き銅はく２枚を重ね、加熱加圧して厚さ
１．６ｍｍの両面銅張積層板を得た。EXAMPLE 2 A melamine resin-modified phenol resin having a melamine content of 18% by weight was impregnated and dried on kraft paper so as to have an adhesion amount of 17 to 20%, and then 100 parts of a tung oil-modified phenol resin having a tung oil content of 35% by weight. (Parts by weight, hereinafter the same), 12 parts of a melamine resin-modified phenol resin having a melamine content of 18% by weight,
A varnish containing 30 parts of triphenyl phosphate and 20 parts of tetrabromobisphenol A diglycidyl ether was impregnated and dried so that the resin adhesion amount was 50 to 54%, to obtain a prepreg. Eight sheets of this prepreg were stacked, and two sheets of copper foil with an adhesive were stacked on both sides thereof, and heated and pressed to obtain a double-sided copper-clad laminate having a thickness of 1.6 mm.
【００１１】実施例３ メラミン量１８重量％のメラミン樹脂変性フェノール樹
脂を、クラフト紙に付着量１７〜２０％になるように含
浸乾燥し、さらに、桐油量３５重量％の桐油変性フェノ
ール樹脂１００部（重量部、以下同じ）に、メラミン量
１８重量％のメラミン樹脂変性フェノール樹脂２０部、
トリフェニルホスフェイト３０部、テトラブロモビスフ
ェノールＡジグリシジルエーテル２０部を配合したワニ
スを、樹脂付着量が５０〜５４％になるように含浸乾燥
しプリプレグを得た。このプリプレグ８枚を重ね、その
両面に接着剤付き銅はく２枚を重ね、加熱加圧して厚さ
１．６ｍｍの両面銅張積層板を得た。Example 3 A melamine resin-modified phenol resin having a melamine content of 18% by weight was impregnated and dried on kraft paper so as to have an adhesion amount of 17 to 20%, and then 100 parts of a tung oil-modified phenol resin having a tung oil content of 35% by weight. (Parts by weight, hereinafter the same), 20 parts of a melamine resin-modified phenol resin having a melamine content of 18% by weight,
A varnish containing 30 parts of triphenyl phosphate and 20 parts of tetrabromobisphenol A diglycidyl ether was impregnated and dried so that the resin adhesion amount was 50 to 54%, to obtain a prepreg. Eight sheets of this prepreg were stacked, and two sheets of copper foil with an adhesive were stacked on both sides thereof, and heated and pressed to obtain a double-sided copper-clad laminate having a thickness of 1.6 mm.
【００１２】比較例 メラミン量１８重量％のメラミン樹脂変性フェノール樹
脂を、クラフト紙に付着量１７〜２０％になるように含
浸乾燥し、さらに、桐油量３５重量％の桐油変性フェノ
ール樹脂１００部（重量部、以下同じ）に、トリフェニ
ルホスフェイト３０部、テトラブロモビスフェノールＡ
ジグリシジルエーテル２０部を配合したワニスを、樹脂
付着量が５０〜５４％になるように含浸乾燥しプリプレ
グを得た。このプリプレグ８枚を重ね、その両面に接着
剤付き銅はく２枚を重ね、加熱加圧して厚さ１．６ｍｍ
の両面銅張積層板を得た。Comparative Example A melamine resin-modified phenol resin having a melamine content of 18% by weight was impregnated and dried on kraft paper so as to have an adhesion amount of 17 to 20%, and 100 parts of a tung oil-modified phenol resin having a tung oil content of 35% by weight ( Parts by weight, hereinafter the same), 30 parts of triphenyl phosphate, tetrabromobisphenol A
A varnish containing 20 parts of diglycidyl ether was impregnated and dried so that the resin adhesion amount was 50 to 54% to obtain a prepreg. Eight sheets of this prepreg are stacked, two sheets of copper foil with an adhesive are stacked on both sides thereof, and heated and pressed to a thickness of 1.6 mm.
Was obtained.
【００１３】以上で得られた両面銅張積層板について、
耐燃性、耐銀マイグレーション性、はんだ耐熱性、打抜
き加工性及び銅はく引きはがし強さを調べた。その結果
を表１に示す。Regarding the double-sided copper-clad laminate obtained above,
Flame resistance, silver migration resistance, solder heat resistance, punching workability, and copper peeling strength were examined. Table 1 shows the results.
【００１４】[0014]
【表１】 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 項目 実施例１ 実施例２ 実施例３ 比較例 ────────────────────────────────── 耐燃性 平均 １．７ １．５ ０．９ ２．５ （秒） 出現範囲 ０〜４ ０〜３ ０〜２ ４〜１３ ────────────────────────────────── 耐銀マイグレーション性 １．３ ２．８ ４．０ ０．５ （×109 Ω） ────────────────────────────────── はんだ耐熱性（秒） ２８ ３２ ３５ ２０ ────────────────────────────────── 打抜加工性 良好 良好 良好 不良 ────────────────────────────────── 引きはがし強さ ６．４ ６．９ ７．４ ５．４ （Ｎ／ｃｍ） ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━[Table 1] Item Example 1 Example 2 Example 3 Comparative Example燃 Flame resistance Average 1.7 1.5 0.9 2.5 ( Seconds) Appearance range 0-40 0-30 0-24 13 Silver migration resistance 1.3 2.8 4.0 0.5 (× 10 9 Ω) ──────────────────────────── ────── Solder heat resistance (second) 28 32 35 20 ────────────────────────────────── Punching workability Good Good Good Bad ────────────────────────────────── Peeling strength 6.4 6.9 7.4 5.4 (N / cm) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━
【００１５】なお、これらの試験法は次の通りである。 耐燃性（ＵＬ９４）：銅はくをエッチングで全面除去し
た試験片を垂直に保持し、下端からバーナーの炎を１０
秒間触れさせて離し、消炎するまでの時間を測定、消炎
後再度１０秒間触れさせて離し、消炎するまでの時間を
測定。試験片５個について、測定値計１０個の平均値。
出現範囲とは、各測定値の最小と最大を意味する。 はんだ耐熱性（ＪＩＳ−Ｃ−６４８１）：２６０℃に加
熱されたはんだ槽に試験片を浮かべ、ふくれを生ずるま
での時間を測定。 引きはがし強さ（ＪＩＳ−Ｃ−６４８１）：エッチング
により幅１０ｍｍ、長さ１００ｍｍのパターンを形成
し、１５０℃に加熱した状態で、銅はくを９０度方向に
毎分５０ｍｍの速さで引張り、その加重を測定。 耐銀マイグレーション性：穴間ピッチ２．０ｍｍ、ラン
ド径１．５ｍｍ、穴径０．７ｍｍ、１００穴連続２回路
の銀マイグレーションテストパターンに、相対湿度９０
％ＲＨ、温度４０℃で直流５０Ｖを２０００時間印加し
た後の回路間絶縁抵抗を測定。 打抜加工性：穴間ピッチ１．７８ｍｍ、穴径０．７ｍｍ
で穴あけしたときの穴間クラックを評価する。The test methods are as follows. Flame resistance (UL94): The test piece from which the copper foil was completely removed by etching was held vertically, and the burner flame was fired from the lower end by 10 times.
Touch and release for 2 seconds and measure the time to extinguish the flame. After extinguishing, touch and release again for 10 seconds and measure the time to extinguish the flame. Average value of 10 test value meters for 5 test pieces.
The appearance range means the minimum and maximum of each measured value. Solder heat resistance (JIS-C-6481): A test piece was floated in a solder bath heated to 260 ° C., and the time until blistering was measured. Peel strength (JIS-C-6481): A pattern having a width of 10 mm and a length of 100 mm is formed by etching, and while being heated to 150 ° C., a copper foil is pulled in a 90 ° direction at a speed of 50 mm / min. , Measure its weight. Silver migration resistance: 2.0 mm pitch between holes, 1.5 mm land diameter, 0.7 mm hole diameter, a 100-hole continuous two-circuit silver migration test pattern with a relative humidity of 90
Measure the insulation resistance between circuits after applying DC 50V for 2000 hours at% RH and temperature of 40 ° C. Punching workability: hole pitch 1.78 mm, hole diameter 0.7 mm
Evaluate the crack between holes when drilling with.
【００１６】[0016]
【発明の効果】本発明によれば、耐銀マイグレーション
性、耐熱性、耐燃性、引きはがし強さ及び打抜き加工性
ともに優れた積層板を得ることができる。According to the present invention, a laminate having excellent silver migration resistance, heat resistance, flame resistance, peeling strength and punching workability can be obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−38789（ＪＰ，Ａ) 特開 昭60−210639（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 1/00 - 35/00 B29B 11/16 B29B 15/08 - 15/14 C08J 5/04 - 5/10 C08J 5/24 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-38789 (JP, A) JP-A-60-210639 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B32B 1/00-35/00 B29B 11/16 B29B 15/08-15/14 C08J 5/04-5/10 C08J 5/24
Claims (2)
フェノール樹脂ワニスを含浸乾燥し、次に、乾性油で変
性したフェノール樹脂にメラミン樹脂で変性した水溶性
フェノール樹脂を配合したワニスを含浸乾燥して得られ
たプリプレグを所定枚数重ねて加熱加圧することを特徴
とする積層板の製造方法。1. A paper base material is impregnated with a water-soluble phenol resin varnish modified with a melamine resin, dried and then impregnated with a varnish prepared by mixing a phenol resin modified with a drying oil with a water-soluble phenol resin modified with a melamine resin. A method for manufacturing a laminate, comprising laminating a predetermined number of prepregs obtained by drying and heating and pressing.
ミン樹脂で変性した水溶性フェノール樹脂との配合比
が、乾性油で変性したフェノール樹脂１００重量部に対
し、メラミン樹脂で変性した水溶性フェノール樹脂３〜
２０重量部である請求項１記載の積層板の製造方法。2. The mixing ratio of a phenol resin modified with a drying oil to a water-soluble phenol resin modified with a melamine resin is such that 100 parts by weight of the phenol resin modified with the drying oil is mixed with the water-soluble phenol resin modified with the melamine resin. 3 ~
The method according to claim 1, wherein the amount is 20 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08517394A JP3317575B2 (en) | 1994-04-25 | 1994-04-25 | Manufacturing method of laminated board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08517394A JP3317575B2 (en) | 1994-04-25 | 1994-04-25 | Manufacturing method of laminated board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07290628A JPH07290628A (en) | 1995-11-07 |
| JP3317575B2 true JP3317575B2 (en) | 2002-08-26 |
Family
ID=13851276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08517394A Expired - Fee Related JP3317575B2 (en) | 1994-04-25 | 1994-04-25 | Manufacturing method of laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3317575B2 (en) |
-
1994
- 1994-04-25 JP JP08517394A patent/JP3317575B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07290628A (en) | 1995-11-07 |
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