JPS62101674A - Adhesive for copper foil suitable for use in copper-clad laminate - Google Patents
Adhesive for copper foil suitable for use in copper-clad laminateInfo
- Publication number
- JPS62101674A JPS62101674A JP24314085A JP24314085A JPS62101674A JP S62101674 A JPS62101674 A JP S62101674A JP 24314085 A JP24314085 A JP 24314085A JP 24314085 A JP24314085 A JP 24314085A JP S62101674 A JPS62101674 A JP S62101674A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy
- copper
- adhesive
- resin
- amine
- 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
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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Landscapes
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野〕 本発明は銅張積層板用銅箔接着剤に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a copper foil adhesive for copper-clad laminates.
（従来の技術）
印刷回路板は銅張積層板の銅箔の不要部分を化学的に蝕
刻して導電回路を形成し、回路基板に穴あけ加工を施し
、スルホール内壁に銅メッキにより導電ｆ＠全形成させ
た後、取付電気部品のターミナルをスルホールに挿入し
浴＃はんだ浴に浸漬し、電気部品をスルホールに固定し
て製造する。この場合銅張績Ｎ版としＣは溶融はんだ浴
に浸漬しでぶ＜ｎ、に生じないこと、穴あけ加工に支障
のないこと、又メッキを施す際メッキ薬品類に侵さｎな
いことなどが必要である。(Prior technology) Printed circuit boards are made by chemically etching unnecessary parts of the copper foil of a copper-clad laminate to form a conductive circuit, drilling holes in the circuit board, and copper plating the inner walls of the through holes to create a conductive circuit. After forming, the terminal of the electrical component to be attached is inserted into the through hole, immersed in a solder bath, and the electrical component is fixed in the through hole for manufacturing. In this case, the copper-clad N plate is used, and the C plate must be immersed in a molten solder bath so that it does not cause any sagging, does not interfere with drilling, and must not be attacked by plating chemicals when plating. be.
電気機器製造の作業性向上のため、こｎらの使用条件は
ますます苛酷になる方向にあや、動感性は２６０℃２０
秒以上のはんだ処理に耐え得ることが望まｎている。し
かもテレビ等の高電圧用途での火災事故対策として最近
（／’１妥Ｈｕｊに耐トラツキング性も要求されるに至
っている。In order to improve the workability of electrical equipment manufacturing, these usage conditions are becoming increasingly severe, and the dynamic sensitivity is 260°C 20°C.
It is desired that the soldering process be able to withstand soldering for more than a second. Moreover, tracking resistance has recently come to be required as a countermeasure against fire accidents in high voltage applications such as televisions.
従来からフェノール樹脂含浸基材を用いた銅張り積層機
用接着剤にはポリビニルブチラールにレゾール型フェノ
ール・ホルムアルデヒド樹脂を加えたものが用いらｎて
いるがこの二成分だけの配合では、得らｎる鋼張積層板
の銅箔と基材との接着力、はんだ耐熱性が笑用土満足で
きないのでこわらを改良するためメラミン位（脂キレー
ト剤等多数の添加剤を使用する方法が提案さｎてきてい
る。しかるにこｎらの接着剤に最近、電気機器の火災等
で問題になっている耐トラツキング性についてに何ら考
慮さγしていなく、例えばＩＥＣ法（ＩＥＣＰｕｂ
１１２）テストでｔａ、ＣＴＩ １００〜２５０Ｖボ
ルトにすぎない。Conventionally, adhesives for copper clad laminating machines using phenolic resin-impregnated base materials have been made by adding resol-type phenol formaldehyde resin to polyvinyl butyral, but with a combination of only these two components, Since the adhesion between the copper foil and the base material of the steel-clad laminate and the soldering heat resistance are not satisfactory, a method using a number of additives such as melamine (fat chelating agent) has been proposed to improve the stiffness. However, these adhesives do not take into account the tracking resistance, which has recently become a problem due to fires in electrical equipment.
112) Tested ta, CTI only 100-250V volts.
有機材料の耐トラツキング性は屋外用レジンがいし実用
化等のため種々検討さｎている。例えば、フェノール核
量の減少や水酸化アルミニウム、シリカ、硼酸塩等の充
填剤全多量に添加すること、不飽和ポリエステル樹脂エ
リア樹脂、アクリル樹脂、シリコン樹脂、ブタジェン樹
脂等の耐トラツキング性の良好な樹脂を用いることが知
らｎている。Various studies have been conducted on the tracking resistance of organic materials for practical use in outdoor resin insulators. For example, reducing the amount of phenol nuclei, adding a large amount of fillers such as aluminum hydroxide, silica, and borates, and improving the tracking resistance of unsaturated polyester resins, acrylic resins, silicone resins, butadiene resins, etc. It is known to use resin.
（発明が解決しようとする問題点ン
耐トラッキング性だけを向上するのであてしばこｎらの
知見を取り入γして実用化すｎ＆’１．工いが銅張積層
板用接着剤には絶対条件としてはばんだ耐熱性、銅はく
と基材との接着強さに優ｎることが必要である。耐トラ
ツキング性を改良するために接着剤中のフェノール・ホ
ルマリン樹脂１ｌｔ−減らすとはんだ耐熱性が大巾に低
下するし又充填剤を酢加すると銅はくと基材との接着強
さが低下することになる。(The problem that the invention aims to solve is to improve only the tracking resistance, so the knowledge of Ashibako et al. will be incorporated and put into practical use.) The conditions are that the solder has excellent heat resistance and adhesion strength between the copper foil and the base material.To improve the tracking resistance, reduce the amount of phenol/formalin resin in the adhesive by 1 liter and solder. The heat resistance is greatly reduced, and the addition of vinegar to the filler also reduces the adhesive strength between the copper foil and the substrate.
そこでフェノール核を減らすために脂肪族エポキシの使
用を検討したが、エポキシとフェノール注水酸基、ブチ
ラール中のアルコール注水酸基の反応は、メチロール基
同志の縮合やメチロール基とフェノール核の縮合に比べ
るとかなりゆるやかであり、メチロール基同志及びメチ
ロール基とフェノール核の反応が先に進行するのでエポ
キシ樹脂に完全に架橋構造に入ることがむずかしく耐熱
性も低下する。Therefore, we investigated the use of aliphatic epoxy to reduce the number of phenol nuclei, but the reaction between epoxy and phenol hydroxide groups, and the alcohol hydroxyl groups in butyral, is considerably slower than the condensation of methylol groups or the condensation of methylol groups with phenol nuclei. Since the reaction is gradual and the reaction between the methylol groups and between the methylol group and the phenol nucleus proceeds first, it is difficult to completely enter the crosslinked structure into the epoxy resin and the heat resistance is also reduced.
本発明は、優７した耐トラツキング性、接層性、耐熱性
を兼ね備えた銅張槓Ｎ板用銅箔接着剤を提供するもので
ある。The present invention provides a copper foil adhesive for copper-clad laminate N plates that has excellent tracking resistance, adhesion properties, and heat resistance.
（問題点を解決するための手段〕
本発明はエポキシ樹脂のフェノール樹脂への反応性を種
々検討した結果、添加するエポキシ樹脂をあらかじめ過
剰のポリアミンと加熱反応しエポキシアミンアダクト全
得フェノール樹脂に配合することによりフェノール性水
酸基、ブチラール中のアルコール注水暇基との反応性を
高め、従来の問題を解決出来ることを見出したことによ
りなさてしたものである。(Means for Solving the Problems) As a result of various studies on the reactivity of epoxy resins to phenolic resins, the present invention was developed by heating and reacting the epoxy resin to be added with excess polyamine in advance, and blending the epoxy amine adduct into the phenol resin. This was done based on the discovery that by doing so, the reactivity with the phenolic hydroxyl group and the alcohol-containing group in butyral could be increased, and the conventional problems could be solved.
ここで用いらｎるエポキシアミンアダクトはエポキシ樹
脂の１エポキシ当量に対して１モル以上のアミンを配甘
し、加熱反応させたものである。このアミンアダクトに
残存する第一級のアミノ基はエポキシ基と比較すると２
エノール樹脂のメチロール基と非常に反応しやすく、又
エポキシ樹脂中の全てのエポキシ基にアミンが反応して
いるので反応が均一でエポキシが未反応のまま残こさｎ
る事がない。ここで用いるエポキシ樹脂は耐トラッキン
グ注向上を考えエポキシ当量１００〜５００の脂環式の
エポキシ樹脂が好ましく又アミンは脂肪族で炭素数が２
〜１０程度の第１級もしくは第２級の２価以上のアミン
が好ましい。The epoxy amine adduct used here is obtained by adding 1 mole or more of amine to 1 epoxy equivalent of the epoxy resin and subjecting it to a heating reaction. The primary amino group remaining in this amine adduct is 2 compared to the epoxy group.
It reacts very easily with the methylol groups of the enol resin, and since the amine reacts with all the epoxy groups in the epoxy resin, the reaction is uniform and no epoxy remains unreacted.
There is nothing to do. The epoxy resin used here is preferably an alicyclic epoxy resin with an epoxy equivalent of 100 to 500 in view of improving tracking resistance, and the amine is aliphatic and has 2 carbon atoms.
A primary or secondary divalent or higher amine of about 10 to 10 is preferred.
熱硬化性樹脂１００Ｎ量部に対してエポキシアミンアダ
クトが５重量部未満では縫イＬ ＋ｉ ｌ’ｌ’−・１
７Ｉ７１態“（１が′透Ｙ躾。If the epoxy amine adduct is less than 5 parts by weight with respect to 100N parts of the thermosetting resin, it will be difficult to sew.
7I71 state" (1 is 'Toru Y discipline.
実施例１
エポキシ樹脂（脂環式エポキシｔｌ脂エポキシ当量１５
０〜２００）１００重量部とエチレンジアミン５０重量
部を混合し８０°Ｃ２時間加熱反応させたのちアセトン
で稀釈して固形分５０％のエボキシアミンアダク）（Ａ
［：（Ｉた。Example 1 Epoxy resin (cycloaliphatic epoxy TL fat epoxy equivalent weight 15
0-200) and 50 parts by weight of ethylenediamine were mixed and reacted by heating at 80°C for 2 hours, then diluted with acetone to obtain an epoxyamine adduct with a solid content of 50% (A
[:(I was.
ポリビニルブチラール樹脂（積木化学工業■商品名ＢＸ
−１）１００重量部、レゾール型フェノールホルマリン
樹脂（日立化成工業■製画品名ＶＰ−１３Ｎ）５０重量
部をアセトンに溶かし固形分１８％の接着剤（Ｂ）を得
た。Polyvinyl butyral resin (Building Chemical Industry ■Product name BX
-1) 100 parts by weight and 50 parts by weight of a resol type phenol-formalin resin (manufactured by Hitachi Chemical Co., Ltd., product name VP-13N) were dissolved in acetone to obtain an adhesive (B) with a solid content of 18%.
この接着剤（８）に溶剤を除く有機材料１００重量部に
対してエポキシアミンアダクト（／１１０重量部加える
。こうして得らγした接着剤を日本電解■製６５μ銅箔
に約５５．９／ｒｒｆ（固形分）の割付で塗布乾燥後塗
工紙（フェノール樹脂含浸紙、日立化成工業■製）と共
に常法により加熱加圧し銅張積層板金作成しγこ。To this adhesive (8), add 110 parts by weight of epoxy amine adduct (/110 parts by weight) to 100 parts by weight of the organic material excluding the solvent.The thus obtained gamma adhesive was applied to 65μ copper foil made by Nippon Denki ■ at approximately 55.9/rrf. After coating and drying, the material was heated and pressed using a conventional method with coated paper (phenol resin impregnated paper, manufactured by Hitachi Chemical Co., Ltd.) to create a copper-clad laminated sheet metal.
実施例２
実施例１同様に接着剤ｔＢ）の溶剤を除く有機材料１０
０重量部に対してエポキシアミンアダクト囚を５０重量
部加え接着剤を得た。この接着剤より実施例１と同様に
して銅張積層板を作成した。Example 2 Organic material 10 except for the solvent of adhesive tB) as in Example 1
An adhesive was obtained by adding 50 parts by weight of epoxy amine adduct to 0 parts by weight. A copper-clad laminate was prepared using this adhesive in the same manner as in Example 1.
実施例５
実施例１同様に接着剤（Ｂ）の溶剤の除く有機材料１０
０重量部に対してエポキシアミンアダクト（Ａ）ｔ−１
０重量部と水酸化アルミ（昭和電工■股間品名ハイシラ
イトＨ−４２Ｍ）を５０重量部ｍえ接着剤全得た。この
接着剤より実施例１と同様にして銅張積Ｊａ阪を作成し
た。Example 5 Same as Example 1, organic material 10 excluding solvent of adhesive (B)
Epoxyamine adduct (A) t-1 relative to 0 parts by weight
0 parts by weight and 50 parts by weight of aluminum hydroxide (Hisilite H-42M manufactured by Showa Denko Corporation) to obtain a total adhesive. A copper-clad laminate was prepared using this adhesive in the same manner as in Example 1.
比較例１
実施例１で用いた接着剤（Ｂ）のみ用い、実施例１と同
様にし℃銅張積層板全作成した。Comparative Example 1 A copper clad laminate was entirely prepared in the same manner as in Example 1 using only the adhesive (B) used in Example 1.
比較例２
実施例１同様に接着剤（Ｂ）の溶剤の除く有機材料１０
０重量部に対して、水酸化アルミ（昭和電工■製部品名
ハイジライ）Ｈ−４２Ｍ）を５０重量部加え接着剤を得
た。この接着剤よジ夾施ｆ１１と同様にして銅張績）＃
板を作成した。Comparative Example 2 Same as Example 1, organic material 10 excluding solvent of adhesive (B)
To 0 parts by weight, 50 parts by weight of aluminum hydroxide (part name: Heijirai H-42M manufactured by Showa Denko ■) was added to obtain an adhesive. Apply this adhesive and apply copper coating in the same way as f11)#
Created a board.
以上のようにして作成した銅張積層＠全そｔぞｎ
引きにがし強さ ＪＩＳ Ｃ６４８１５，７はんだ
耐熱性 ＪＩＳ Ｃ６４８１５，５耐トラツキン
グ性 Ｉ ＥＣ（ＩＥＣＰｕｂ １１２）に基づき試験
を行った。別表に結果を示す。The copper clad laminate prepared as described above was tested in accordance with Peeling Strength JIS C64815, 7 Soldering Heat Resistance JIS C64815, 5 Tracking Resistance IEC (IECPub 112). The results are shown in the attached table.
以下余白
（発明の効果）
以上説明したようにこのエポキシアミンアダクトは接着
剤に比較的小量添加するだけで、（１）酊トラッキング
性の良好な接着剤が得らτしる。Margins below (Effects of the Invention) As explained above, by adding a relatively small amount of this epoxy amine adduct to an adhesive, (1) an adhesive with good moisture tracking properties can be obtained.
（２）無機添加剤との併用しても接Ｎ注、耐熱性の低下
が見らｎず併用が可能である。(2) Even when used in combination with inorganic additives, there is no decrease in contact and heat resistance, and the combined use is possible.
の効果が達成さｎる。effect is achieved.
Claims (1)
ムアルデヒド樹脂とよりなる熱硬化性樹脂１００重量部
に対してエポキシアミンアダクトを５〜１００重量部を
添加してなる銅張積層板用銅箔接着剤。 ２、エポキシアミンアダクトのエポキシ樹脂がエポキシ
当量１００〜５００で脂環式のエポキシ樹脂である特許
請求の範囲第１項記載の銅張積層板用銅箔接着剤。 ３、エポキシアミンアダクトのアミンが脂肪族で炭素数
が２〜１０の第１級もしくは第２級の２価以上のアミン
である特許請求の範囲第１項又は第２項記載の銅張積層
板用銅箔接着剤。[Claims] 1. Copper foil for copper-clad laminates prepared by adding 5 to 100 parts by weight of epoxy amine adduct to 100 parts by weight of a thermosetting resin consisting of polyvinyl butyral and resol type phenol formaldehyde resin. glue. 2. The copper foil adhesive for copper-clad laminates according to claim 1, wherein the epoxy resin of the epoxy amine adduct is an alicyclic epoxy resin with an epoxy equivalent of 100 to 500. 3. The copper-clad laminate according to claim 1 or 2, wherein the amine of the epoxy amine adduct is an aliphatic primary or secondary divalent or higher amine having 2 to 10 carbon atoms. Copper foil adhesive for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24314085A JPS62101674A (en) | 1985-10-30 | 1985-10-30 | Adhesive for copper foil suitable for use in copper-clad laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24314085A JPS62101674A (en) | 1985-10-30 | 1985-10-30 | Adhesive for copper foil suitable for use in copper-clad laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62101674A true JPS62101674A (en) | 1987-05-12 |
Family
ID=17099383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24314085A Pending JPS62101674A (en) | 1985-10-30 | 1985-10-30 | Adhesive for copper foil suitable for use in copper-clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62101674A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0691389A1 (en) * | 1994-06-28 | 1996-01-10 | Gould Electronics Inc. | Adhesive compositions and copper foil and copper clad laminates using same |
| EP1829944A1 (en) * | 2006-03-01 | 2007-09-05 | Cytec Surface Specialties Austria GmbH | Water-borne cationic binders for wash primers |
| JP2008031343A (en) * | 2006-07-31 | 2008-02-14 | Dainippon Ink & Chem Inc | Resin composition for adhesion |
-
1985
- 1985-10-30 JP JP24314085A patent/JPS62101674A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0691389A1 (en) * | 1994-06-28 | 1996-01-10 | Gould Electronics Inc. | Adhesive compositions and copper foil and copper clad laminates using same |
| US6132851A (en) * | 1994-06-28 | 2000-10-17 | Ga-Tek Inc. | Adhesive compositions and copper foils and copper clad laminates using same |
| USRE39615E1 (en) * | 1994-06-28 | 2007-05-08 | Nikko Materials Usa, Inc. | Adhesive compositions and copper foils and copper clad laminates using same |
| EP1829944A1 (en) * | 2006-03-01 | 2007-09-05 | Cytec Surface Specialties Austria GmbH | Water-borne cationic binders for wash primers |
| WO2007098947A1 (en) * | 2006-03-01 | 2007-09-07 | Cytec Surface Specialties Austria Gmbh | Water-borne cationic binders for wash primers |
| JP2008031343A (en) * | 2006-07-31 | 2008-02-14 | Dainippon Ink & Chem Inc | Resin composition for adhesion |
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