JPH0678514B2 - Adhesive for metal-clad laminates - Google Patents
Adhesive for metal-clad laminatesInfo
- Publication number
- JPH0678514B2 JPH0678514B2 JP33119489A JP33119489A JPH0678514B2 JP H0678514 B2 JPH0678514 B2 JP H0678514B2 JP 33119489 A JP33119489 A JP 33119489A JP 33119489 A JP33119489 A JP 33119489A JP H0678514 B2 JPH0678514 B2 JP H0678514B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- resin
- metal
- melamine resin
- clad laminates
- 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
- 239000000853 adhesive Substances 0.000 title claims description 26
- 230000001070 adhesive effect Effects 0.000 title claims description 26
- 229920000877 Melamine resin Polymers 0.000 claims description 17
- 239000004640 Melamine resin Substances 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、電気機器、電子機器、計算機器、通信機器等
に用いられる金属張積層板用接着剤に関するものであ
る。TECHNICAL FIELD The present invention relates to an adhesive for metal-clad laminates used in electric equipment, electronic equipment, computing equipment, communication equipment and the like.
従来から、電気機器、電子機器、計算機器、通信機器等
に用いられる金属張積層板には、耐トラッキング性、耐
熱性、回路接着力が強く要望されている。金属箔用の接
着剤として、エポキシ樹脂、ポリビニルブチラールを主
体としたものが広く用いられているが、耐トラッキング
性向上のために更にメラミン樹脂を配合することが行な
われている（特開昭62−132987号公報）など。BACKGROUND ART Conventionally, metal-clad laminates used for electric equipment, electronic equipment, computing equipment, communication equipment, etc. are strongly required to have tracking resistance, heat resistance and circuit adhesive strength. Epoxy resins and polyvinyl butyral-based adhesives are widely used as adhesives for metal foils, but melamine resins have been added to improve the tracking resistance (JP-A-62-62). -132987).
しかしながら、経日変化が大きく経日変化による半田耐
熱性の低下、塗布性の低下が問題であった。However, there is a problem that the solder heat resistance and the coatability are deteriorated due to a large change with time.
本発明の目的とするところは、経日変化が少なく、従っ
て塗布性の低下や半田耐熱性の低下のない金属張積層板
用接着剤を提供することにある。An object of the present invention is to provide an adhesive for metal-clad laminates, which is less prone to changes with time and therefore has no deterioration in coating properties and solder heat resistance.
本発明は、エポキシ樹脂に、ポリビニルブチラール、イ
ソシアネート、及び予じめPHを５〜７に調整されたメラ
ミン樹脂を加え、有機溶剤に溶解したことを特徴とする
金属張積層板用接着剤であり、このメラミン樹脂が経日
変化を抑制し半田耐熱性、塗布性の低下を抑制すること
ができたものである。The present invention is an adhesive for metal-clad laminates, characterized by adding polyvinyl butyral, isocyanate, and a melamine resin having a pre-adjusted PH of 5 to 7 to an epoxy resin and dissolving it in an organic solvent. The melamine resin was able to suppress the change over time and suppress the deterioration of solder heat resistance and coatability.
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1000〜2000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4000−２（電
気化学工業製）などがある。The polyvinyl butyral resin used in the present invention is not particularly limited in the degree of butyralization and the degree of polymerization, but the degree of butyralization is 60 to 65 mol% and the degree of polymerization is preferably about 1000 to 2000. Examples of commercially available products include S-REC BX-1 (manufactured by Sekisui Chemical Co., Ltd.) and Denka Butyral 4000-2 (manufactured by Denki Kagaku Kogyo Co., Ltd.).
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10
01、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。The epoxy resin is not particularly limited, but a bisphenol type or novolak type is preferably used. As a commercially available product, Epicoat 10 is used for the bisphenol type.
01, 1004 (manufactured by Shell Chemical Co., Ltd.), and Novolac type have Epicoat 152, 154 (manufactured by Shell Chemical Chemical Co., Ltd.)
メラミン樹脂は、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 melamine resin is usually obtained by reacting melamine (M) and formaldehyde (F) at a molar ratio F / M = 1.5 to 4.0 in a neutral or weak alkali, optionally adding a lower alcohol such as methanol. is there. 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.
本発明においてはメラミン樹脂の反応が終了した後、酸
によりPHを５〜７に調整する。In the present invention, after the reaction of the melamine resin is completed, the pH is adjusted to 5 to 7 with acid.
ポリイソシアネート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。The polyisocyanate is also not particularly limited, but tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and the like are preferable.
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10〜50％、好ましくは15〜30％、ポリイソシア
ネート１〜15％、好ましくは２〜10％である。In the present invention, the blending ratio of each component used is not particularly limited, but is usually polyvinyl butyral resin 30 to 70% by weight (hereinafter referred to as%), preferably 35 to 55.
%, Epoxy resin 5 to 30%, preferably 10 to 20%, melamine resin 10 to 50%, preferably 15 to 30%, polyisocyanate 1 to 15%, preferably 2 to 10%.
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。If the content of polyvinyl butyral resin is less than 30%, the adhesive strength will decrease, and if it exceeds 70%, the solder heat resistance will tend to decrease.
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。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.
メラミン樹脂が10％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、50％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が１％
未満では接着力が低下し、15％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 melamine resin content is less than 10%, the adhesive strength at the time of heating will decrease and the tracking resistance will be insufficient, and if it exceeds 50%, the adhesive strength will tend to decrease. 1% polyisocyanate
If it is less than 15%, the adhesive strength tends to decrease, and if it exceeds 15%, the tracking resistance tends to deteriorate.
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。The solvent used in the present invention is not particularly limited as long as it can dissolve the above components.
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。According to the present invention, an adhesive having excellent tracking resistance of a copper-clad laminate and having very little deterioration in adhesive strength under heat can be obtained.
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、エポキシ樹脂及びメラミン樹脂が、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。The reason why the adhesive of the present invention has excellent tracking resistance is that the epoxy resin and the melamine resin have a chemical structure and suppress arcs that occur when a conductive circuit in a high-voltage circuit breaks, and prevent ignition of the resin. It is thought that this is because it has a suppressing effect.
また、熱時の接着力が優れている理由は、少量添加され
ているポリイソシアネートの極性により接着力が向上す
るためと考えられる。Further, it is considered that the reason why the adhesive strength at the time of heating is excellent is that the adhesive strength is improved by the polarity of the polyisocyanate added in a small amount.
更に、本発明ではメラミン樹脂のPHを５〜７に調整して
いるので、保存中に経日変化が小さく、従って半田耐熱
性の低下、塗布性の低下が極めて小さい。Furthermore, in the present invention, since the pH of the melamine resin is adjusted to 5 to 7, the change over time during storage is small, and therefore, the solder heat resistance and the coatability are extremely small.
本発明を実施例により説明する。 The present invention will be described with reference to examples.
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。次にPHを酢酸で6.0で調整した。Example of production of melamine resin Melamine (M) and paraformaldehyde (F) at a molar ratio F / M = 2.5, pH was adjusted to 7.5 with ammonia, and reacted at 70 ° C. for 2 hours in a methanol solvent to obtain a resin content of 50%. A melamine resin was obtained. The PH was then adjusted with acetic acid at 6.0.
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）40重量部（以下、部という）、エポキシ樹脂エピコ
ート1001（シェル化学製）10部、前記メラミン樹脂（固
形分）33部及びポリイソシアネートとしてMDI4部を加
え、メタノールとメチルエチルケトンの当量混合溶剤に
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.) 40 parts by weight (hereinafter referred to as "part"), Epoxy resin Epicoat 1001 (manufactured by Shell Chemical Co., Ltd.), 33 parts of the melamine resin (solid content) and MDI4 as polyisocyanate Parts were added and dissolved in an equivalent mixed solvent of methanol and methyl ethyl ketone so that the resin amount was 30% to obtain an adhesive for copper clad laminate.
従来例 メラミン樹脂としてPHを調整しないものを使用した以外
は実施例と同様にして銅張積層板用接着剤を得た。Conventional Example An adhesive for a copper-clad laminate was obtained in the same manner as in the example except that a melamine resin whose PH was not adjusted was used.
実施例及び従来例の接着剤を日本電解工業（株）製の35
μ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。The adhesives of the examples and the conventional examples were manufactured by Nippon Denki Kogyo Co., Ltd.
A copper foil with an adhesive was obtained by applying and drying the resin on a μ copper foil at a rate of 30 g / m 2 .
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。Next, the above-mentioned copper foil with an adhesive was laminated on eight phenol resin-impregnated paper base materials and heat-pressed by a conventional method to obtain a copper-clad laminate.
性能試験の結果を第１表に示す。The results of the performance test are shown in Table 1.
各性能の試験方法は次のとおりである。 The test method for each performance is as follows.
耐トラッキング性 IEC法による はんだ耐熱性 JIS Ｃ 6481による。Tracking resistance Solder heat resistance according to IEC method According to JIS C 6481.
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、メラミン樹脂のPHを５〜７に調整しているので
従来の接着剤を用いた場合に比較して、経日変化が小さ
く、経日後の耐トラッキング性及び耐熱性が優れてい
る。As described above, the copper-clad laminate obtained using the adhesive of the present invention adjusts the PH of the melamine resin to 5 to 7, and therefore, compared with the case of using the conventional adhesive, Diurnal change is small and tracking resistance and heat resistance after day are 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 Ｈ０５Ｋ 3/38 Ｅ 7011−4Ｅ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location H05K 3/38 E 7011-4E
Claims (1)
イソシアネート、及び予じめPHを５〜７に調整されたメ
ラミン樹脂を加え有機溶剤に溶解したことを特徴とする
金属張積層板用接着剤。1. An epoxy resin, polyvinyl butyral,
An adhesive for a metal-clad laminate, which is obtained by adding an isocyanate and a melamine resin adjusted to a predetermined PH of 5 to 7 and dissolving it in an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33119489A JPH0678514B2 (en) | 1989-12-22 | 1989-12-22 | Adhesive for metal-clad laminates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33119489A JPH0678514B2 (en) | 1989-12-22 | 1989-12-22 | Adhesive for metal-clad laminates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03192184A JPH03192184A (en) | 1991-08-22 |
| JPH0678514B2 true JPH0678514B2 (en) | 1994-10-05 |
Family
ID=18240941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33119489A Expired - Fee Related JPH0678514B2 (en) | 1989-12-22 | 1989-12-22 | Adhesive for metal-clad laminates |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0678514B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0565466A (en) * | 1991-09-05 | 1993-03-19 | Hitachi Chem Co Ltd | Adhesive for copper-clad laminate board |
-
1989
- 1989-12-22 JP JP33119489A patent/JPH0678514B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03192184A (en) | 1991-08-22 |
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|---|---|---|---|
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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