JP3111577B2 - Manufacturing method of laminated board - Google Patents
Manufacturing method of laminated boardInfo
- Publication number
- JP3111577B2 JP3111577B2 JP04001822A JP182292A JP3111577B2 JP 3111577 B2 JP3111577 B2 JP 3111577B2 JP 04001822 A JP04001822 A JP 04001822A JP 182292 A JP182292 A JP 182292A JP 3111577 B2 JP3111577 B2 JP 3111577B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- melamine
- resistance
- laminate
- phenol resin
- 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
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
Landscapes
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐銀マイグレーション
性、耐電食性、耐燃性、耐トラッキング性及び打抜き加
工性に優れた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 method for producing a laminate excellent in silver migration resistance, electrolytic corrosion resistance, flame resistance, tracking resistance and punching workability.
【０００２】[0002]
【従来の技術】紙を基材とする積層板の製造方法におい
て、原紙に樹脂を含浸する方法として２段含浸法があ
る。２段含浸法は、紙との親和性のよい樹脂ワニスを含
浸（前処理という）した後、熱硬化性樹脂ワニスを、含
浸（上塗りという）する方法である。積層板に耐燃性を
付与し、耐湿性をよくするために、前処理用樹脂ワニス
として、メラミン樹脂又はメラミンを含む水溶性フェノ
ール樹脂を用いる場合が多い。2. Description of the Related Art In a method for producing a laminate using paper as a base material, there is a two-stage impregnation method as a method for impregnating a base paper with a resin. The two-stage impregnation method is a method in which a resin varnish having good affinity for paper is impregnated (referred to as pretreatment), and then a thermosetting resin varnish is impregnated (referred to as overcoating). In order to impart flame resistance to the laminate and improve moisture resistance, a melamine resin or a water-soluble phenol resin containing melamine is often used as a resin varnish for pretreatment.
【０００３】樹脂を耐燃性とするために、一般に、リン
酸エステルなどのリン系化合物、ブロム化フェノール
類、ブロム化エポキシ化合物、ブロム化ビフェニルエー
テル類などのブロム系化合物、メラミン化合物及びトリ
アジン化合物などの窒素系化合物又はアンチモンなどの
無機化合物を単独または併用して熱硬化性樹脂に添加し
ている。[0003] In order to make the resin flame-resistant, phosphorus compounds such as phosphoric acid esters, brominated compounds such as brominated phenols, brominated epoxy compounds, brominated biphenyl ethers, melamine compounds and triazine compounds are generally used. Or an inorganic compound such as antimony alone or in combination is added to the thermosetting resin.
【０００４】積層板の打ち抜き加工性をよくするため
に、エポキシ化ポリブタジエンをレゾール型フェノール
樹脂に化学結合して得た変性フェノール樹脂を用いるこ
とも知られている（特開昭６１−２９６０１６号公報参
照）。It is also known to use a modified phenolic resin obtained by chemically bonding epoxidized polybutadiene to a resole type phenolic resin in order to improve the punching workability of a laminated plate (Japanese Patent Application Laid-Open No. 61-296016). reference).
【０００５】[0005]
【発明が解決しようとする課題】最近、電子機器の多機
能化及び高信頼性化等を目的として、紙基材を用いた積
層板でもプリント配線板の表裏にある導体パターン間を
銅めっきや銀ペーストによるスルーホールで接続するよ
うになっている。このため、特に耐銀マイグレーション
性、耐電食性に優れたプリント配線板用積層板が必要と
なっている。また、安全の面から積層板の耐燃性の要求
が一段と厳しくなり、米国ＵＬ規格などの法制や規格が
整備され、その規制が強化されてきている。Recently, for the purpose of multifunctionality and high reliability of electronic equipment, even for a laminated board using a paper base material, copper plating or the like between conductive patterns on the front and back of a printed wiring board is required. The connection is made by through holes made of silver paste. For this reason, a laminate for a printed wiring board having particularly excellent silver migration resistance and electric corrosion resistance is required. In addition, from the viewpoint of safety, the requirements for the flame resistance of the laminated board have become more severe, and laws and regulations such as the UL standard in the United States have been prepared, and the regulations thereof have been strengthened.
【０００６】紙基材を、メラミンを含む水溶性フェノー
ル樹脂で前処理した後、熱硬化性樹脂を含浸して得たプ
リプレグを使用することによっても、積層板の耐銀マイ
グレーション性、耐電食性が良くなる。但し、この方法
による場合、耐燃性、耐トラッキング性及び打抜き加工
性を良くすることができない。また、紙基材をメラミン
樹脂で前処理したのち熱硬化性樹脂を含浸する方法によ
ると、耐燃性、耐トラッキング性及び打抜き加工性が良
いが、耐銀マイグレーション性、耐電食性が良くない。[0006] By using a prepreg obtained by pretreating a paper base material with a water-soluble phenol resin containing melamine and then impregnating it with a thermosetting resin, the silver migration resistance and the electrolytic corrosion resistance of the laminate can also be improved. Get better. However, this method cannot improve the flame resistance, tracking resistance and punching workability. According to the method in which a paper base material is pretreated with a melamine resin and then impregnated with a thermosetting resin, flame resistance, tracking resistance and punching workability are good, but silver migration resistance and electric corrosion resistance are not good.
【０００７】本発明は、紙基材を前処理樹脂で処理した
後更に熱硬化性樹脂を含浸して得たプリプレグを使用し
て加熱加圧する積層板の製造方法において、耐銀マイグ
レーション性、耐電食性、耐燃性、耐トラッキング性及
び打抜き加工性のすべてに優れた積層板の製造方法を提
供することを目的とする。[0007] The present invention relates to a method for producing a laminated board, in which a prepreg obtained by treating a paper base material with a pretreatment resin and further impregnating with a thermosetting resin is heated and pressurized. It is an object of the present invention to provide a method for manufacturing a laminate having excellent corrosion resistance, flame resistance, tracking resistance, and punching workability.
【０００８】[0008]
【課題を解決するための手段】本発明は、５〜１８重量
％のメラミンを含むフェノール樹脂を紙基材に含浸し、
次に熱硬化性樹脂を含浸して得たプリプレグを表層と
し、２０重量％以上のメラミンを含むフェノール樹脂を
紙基材に含浸し、次に熱硬化性樹脂を含浸して得たプリ
プレグを内層として、積層成形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 substrate is impregnated with a phenol resin containing 5 to 18% by weight of melamine,
Next, a prepreg obtained by impregnating a thermosetting resin is used as a surface layer, a phenol resin containing at least 20% by weight of melamine is impregnated into a paper base material, and then a prepreg obtained by impregnating the thermosetting resin is used as an inner layer. The present invention provides a method for producing a laminated plate, which comprises laminating and molding.
【０００９】メラミンを含むフェノール樹脂としては、
メラミンとフェノール樹脂とを反応させたメラミン変性
フェノール樹脂及びメラミン樹脂とフェノール樹脂との
混和物のいずれも使用できる。As the phenol resin containing melamine,
Any of a melamine-modified phenol resin obtained by reacting melamine and a phenol resin and a mixture of the melamine resin and the phenol resin can be used.
【００１０】表層用プリプレグの前処理にに用いる樹脂
に含まれるメラミン量が、５重量％未満では耐トラッキ
ング性がよくない。また、１８重量％を超えると、耐湿
性が低下する。表層用プリプレグの前処理にに用いる樹
脂に含まれるメラミン量は、５〜１５％の範囲が最も好
ましい。If the amount of melamine contained in the resin used for the pretreatment of the surface prepreg is less than 5% by weight, the tracking resistance is not good. On the other hand, when the content exceeds 18% by weight, the moisture resistance decreases. Most preferably, the amount of melamine contained in the resin used for the pretreatment of the surface prepreg is in the range of 5 to 15%.
【００１１】内層用プリプレグの前処理に用いる樹脂に
含まれるメラミン量が、２０重量％以下であると、耐燃
性及び耐トラッキング性が悪くなる。内層用プリプレグ
の前処理にに用いる樹脂に含まれるメラミン量は、２０
〜３０％の範囲が最も好ましい。When the amount of melamine contained in the resin used for the pretreatment of the prepreg for the inner layer is less than 20% by weight, the flame resistance and the tracking resistance deteriorate. The amount of melamine contained in the resin used for the pretreatment of the prepreg for the inner layer is 20%.
The range of -30% is most preferred.
【００１２】前処理用樹脂は、メタノール、トルエン、
アルコール、メチルエチルケトン、アセトン、ジメチル
ホルムアミド、スチレンなどの溶剤に溶解してワニスと
し、原紙に含浸する。原紙としては、クラフト紙、リン
ター紙、コットン紙、などが使用でき、厚み、混抄の有
無は問わない。前処理用樹脂ワニスを含浸し、乾燥した
後、上塗り用熱硬化性樹脂ワニスを含浸乾燥する。The resin for pretreatment is methanol, toluene,
It is dissolved in a solvent such as alcohol, methyl ethyl ketone, acetone, dimethylformamide, and styrene to form a varnish and impregnated into base paper. Kraft paper, linter paper, cotton paper, and the like can be used as the base paper, regardless of the thickness and whether or not mixed paper is used. After impregnating and drying the pretreatment resin varnish, the thermosetting resin varnish for top coating is impregnated and dried.
【００１３】このようにして得られた内層用プリプレグ
を所定枚数重ね、その両面に表層用プリプレグを配し、
加熱加圧して積層板とする。積層板構成の外側に銅箔を
組み合わせると銅張積層板となる。銅箔は接着剤付を用
いると接着強度は向上する。A predetermined number of inner layer prepregs thus obtained are stacked, and surface prepregs are arranged on both sides thereof.
Heat and press to make a laminate. When a copper foil is combined with the outside of the laminate structure, a copper-clad laminate is obtained. Adhesive strength is improved when copper foil is used with an adhesive.
【００１４】上塗りに用いる熱硬化性樹脂は、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で
ある。特に、乾性油変性フェノール樹脂を用いると、打
ち抜き加工性が良好となる。乾性油としては、桐油、脱
水ひまし油、オイチシカ油などが使用でき、フェノール
類としては、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などが使用できる。The thermosetting resin used for the overcoat is a phenol resin, a melamine resin, an unsaturated polyester resin, or the like. In particular, when a dry oil-modified phenol resin is used, the punching workability is improved. As the drying oil, tung oil, dehydrated castor oil, deer castor oil, etc. can be used. Etc. can be used.
【００１５】[0015]
【作用】メラミン樹脂は、分子中にＣ−Ｎ結合があるた
め、電圧印加によって分解し、トラッキングを発生しな
いようにする。ところがメラミンが多いと、積層板が吸
湿しやすくなり、耐電食性、耐銀マイグレーション性が
悪くなる。フェノール樹脂は、原紙の−ＯＨ基と結合す
るので、積層板の耐湿性がよくなり、耐電食性、耐銀マ
イグレーション性がよくなる。ところが、フェノール樹
脂が多いと、耐燃性と打抜き加工性が悪くなる。The melamine resin has a C--N bond in the molecule, so that it is decomposed by applying a voltage to prevent tracking. However, when the amount of melamine is large, the laminated board tends to absorb moisture, and the corrosion resistance and the silver migration resistance deteriorate. Since the phenol resin bonds to the -OH group of the base paper, the laminate has improved moisture resistance, and has improved resistance to electric corrosion and silver migration. However, when the amount of the phenol resin is large, the flame resistance and the punching workability deteriorate.
【００１６】そこで、表層部のメラミン量を少なくし、
内層部のメラミン量を多くすれば、表層部で耐湿性をカ
バーし、内層部で打抜き加工性、耐燃性及び耐トラッキ
ング性をカバーできる。Therefore, the amount of melamine in the surface layer is reduced,
By increasing the amount of melamine in the inner layer, the surface layer can cover the moisture resistance, and the inner layer can cover the punching workability, flame resistance, and tracking resistance.
【００１７】[0017]
実施例１ メラミン量１２％のメラミン変性フェノール樹脂を表層
用プリプレグの前処理樹脂とし、メラミン量３０％のメ
ラミン変性フェノール樹脂を内層用プリプレグの前処理
樹脂とした。これら前処理樹脂をメタノールに溶解し、
それぞれクラフト紙に樹脂付着量が１７〜２０％となる
ように含浸乾燥して表層用前処理基材及び内層用前処理
基材を得た。更に、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２８
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、トルエンに溶解して上塗りワニスを
得た。Example 1 A melamine-modified phenol resin having a melamine content of 12% was used as a pretreatment resin for a prepreg for a surface layer, and a melamine-modified phenol resin having a melamine content of 30% was used as a pretreatment resin for a prepreg for an inner layer. Dissolve these pre-treated resins in methanol,
Each of the kraft papers was impregnated and dried so that the resin adhesion amount was 17 to 20% to obtain a pretreatment base material for the surface layer and a pretreatment base material for the inner layer. Furthermore, triphenyl phosphate 28 was added to 100 parts of tung oil-modified phenol resin
Parts, and 20 parts of tetrabromobisphenol A diglycidyl ether were blended and dissolved in toluene to obtain an overcoated varnish.
【００１８】上記の表層用前処理基材及び内層用前処理
基材に、上記上塗りワニスを全樹脂付着量が５０〜５４
重量％となるように含浸乾燥して表層用プリプレグと内
層用プリプレグを得た。この内層用プリプレグ６枚を積
層し、その両面に表層用プリプレグを各１枚重ね、更に
その両面に銅箔を配し加熱加圧して厚み１．６ｍｍの両
面銅張積層板を得た。The above-mentioned top-coating varnish is applied to the above-mentioned pretreated base material for the surface layer and the pretreated base material for the inner layer so that the total resin adhesion amount is 50 to 54.
The prepreg for the surface layer and the prepreg for the inner layer were obtained by impregnating and drying so as to have a weight%. Six prepregs for the inner layer were laminated, one prepreg for the surface layer was laminated on both surfaces thereof, and a copper foil was further disposed on both surfaces thereof, and heated and pressed to obtain a double-sided copper-clad laminate having a thickness of 1.6 mm.
【００１９】実施例２ メラミン樹脂１０部とフェノール樹脂９０部とを混合し
た樹脂組成物を表層用プリプレグの前処理樹脂とし、メ
ラミン樹脂３５部とフェノール樹脂６５部とを混合した
樹脂組成物を内層用プリプレグの前処理樹脂とした他
は、実施例１と同様にして厚み１．６ｍｍの両面銅張り
積層板を得た。Example 2 A resin composition obtained by mixing 10 parts of melamine resin and 90 parts of phenol resin was used as a pretreatment resin for a prepreg for a surface layer, and a resin composition obtained by mixing 35 parts of melamine resin and 65 parts of phenol resin was used as an inner layer. A double-sided copper-clad laminate having a thickness of 1.6 mm was obtained in the same manner as in Example 1 except that the resin was used as a pretreatment resin for the prepreg.
【００２０】比較例 水溶性フェノール樹脂を表層用及び内層用プリプレグの
前処理樹脂とした他は実施例１と同様にして１．６ｍｍ
の両面銅張り積層板を得た。Comparative Example 1.6 mm in the same manner as in Example 1 except that a water-soluble phenol resin was used as a pretreatment resin for the prepreg for the surface layer and the inner layer.
Was obtained.
【００２１】試験 実施例及び比較例で得た銅張積層板の耐銀マイグレーシ
ョン性、打抜き加工性、耐燃性及び耐マイグレーション
性をそれぞれ、次の方法で試験した。Tests The copper-clad laminates obtained in Examples and Comparative Examples were tested for silver migration resistance, punching workability, flame resistance and migration resistance by the following methods.
【００２２】耐銀マイグレーション性及び耐電食性 穴間ピッチ２．０ｍｍ、ランド径１．５ｍｍ、穴径０．
７ｍｍ、９０穴連続２回路の銀マイグレーションテスト
パターンを用い、印加電圧５０Ｖ、相対湿度９０％Ｒ
Ｈ、温度４０℃で２０００時間処理後の回路間絶縁抵抗
を測定した。その結果、実施例１によって得られた積層
板は１．３×１０9 Ω、実施例２によって得られた積層
板は２．８×１０9 Ω、比較例によって得られた積層板
は６．０×１０9 Ωであった。Silver migration resistance and electrolytic corrosion resistance Pitch between holes: 2.0 mm, land diameter: 1.5 mm, hole diameter: 0.1 mm
Using a silver migration test pattern of 7 mm, 90 holes continuous 2 circuits, applied voltage 50 V, relative humidity 90% R
H, the insulation resistance between circuits after the treatment at a temperature of 40 ° C. for 2000 hours was measured. As a result, the laminate obtained in Example 1 was 1.3 × 10 9 Ω, the laminate obtained in Example 2 was 2.8 × 10 9 Ω, and the laminate obtained in Comparative Example was 6.6 × 10 9 Ω. It was 0 × 10 9 Ω.
【００２３】打抜き加工性 穴間ピッチ２．０ｍｍ、穴径０．７ｍｍで穴あけしたと
きのはくり目白の発生を評価した。その結果、実施例１
及び２によって得られた積層板は、いずれも良好であっ
たが、比較例によって得られた積層板は不良であった。Punching workability The occurrence of peeling white spots when drilling holes with a hole pitch of 2.0 mm and a hole diameter of 0.7 mm was evaluated. As a result, Example 1
The laminates obtained by Comparative Examples 1 and 2 were all good, but the laminates obtained by the comparative examples were poor.
【００２４】耐燃性 ＵＬ法にしたがい、１０秒間接炎を２回繰返し、消炎す
るまでの時間を測定した。その結果、実施例１によって
得られた積層板は１．７（０〜４）秒、実施例２によっ
て得られた積層板は１．５（０〜３）秒、比較例によっ
て得られた積層板は６．０（１〜１３）秒であった。Flame resistance According to the UL method, the indirect flame was repeated twice for 10 seconds, and the time until the flame was extinguished was measured. As a result, the laminate obtained in Example 1 was 1.7 (0 to 4) seconds, the laminate obtained in Example 2 was 1.5 (0 to 3) seconds, and the laminate obtained in the comparative example. The plate was 6.0 (1-13) seconds.
【００２５】耐トラッキング性 ＩＥＣ法により印加電圧６００Ｖで試験した。その結
果、実施例１によって得られた積層板は８５〜１００、
実施例２によって得られた積層板は８０〜９５、比較例
によって得られた積層板は１０〜２０であった。Tracking resistance The test was performed by the IEC method at an applied voltage of 600V. As a result, the laminate obtained according to Example 1 was 85 to 100,
The laminate obtained in Example 2 was 80 to 95, and the laminate obtained in Comparative Example was 10 to 20.
【００２６】[0026]
【発明の効果】本発明によれば、表層用前処理樹脂のメ
ラミン量を少なくし、内層部のメラミン量を多くするこ
とによって、表層の持つ特性と内層の持つ特性とが互い
に補いあって耐銀マイグレーション性、耐電食性、耐燃
性、耐トラッキング性及び打抜き加工性の何れにも優れ
た積層板を得ることができる。According to the present invention, by reducing the amount of melamine in the pretreatment resin for the surface layer and increasing the amount of melamine in the inner layer portion, the characteristics of the surface layer and the characteristics of the inner layer complement each other, and the resistance is improved. A laminate excellent in silver migration property, electrolytic corrosion resistance, flame resistance, tracking resistance and punching workability can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｂ２９Ｋ 61:04 105:06 (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 15/08 105 B32B 7/02 H05K 1/03 610 ──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. 7 identification code FI // B29K 61:04 105: 06 (58) Investigated field (Int.Cl. 7 , DB name) B32B 15/08 105 B32B 7 / 02 H05K 1/03 610
Claims (3)
ール樹脂を紙基材に含浸し、次に熱硬化性樹脂を含浸し
て得たプリプレグを表層とし、２０重量％以上のメラミ
ンを含むフェノール樹脂を紙基材に含浸し、次に熱硬化
性樹脂を含浸して得たプリプレグを内層として、積層成
形することを特徴とする積層板の製造方法。1. A prepreg obtained by impregnating a paper substrate with a phenol resin containing 5 to 18% by weight of melamine and then impregnating a thermosetting resin with a phenol containing 20% by weight or more of melamine as a surface layer. A method for manufacturing a laminate, comprising: impregnating a paper base material with a resin, and then impregnating a thermosetting resin, and laminating and forming a prepreg obtained as an inner layer.
ミン変性フェノール樹脂であることを特徴とする請求項
１記載の積層板の製造方法。2. The method according to claim 1, wherein the melamine-containing phenol resin is a melamine-modified phenol resin.
ミン樹脂とフェノール樹脂との混和物であることを特徴
とする請求項１記載の積層板の製造方法。3. The method according to claim 1, wherein the phenol resin containing melamine is a mixture of the melamine resin and the phenol resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04001822A JP3111577B2 (en) | 1992-01-09 | 1992-01-09 | Manufacturing method of laminated board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04001822A JP3111577B2 (en) | 1992-01-09 | 1992-01-09 | Manufacturing method of laminated board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05185527A JPH05185527A (en) | 1993-07-27 |
| JP3111577B2 true JP3111577B2 (en) | 2000-11-27 |
Family
ID=11512258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04001822A Expired - Fee Related JP3111577B2 (en) | 1992-01-09 | 1992-01-09 | Manufacturing method of laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3111577B2 (en) |
-
1992
- 1992-01-09 JP JP04001822A patent/JP3111577B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05185527A (en) | 1993-07-27 |
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