JPH05163479A - Adhesive for copper-clad laminate - Google Patents
Adhesive for copper-clad laminateInfo
- Publication number
- JPH05163479A JPH05163479A JP33362691A JP33362691A JPH05163479A JP H05163479 A JPH05163479 A JP H05163479A JP 33362691 A JP33362691 A JP 33362691A JP 33362691 A JP33362691 A JP 33362691A JP H05163479 A JPH05163479 A JP H05163479A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- adhesive
- copper
- clad laminate
- adhesive strength
- 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.)
- Granted
Links
Landscapes
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気機器、電子機器等
に用いられる銅張積層板において、銅箔と電気絶縁層と
の接着のために用いられる接着剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive used for bonding a copper foil and an electric insulating layer in a copper clad laminate used for electric equipment, electronic equipment and the like.
【０００２】[0002]
【従来の技術】印刷回路板は、銅張積層板に導電回路を
形成し、打抜き又はドリル加工によって穴明け加工を施
し、電気部品を搭載し、電気部品と導電回路をはんだに
より接続固着して製造されている。この場合、銅張積層
板の特性として溶融はんだ浴に浸漬して膨れないこと、
導電回路の銅箔と絶縁基板との接着が十分であること等
が必要である。電気・電子機器の高密度化、高精度化に
よって導電回路の細線化が進み、部品と導電回路を接続
する方式も従来の溶融はんだによるフローソルダー方式
に加えて、チップ部品の表面実装によるリフローソルダ
ー方式など多種多様となり、加熱工程が増加し、使用条
件は益々厳しくなって来ている。2. Description of the Related Art In printed circuit boards, a conductive circuit is formed on a copper clad laminate, punched or drilled to form a hole, an electric component is mounted, and the electric component and the conductive circuit are connected and fixed by soldering. Being manufactured. In this case, the characteristic of the copper clad laminate is that it does not swell when immersed in a molten solder bath,
Adhesion between the copper foil of the conductive circuit and the insulating substrate must be sufficient. Conductive circuits are becoming finer due to higher density and higher precision of electrical and electronic equipment, and in addition to the conventional flow solder method using molten solder, the method of connecting parts and conductive circuits is also reflow soldering by surface mounting of chip parts. There are various types of methods, the number of heating processes has increased, and the usage conditions have become more severe.
【０００３】更に、テレビ等の高電圧用途での火災事故
対策として、導電回路側の耐トラッキング性向上の要求
が強まっている。従来から、フェノール樹脂系銅張積層
板用接着剤としては、ポリビニルブチラール樹脂にレゾ
ール型フェノール樹脂及びエポキシ樹脂を加えたものが
主として用いられており、はんだ耐熱性や常温での接着
強度は実用上ある程度満足できるレベルであった。しか
し、このような接着剤系では、前述のごとく最近テレビ
等の高電圧電気機器の火災で問題となっている耐トラッ
キング性については、ＩＥＣ法でＣＴＩ１００〜２００
Ｖのレベルであり、最近の要求からは程遠いものであ
る。Further, as countermeasures against fire accidents in high voltage applications such as televisions, there is an increasing demand for improvement in tracking resistance on the conductive circuit side. Conventionally, as a phenol resin-based copper clad laminate adhesive, polyvinyl butyral resin plus resol-type phenol resin and epoxy resin has been mainly used, and solder heat resistance and adhesive strength at room temperature are practically used. The level was satisfactory to some extent. However, in such an adhesive system, as described above, regarding the tracking resistance, which has recently become a problem due to the fire of high-voltage electric devices such as televisions, the CTI 100-200 according to the IEC method.
V level, far from the recent demand.
【０００４】また、基板に搭載接続した電気・電子部品
をはんだごてで修正する場合など、熱時の接着強度が弱
いと、導電回路が基板から剥がれることがある。従っ
て、この熱時の接着強度の向上が強く要求されている。
しかし、従来の接着剤系ではこのような要求を満たすよ
うに熱時接着強度を向上させることは困難である。Further, when the electric / electronic components mounted and connected to the board are repaired with a soldering iron, if the adhesive strength at the time of heating is weak, the conductive circuit may peel off from the board. Therefore, there is a strong demand for improvement in the adhesive strength under heat.
However, it is difficult for the conventional adhesive system to improve the adhesive strength under heat so as to satisfy such requirements.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記欠点を改
良せんがため、種々研究して完成されたものであり、そ
の目的とするところは、耐熱性及び電気特性を劣化させ
ることなく、耐トラッキング性を向上させ、接着強度の
熱時劣化が少なく、かつ接着剤の経時変化が小さい銅張
積層板用接着剤を提供することにある。SUMMARY OF THE INVENTION The present invention has been completed through various researches in order to improve the above-mentioned drawbacks, and an object of the present invention is to improve heat resistance and electrical characteristics without deteriorating. An object of the present invention is to provide an adhesive for copper-clad laminates, which has improved tracking properties, less deterioration of adhesive strength due to heat, and less change with time of the adhesive.
【０００６】[0006]
【課題を解決するための手段】本発明は、ポリビニルブ
チラール樹脂及びエポキシ樹脂にメラミン樹脂、ポリイ
ソシアネート樹脂及びエポキシアクリレート樹脂を配合
してなる銅張積層板用接着剤に関するものである。本発
明に使用するポリビニルブチラール樹脂については、ブ
チラール化度、重合度には特に制限はないが、ブチラー
ル化度６０〜６５モル％、重合度１０００〜３０００程
度のものが好ましい。市販のものとしては、例えば、エ
スレックＢＸ−１（積水化学製）、電化ブチラール４０
００−２（電気化学工業製）などがある。SUMMARY OF THE INVENTION The present invention relates to an adhesive for copper-clad laminates, which comprises a polyvinyl butyral resin and an epoxy resin mixed with a melamine resin, a polyisocyanate resin and an epoxy acrylate resin. The polyvinyl butyral resin used in the present invention is not particularly limited in the degree of butyralization and the degree of polymerization, but a degree of butyralization of 60 to 65 mol% and a degree of polymerization of about 1000 to 3000 are preferable. Examples of commercially available products include S-REC BX-1 (manufactured by Sekisui Chemical Co., Ltd.) and electrified butyral 40.
00-2 (manufactured by Denki Kagaku Kogyo) and the like.
【０００７】エポキシ樹脂は特に限定されないが、ビス
フェノール型あるいはノボラック型のものが好ましく使
用される。市販のものとしては、ビスフェノール型では
エピコート１００１，１００４（シェル化学製）、ノボ
ラック型ではエピコート１５２，１５４（シェル化学
製）等がある。メラミン樹脂は特に限定されないが、通
常メラミン（Ｍ）とホルムアルデヒド（Ｆ）とをモル比
（Ｆ／Ｍ）＝１.５〜４.０で中性ないし弱アルカリ下に
おいて、必要によりメタノール等の低級アルコールを加
えて、反応させたものである。ＰＨの調整にはアルカリ
金属化合物を使用しないのが好ましい。溶剤については
水を含んでもよいが、アルコール、ケトン等の有機溶剤
に相溶するものが好ましい。The epoxy resin is not particularly limited, but a bisphenol type or novolac type is preferably used. Examples of commercially available products include Epicoat 1001 and 1004 (manufactured by Shell Chemical) for the bisphenol type, and Epicoat 152 and 154 (manufactured by Shell Chemical) for the novolac type. The melamine resin is not particularly limited, but usually, melamine (M) and formaldehyde (F) are mixed at a molar ratio (F / M) of 1.5 to 4.0 under neutral or weak alkali, and if necessary, a lower solvent such as methanol. It is a reaction product obtained by adding alcohol. It is preferable not to use an alkali metal compound for adjusting the pH. The solvent may contain water, but those compatible with organic solvents such as alcohol and ketone are preferable.
【０００８】ポリイソシアネート樹脂についても特に限
定されないが、トリレンジイソシアネート(ＴＤＩ)、ジ
フェニルメタンジイソシアネート(ＭＤＩ)等が好まし
い。エポキシアクリレート樹脂も特に限定されないが、
ビスフェノールＡ型あるいはノボラック型のものが好ま
しく使用される。市販のものとしては、ビスフェノール
Ａ型ではＲ−１３０，Ｒ−１９０（日本化薬製）、ノボ
ラック型では、Ｒ−０１１，Ｒ−３００（日本化薬製）
などがある。The polyisocyanate resin is not particularly limited, but tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and the like are preferable. The epoxy acrylate resin is also not particularly limited,
Bisphenol A type or novolak type is preferably used. As commercially available products, bisphenol A type is R-130 and R-190 (manufactured by Nippon Kayaku), and novolac type is R-011 and R-300 (manufactured by Nippon Kayaku).
and so on.
【０００９】本発明において、使用される各成分の配合
比率は、特に限定するものではないが、通常ポリビニル
ブチラール樹脂３０〜７０重量％(以下、％という)、好
ましくは３５〜５５％、エポキシ樹脂５〜３０％、好ま
しくは１０〜２０％、メラミン樹脂５〜４０％、好まし
くは１０〜２５％、ポリイソシアネート樹脂 ０.５〜１
０％、好ましくは２〜５％、エポキシアクリレート樹脂
５〜４０％、好ましくは１５〜３０％である。In the present invention, the blending ratio of each component used is not particularly limited, but is usually 30 to 70% by weight of polyvinyl butyral resin (hereinafter referred to as%), preferably 35 to 55%, epoxy resin. 5-30%, preferably 10-20%, melamine resin 5-40%, preferably 10-25%, polyisocyanate resin 0.5-1
0%, preferably 2-5%, epoxy acrylate resin 5-40%, preferably 15-30%.
【００１０】ポリビニルブチラール樹脂が３０％未満で
は接着力が低下し、７０％を越えるとはんだ耐熱性が低
下する傾向となる。エポキシ樹脂が５％未満では熱時接
着力が低下すると共に電気的性能が低下し、３０％を越
えると接着力が低下する傾向となる。メラミン樹脂が５
％未満では熱時接着力が低下すると共に耐トラッキング
性が不十分となり、４０％を越えると接着力が低下する
傾向となる。ポリイソシアネート樹脂が ０.５％未満で
は接着力が低下し、１０％を越えると耐トラッキング性
が低下する傾向がある。If the content of the polyvinyl butyral resin is less than 30%, the adhesive strength will decrease, and if it exceeds 70%, the solder heat resistance will decrease. If the epoxy resin content is less than 5%, the adhesive strength at the time of heating will decrease and the electrical performance will decrease, and if it exceeds 30%, the adhesive strength tends to decrease. Melamine resin is 5
If it is less than 40%, the adhesive force at the time of heating is lowered and the tracking resistance becomes insufficient, and if it exceeds 40%, the adhesive force tends to be lowered. If the polyisocyanate resin content is less than 0.5%, the adhesive strength will decrease, and if it exceeds 10%, the tracking resistance will tend to decrease.
【００１１】エポキシアクリレート樹脂は、５％未満で
は耐トラッキング性及び接着力が低下し、４０％を越え
るとはんだ耐熱性が低下する傾向となる。なお、本発明
において使用する溶剤は、前記各成分を溶解するもので
あれば特に限定されない。If the epoxy acrylate resin is less than 5%, the tracking resistance and the adhesive strength will be deteriorated, and if it exceeds 40%, the solder heat resistance will be deteriorated. The solvent used in the present invention is not particularly limited as long as it can dissolve the above components.
【００１２】[0012]
【作用】本発明に従うと、銅張積層板の耐トラッキング
性が優れ、接着力の熱時劣化も極めて少ない接着剤が得
られる。本発明の接着剤が耐トラッキング性が優れてい
る理由は、エポキシ樹脂、メラミン樹脂及びエポキシア
クリレート樹脂が、化学構造的にみて、高電圧回路にお
ける導通回路の破断時に発生するアークを抑制し、樹脂
への着火を抑制する作用を有するためと考えられる。ま
た、熱時の接着力が優れている理由は、エポキシアクリ
レート樹脂及び少量添加されているポリイソシアネート
樹脂の極性により接着力が向上するためと考えられる。According to the present invention, an adhesive can be obtained in which the copper-clad laminate has excellent tracking resistance and the adhesive strength is very little deteriorated by heat. The reason why the adhesive of the present invention is excellent in tracking resistance is that the epoxy resin, melamine resin and epoxy acrylate resin have a chemical structure, and suppress the arc generated when the conductive circuit in the high voltage circuit is broken, It is considered that this is because it has the effect of suppressing ignition to the. Further, the reason why the adhesive strength at the time of heating is excellent is considered to be that the adhesive strength is improved by the polarities of the epoxy acrylate resin and the polyisocyanate resin added in a small amount.
【００１３】[0013]
【実施例】本発明を実施例により説明する。メラミン樹脂の製造例 メラミン（Ｍ）とパラホルムアルデヒド（Ｆ）とをモル
比Ｆ／Ｍ＝ ２.５で、アンモニアによりＰＨを ７.５と
し、メタノール溶剤下で７０℃で２時間反応し、樹脂分
５０％のメラミン樹脂を得た。EXAMPLES The present invention will be described with reference to examples. Example of production of melamine resin Melamine (M) and paraformaldehyde (F) are used at a molar ratio F / M = 2.5, pH is adjusted to 7.5 with ammonia, and the mixture is reacted in a methanol solvent at 70 ° C. for 2 hours to obtain a resin. 50% melamine resin was obtained.
【００１４】実施例 ポリビニルブチラール樹脂エスレックＢＸ−１（積水化
学製）３２重量部（以下、部という）、エポキシ樹脂エ
ピコート１００１（油化シェル製）２０部、前記メラミ
ン樹脂（固形分）２５部、ポリイソシアネート樹脂とし
てＭＤＩ３部及びビスフェノールＡ型エポキシアクリレ
ート樹脂Ｒ−１９０（日本化薬製）２０部を加え、メタ
ノールとメチルエチルケントの等量混合溶剤に樹脂量が
３０％になるように溶解し、銅張積層板用接着剤を得
た。従来例 ポリビニルブチラール樹脂４０部、レゾール型フェノー
ル樹脂３０部（固形分）及びエポキシ樹脂３０部（各成
分は実施例で使用したものと同じ）をメタノールとメチ
ルエチルケントの等量混合溶剤に樹脂量が３０％になる
ように溶解し、銅張積層板用接着剤を得た。 Example Polyvinyl butyral resin S-REC BX-1 (manufactured by Sekisui Chemical Co., Ltd.) 32 parts by weight (hereinafter referred to as "part"), epoxy resin Epicoat 1001 (manufactured by Yuka Shell) 20 parts, the melamine resin (solid content) 25 parts, As polyisocyanate resin, 3 parts of MDI and 20 parts of bisphenol A type epoxy acrylate resin R-190 (manufactured by Nippon Kayaku Co., Ltd.) were added, and dissolved in an equal amount mixed solvent of methanol and methyl ethyl kent so that the resin amount was 30%, An adhesive for copper clad laminate was obtained. Conventional example 40 parts of polyvinyl butyral resin, 30 parts of resol type phenolic resin (solid content) and 30 parts of epoxy resin (each component is the same as that used in the example) in an equal amount mixed solvent of methanol and methyl ethyl kent resin amount To 30% to obtain a copper-clad laminate adhesive.
【００１５】実施例及び従来例の接着剤を日本電解
（株）製の３５μｍ銅箔に樹脂量３０ｇ／ｍ2 の割合で
塗布乾燥して接着剤付き銅箔を得た。次に、フェノール
樹脂含浸紙基材を８枚重ねた上に前記接着剤付き銅箔を
重ね、常法により加熱加圧成形して銅張積層板を得た。
性能試験の結果を表１に示す。The adhesives of Examples and Conventional Examples were applied to 35 μm copper foil manufactured by Nippon Denki Co., Ltd. at a resin amount of 30 g / m 2 and dried to obtain adhesive-coated copper foil. Next, the above-mentioned copper foil with adhesive was laminated on 8 sheets of paper base material impregnated with phenolic resin, and heat-pressed by a conventional method to obtain a copper-clad laminate.
The results of the performance test are shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】各性能の試験方法は次のとおりである。 耐トラッキング性 ＩＥＣ法による。 接着強度 ＪＩＳ Ｃ ６４８１による。 はんだ耐熱性 ＪＩＳ Ｃ ６４８１による。The test method for each performance is as follows. Tracking resistance According to IEC method. Adhesive strength According to JIS C 6481. Solder heat resistance According to JIS C 6481.
【００１８】[0018]
【発明の効果】以上のように、本発明の接着剤を用いて
得られた銅張積層板は、従来の接着剤を用いた場合に比
較して、耐トラッキング性及び接着強度、特に熱時の接
着強度が優れている。更に、接着剤の保存性も優れてい
る。INDUSTRIAL APPLICABILITY As described above, the copper clad laminate obtained by using the adhesive of the present invention has tracking resistance and adhesive strength, especially when heated, as compared with the case of using the conventional adhesive. Has excellent adhesive strength. In addition, the storage stability of the adhesive is excellent.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 163/10 Ｈ０５Ｋ 3/38 Ｅ 7011−4Ｅ Continuation of front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location C09J 163/10 H05K 3/38 E 7011-4E
Claims (1)
樹脂にメラミン樹脂、ポリイソシアネート樹脂及びエポ
キシアクリレート樹脂を配合してなる銅張積層板用接着
剤。1. An adhesive for a copper-clad laminate, which comprises a polyvinyl butyral resin and an epoxy resin mixed with a melamine resin, a polyisocyanate resin and an epoxy acrylate resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33362691A JP3209767B2 (en) | 1991-12-17 | 1991-12-17 | Adhesive for copper clad laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33362691A JP3209767B2 (en) | 1991-12-17 | 1991-12-17 | Adhesive for copper clad laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05163479A true JPH05163479A (en) | 1993-06-29 |
| JP3209767B2 JP3209767B2 (en) | 2001-09-17 |
Family
ID=18268155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33362691A Expired - Fee Related JP3209767B2 (en) | 1991-12-17 | 1991-12-17 | Adhesive for copper clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3209767B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07122851A (en) * | 1993-10-25 | 1995-05-12 | Hitachi Chem Co Ltd | Copper foil with adhesive and manufacture of copper-clad laminated board for multilayer printed-wiring board using said copper foil with adhesive |
| CN110218546A (en) * | 2019-06-20 | 2019-09-10 | 佛山南宝高盛高新材料有限公司 | A kind of Halogen is from flame retardant polyurethane hot melt adhesive and preparation method thereof |
| CN113292900A (en) * | 2020-02-21 | 2021-08-24 | 东莞市立基电子材料有限公司 | Aluminum-based copper-clad plate silk-screen printing insulating glue and silk-screen printing method |
| CN113388349A (en) * | 2021-05-13 | 2021-09-14 | 福建利豪电子科技股份有限公司 | Preparation process of copper foil adhesive special for high CTI (comparative tracking index) and application of copper foil adhesive to paper-based copper-clad plate |
-
1991
- 1991-12-17 JP JP33362691A patent/JP3209767B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07122851A (en) * | 1993-10-25 | 1995-05-12 | Hitachi Chem Co Ltd | Copper foil with adhesive and manufacture of copper-clad laminated board for multilayer printed-wiring board using said copper foil with adhesive |
| CN110218546A (en) * | 2019-06-20 | 2019-09-10 | 佛山南宝高盛高新材料有限公司 | A kind of Halogen is from flame retardant polyurethane hot melt adhesive and preparation method thereof |
| CN113292900A (en) * | 2020-02-21 | 2021-08-24 | 东莞市立基电子材料有限公司 | Aluminum-based copper-clad plate silk-screen printing insulating glue and silk-screen printing method |
| CN113388349A (en) * | 2021-05-13 | 2021-09-14 | 福建利豪电子科技股份有限公司 | Preparation process of copper foil adhesive special for high CTI (comparative tracking index) and application of copper foil adhesive to paper-based copper-clad plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3209767B2 (en) | 2001-09-17 |
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