JPH04154885A - Adhesive of metallic foil for laminate - Google Patents
Adhesive of metallic foil for laminateInfo
- Publication number
- JPH04154885A JPH04154885A JP2282937A JP28293790A JPH04154885A JP H04154885 A JPH04154885 A JP H04154885A JP 2282937 A JP2282937 A JP 2282937A JP 28293790 A JP28293790 A JP 28293790A JP H04154885 A JPH04154885 A JP H04154885A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- adhesive
- weight
- metal foil
- mol
- 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
- 239000000853 adhesive Substances 0.000 title claims abstract description 26
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 26
- 239000011888 foil Substances 0.000 title claims description 17
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 14
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 14
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 12
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 8
- 239000004640 Melamine resin Substances 0.000 claims abstract description 7
- 239000001530 fumaric acid Substances 0.000 claims abstract description 6
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 6
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000003860 storage Methods 0.000 abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 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 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 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
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 210000004417 patella Anatomy 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- -1 methyl compound Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 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
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プリント配線板などに供される積層板用の金
属箔の接着剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a metal foil adhesive for laminated boards used in printed wiring boards and the like.
近年、プリント配線板には電子部品がますます高密度に
実装される様になって来ている。このためにますます狭
くなる回路において、その回路間の絶縁性能、特に耐ト
ラツキング性の向上が必要になってきている。耐トラツ
キング性に優れた積層板用の金属箔の接着剤が、特開昭
６２−１７４０７６号公報の実施例に開示されている。In recent years, electronic components have become increasingly densely mounted on printed wiring boards. For this reason, in circuits that are becoming narrower and narrower, it has become necessary to improve the insulation performance between the circuits, particularly the tracking resistance. A metal foil adhesive for laminated plates having excellent tracking resistance is disclosed in Examples of JP-A-62-174076.
この接着剤はエポキシ樹脂、ポリビニルブチラール樹脂
、イソシアネート、ＢＦ３モノエチルアミン錯化合物な
どからな条ものでる。しかし、このものは、接着剤の貯
蔵安定性が悪く、製造直後から精々１週間位の間に使用
しなければならない問題を有していた。This adhesive is made of epoxy resin, polyvinyl butyral resin, isocyanate, BF3 monoethylamine complex, and the like. However, this adhesive had a problem in that the storage stability of the adhesive was poor and the adhesive had to be used within about one week at most immediately after production.
本発明は、金属張り積層板を作る際に用いる金属箔に塗
布される接着剤において、優れた耐トラツキング性を有
し、貯蔵安定性に優れた接着剤を提供することにある。An object of the present invention is to provide an adhesive that has excellent tracking resistance and excellent storage stability in an adhesive that is applied to metal foil used in making a metal-clad laminate.
本発明は、上記の点に鑑みて為されたものであリ、（ａ
） エポキシ＃Ａ脂５〜１５重量％、（ｂ） ポリ
ビニルブチラール樹脂４０〜６０重量％（ｃ） ポリ
イソシアネート樹脂１〜１０重量％、（ｄ） エーテ
ル化メラミン樹脂２０〜４０重量％、（ｅ） および
、エポキシ樹脂１００ｇ当たりｌＸｌ０−３〜Ｉ Ｘ
１０−３〜１×１０−１ｍｏｌ の範囲となる量のカル
ボン酸類を含有することを特徴とする積層板用金属箔の
接着剤を捉供することにある。The present invention has been made in view of the above points, and includes (a)
) Epoxy #A resin 5-15% by weight, (b) Polyvinyl butyral resin 40-60% by weight, (c) Polyisocyanate resin 1-10% by weight, (d) Etherified melamine resin 20-40% by weight, (e) and lXl0-3 to IX per 100g of epoxy resin
An object of the present invention is to provide an adhesive for metal foil for laminated plates, which is characterized by containing carboxylic acids in an amount ranging from 10-3 to 1 x 10-1 mol.
以下に、本発明について詳説する。The present invention will be explained in detail below.
エポキシ樹脂としては、ノボランク型エポキシ樹脂や、
ビスフェノールＡ型エポキシ樹脂およびこれに難燃性を
付与したハロゲン化の各エポキシ樹脂、あるいはこれら
の混合物などを用いることができる。その使用量は、５
〜１５重量％の範囲が特に好ましいのである。Epoxy resins include novolanc epoxy resins,
Bisphenol A type epoxy resins, halogenated epoxy resins with flame retardance added thereto, or mixtures thereof can be used. The amount used is 5
A range of 15% by weight is particularly preferred.
ポリビニルブチラール樹脂については、特に制限するも
のではないが、ブチラール化度６０〜９０モル％、重合
度８００〜３０００程度のものが好ましい特性を示し、
これらの単独、または混合物を、４０〜６０重量％の範
囲で用いることができる。Although there are no particular restrictions on the polyvinyl butyral resin, those with a degree of butyralization of about 60 to 90 mol% and a degree of polymerization of about 800 to 3000 exhibit preferable characteristics,
These can be used alone or in a mixture in an amount of 40 to 60% by weight.
ポリイソシアネート樹脂としては、重量平均分子量５０
０〜１０（１００の範囲のものを、１〜ＩＯ重量％の範
囲で用いることができる。The weight average molecular weight of the polyisocyanate resin is 50.
Those in the range of 0 to 10 (100) can be used in the range of 1 to IO weight %.
エーテル化メラミン樹脂としては、とくに限定するもの
ではないが、メチル化合物メラミン樹脂、エチル化メラ
ミン樹脂、ブチル化メラミン樹脂などを２０〜４０重量
％の範囲で用いることができる。The etherified melamine resin is not particularly limited, but methyl compound melamine resin, ethylated melamine resin, butylated melamine resin, etc. can be used in a range of 20 to 40% by weight.
カルボン酸類としては、フマル酸、アジピン酸、セパチ
ン酸、トリメリット酸などを用いることができ、中でも
フマル酸が特ムこ好ましい。その使用量は、前記エポキ
シ樹脂の１００重量部に対してｌＸｌ０−’〜ｌＸｌ０
−３〜１×１０−１ｍｏｌの範囲で用いることが必要で
ある。カルボン酸類の配合量をこの範囲に限定するのは
Ｉ Ｘ １０−３ｍｏ１未満の配合量では、得られる接
着剤の貯蔵安定性が十分ではなく、Ｉ Ｘ １０−３〜
１×１０−１ｍｏｌを超える配合量では金属箔の絶縁基
板に対する接着力が著しく低下し、積層板としての吸水
性や耐熱性が悪くなるからである。より好ましいのは、
Ｉ Ｘ １０−３〜Ｉ Ｘ ｌ ０−２１１１ｏｌ の
範囲である。As the carboxylic acids, fumaric acid, adipic acid, sepatic acid, trimellitic acid, etc. can be used, and among them, fumaric acid is particularly preferred. The amount used is lXl0-' to lXl0 per 100 parts by weight of the epoxy resin.
It is necessary to use it in the range of -3 to 1×10 −1 mol. The reason why the amount of carboxylic acids is limited to this range is that if the amount is less than IX 10-3 mo1, the resulting adhesive will not have sufficient storage stability.
This is because if the amount exceeds 1×10 −1 mol, the adhesive force of the metal foil to the insulating substrate will be significantly reduced, and the water absorption and heat resistance of the laminate will deteriorate. More preferable is
It is in the range of I x 10-3 to I x l 0-2111 ol.
以上の４つの樹脂成分を上記の範囲に限定するのは、こ
の範囲でないと硬化が十分に進まず、電気特性、吸水性
、金属箔のビール強度などに致命的な欠点を生じる金属
箔張り積層板しか得られないからである。The reason why the above four resin components are limited to the above ranges is that if they are not within these ranges, curing will not proceed sufficiently, resulting in fatal defects in electrical properties, water absorption, beer strength of metal foil, etc. This is because all you can get is a board.
以上の成分を接着剤の樹脂フェスとする溶媒としては、
ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミ
ド、ジオキサン、メチルエチルケトン（ＭＥＫ）、アセ
トン、メチルセロソルブ、トルエン、キシレン、メタノ
ール、エタノール、ブタノールなどの単独又は、混合し
たものを用いることができる。好ましくは高沸点の溶媒
と低沸点の溶媒の混合溶媒が、乾燥での溶媒の揮発が次
第に起こるので接着剤層に発生する気泡を少なくするの
に効果がある。なお、前記の４つの樹脂成分の合計の樹
脂含有率５〜５０重量％の樹脂フェス、好ましくは１０
〜３０重量％の樹脂フェスとなる量の溶媒を使用できる
。As a solvent for making the above ingredients into a resin face of adhesive,
Dimethylformamide (DMF), dimethylacetamide, dioxane, methyl ethyl ketone (MEK), acetone, methyl cellosolve, toluene, xylene, methanol, ethanol, butanol and the like can be used alone or in combination. Preferably, a mixed solvent of a high boiling point solvent and a low boiling point solvent is effective in reducing bubbles generated in the adhesive layer since the solvent gradually evaporates during drying. In addition, the resin face has a total resin content of 5 to 50% by weight of the above four resin components, preferably 10% by weight.
An amount of solvent can be used that results in a resin face of ~30% by weight.
金属箔としては、銅箔、アルミニウム箔、ステンレス箔
などがあるが、銅箔が電気伝導性の良好な点で好ましく
、この場合、電解銅箔、圧延銅箔いずれでも良く特に限
定するものではない。Examples of the metal foil include copper foil, aluminum foil, and stainless steel foil, but copper foil is preferable because of its good electrical conductivity.In this case, either electrolytic copper foil or rolled copper foil may be used, and there is no particular limitation. .
積層板用の金属箔は次の様にして作ることができる。す
なわち、前記４つの樹脂成分を含有する樹脂フェスをロ
ールコータ−で金属箔に乾燥後の−塗布量で２０〜７０
ｇ／ｍ”塗布、好ましくは２５〜４０ｇ／ｍ”塗布し、
１１０．−１７０°Ｃ，１〜１５分間、好ましくは１３
０〜１５０°Ｃ，１〜５分間乾燥機で樹脂フェスの溶媒
を飛ばすとともに樹脂の硬化を進めて半硬化させること
によって得られ、取扱い易い性状の樹脂性の金属箔とな
る。ここで言う半硬化の樹脂とは、さらに熱が加われば
樹脂が溶融し、硬化反応が起こり、かつ手で触れてもベ
トッキがなくこれらを重ねて置くことのできる性状のも
のを言う。Metal foil for laminates can be made as follows. That is, the coating amount after drying of the resin face containing the above four resin components on the metal foil with a roll coater is 20 to 70%.
g/m" coating, preferably 25 to 40 g/m" coating,
110. -170°C for 1 to 15 minutes, preferably 13
It is obtained by evaporating the solvent of the resin face in a dryer at 0 to 150°C for 1 to 5 minutes and curing the resin to semi-cure it, resulting in a resinous metal foil with easy-to-handle properties. The term "semi-cured resin" as used herein refers to a resin that melts when heat is applied, causing a curing reaction, and that is non-sticky when touched by hand and can be stacked one on top of the other.
この金属箔をプリプレグの少なくとも１枚以上の表面に
重ね合わせたものを、圧力３０〜７０ｋｇ１Ｃａ、温度
１２０〜１８０°Ｃで９０〜１５０分間、加熱加圧成形
し、金属張積層板を得ることができる。This metal foil is superimposed on the surface of at least one sheet of prepreg and then heated and pressure molded at a pressure of 30 to 70 kg/Ca and a temperature of 120 to 180°C for 90 to 150 minutes to obtain a metal clad laminate. can.
このプリプレグは、公知のエポキシ樹脂、ポリイミド樹
脂、フェノール樹脂、ポリエステル樹脂および、これら
の変性樹脂などの熱硬化性樹脂を用途に応じて適宜選択
して単独又は、組合せた樹脂を、基材に含浸させ、半硬
化させて得られる。This prepreg is made by impregnating a base material with thermosetting resins such as well-known epoxy resins, polyimide resins, phenol resins, polyester resins, and modified resins of these resins, selected individually or in combination as appropriate depending on the application. It is obtained by semi-curing.
なお、この基材の種類も特に限定されない。通常は、紙
、ガラスクロス等が用いられる。この他にポリイミド樹
脂繊維布等の高耐熱性有機繊維布や石英繊維布等の無機
繊維布等を用いてもよい。Note that the type of this base material is not particularly limited either. Usually, paper, glass cloth, etc. are used. In addition, highly heat-resistant organic fiber cloth such as polyimide resin fiber cloth, inorganic fiber cloth such as quartz fiber cloth, etc. may be used.
次に本発明を実施例と比較例によって説明する。Next, the present invention will be explained with reference to Examples and Comparative Examples.
〔実施例］
実施例 １〜４
エポキシ樹脂（東部化成製、 ＹＤＣＮ７０４） １０
重量部、ポリビニルブチラール樹脂（積水化学製、ニス
レットＫＳ−５Ｚ） ５２重量部、ポリイソシアネート
樹脂（大日本インキ製、プライオーフェンＺＰ−３０６
６）８重量部、ブチルエーテル化メラミン（三井東圧製
、ニーパン２２Ｒ） ３０重量部をベース樹脂として別
表第１表に示した各種カルボン酸類をエポキシ樹脂１０
０重量部に対して１．ＯＸ １０−２ｍｏｌ量を配合し
、これらをトルエン：メチルエヂルケトン（ＭＥＫ）：
メチルアルコールを５：５：４の混合溶媒４００重量部
に熔解して金属箔用の接着剤を調製した。これらの接着
剤を用い、一方は直ちに３５μｍ厚みの銅箔に、約３０
ｇ／ボの塗布量になるように塗布し、溶媒を飛ばすと同
時に接着剤の反応を進行させる乾燥をおこない接着剤付
の銅箔を得た。他方は、５０°Ｃに７日間放置した後、
同様に用いて、接着剤付の銅箔を得た。[Example] Examples 1 to 4 Epoxy resin (manufactured by Tobu Kasei, YDCN704) 10
Parts by weight, polyvinyl butyral resin (Sekisui Chemical Co., Ltd., Nislet KS-5Z) 52 parts by weight, polyisocyanate resin (Dainippon Ink Co., Ltd., Plyophen ZP-306)
6) Using 8 parts by weight of butyl etherified melamine (manufactured by Mitsui Toatsu, Kneepan 22R) as a base resin and 30 parts by weight as a base resin, various carboxylic acids shown in Table 1 were added to an epoxy resin of 10 parts by weight.
1.0 parts by weight. Blend 10-2 mol of OX and combine these with toluene: methyl edyl ketone (MEK):
An adhesive for metal foil was prepared by dissolving methyl alcohol in 400 parts by weight of a 5:5:4 mixed solvent. Using these adhesives, one side was immediately attached to a 35 μm thick copper foil by approximately 30 μm.
The copper foil coated with the adhesive was obtained by applying the adhesive in a coating amount of g/bo and drying to evaporate the solvent and at the same time advance the reaction of the adhesive. After leaving the other one at 50°C for 7 days,
Using the same method, copper foil with adhesive was obtained.
これらの銅箔を、通常の紙基材フェノール樹脂含浸プリ
プレグの表面に重ね、加熱加圧成形して得た銅張り積層
板から、５ ｃｍ平方角の試験片を切り出した。These copper foils were laminated on the surface of an ordinary paper-based phenol resin-impregnated prepreg, and a 5 cm square test piece was cut out from a copper-clad laminate obtained by hot-pressing molding.
貯蔵安定性の評価は、上記の試験片を２６０°Ｃの半田
浴に浮かした時に、積層板の表面に膨れを生じる迄の時
間で行った。結果を別表第１表に示した。貯蔵安定性が
悪いと接着性能が劣化し、プリプレグと銅箔の間の接着
力が不十分になり、加熱処理によって銅箔表面に膨れが
生じるのである。The storage stability was evaluated based on the time taken until blisters appeared on the surface of the laminate when the above test piece was floated in a solder bath at 260°C. The results are shown in Appendix Table 1. If the storage stability is poor, the adhesive performance deteriorates, the adhesive force between the prepreg and the copper foil becomes insufficient, and the surface of the copper foil becomes blistered during heat treatment.
実施例 ５〜８
エポキシ樹脂（東部化成製、 ＹＤＣＮ７０４） １０
重量部、ポリビニルブチラール樹脂（積水化学製、ニス
レットＭＳ−５２） ４７重量部、ポリイソシアネート
樹脂（大日本インキ製、プライオーフェンＺＦ−３０６
６）８重量部、ブチルエーテル化メラミン（三井東圧製
、ニーパン２２Ｒ） ３５重量部をベース樹脂として、
別表第２表に示したように、各実施例ごとに、フマル酸
の配合量を変えたものとアジピン酸で行った。他は、実
施例１と同様に行い、結果を別表第２表に示した。Examples 5 to 8 Epoxy resin (manufactured by Tobu Kasei, YDCN704) 10
Parts by weight, polyvinyl butyral resin (Sekisui Chemical Co., Ltd., Nislet MS-52) 47 parts by weight, polyisocyanate resin (Dainippon Ink Co., Ltd., Plyophen ZF-306)
6) 8 parts by weight, butyl etherified melamine (manufactured by Mitsui Toatsu, Kneepan 22R) 35 parts by weight as a base resin,
As shown in Table 2, each example was tested using different amounts of fumaric acid and adipic acid. The rest was carried out in the same manner as in Example 1, and the results are shown in Appendix Table 2.
比較例１
実施例５と同じベース樹脂に対してカルボン酸類を無添
加とした以外は実施例５と同様に行い、結果を別表第２
表に示した。Comparative Example 1 The same procedure as in Example 5 was carried out except that no carboxylic acids were added to the same base resin as in Example 5, and the results are shown in Appendix Table 2.
Shown in the table.
第２表よりカルボン酸類の無添加の比較例１はカルボン
酸類の添加の実施例１〜４に比べ、５０°Ｃ１保存した
後の半田耐熱での、膨れの発生するまでの時間が長く、
優れているのがわかる。From Table 2, compared to Examples 1 to 4 in which carboxylic acids were added, Comparative Example 1 without the addition of carboxylic acids took a longer time to generate blisters during soldering heat resistance after storage at 50°C.
I know it's excellent.
第１表より、カルボン酸類のなかでも、フマル酸が５０
°Ｃ３７日間保存した後の半田耐熱での、膨れの発生す
るまでの時間が最も長く、優れているのがわかる。From Table 1, among carboxylic acids, fumaric acid has a 50%
It can be seen that the soldering heat resistance after storage for 37 days at °C shows that it takes the longest time until blistering occurs, which is excellent.
なお、実施例、比較例とも、ＩＥＣ法による銅箔エツチ
ング面で行った耐トラツキング性はいずれも５００Ｖ以
上であった。In addition, in both Examples and Comparative Examples, the tracking resistance measured on the etched surface of the copper foil by the IEC method was 500 V or more.
本発明によって、耐トラツキング性に優れ、貯蔵安定性
に優れた接着剤を得ることができるのである。According to the present invention, it is possible to obtain an adhesive that has excellent tracking resistance and storage stability.
特許出願人 松下電工株式会社 代理人 佐藤 成示（ほか１名） 第１表Patent applicant Matsushita Electric Works Co., Ltd. Agent: Nariji Sato (and 1 other person) Table 1
Claims (2)
−＾３〜１×１０＾−＾１ｍｏｌの範囲となる量のカル
ボン酸類を含有することを特徴とする積層板用金属箔の
接着剤。(1) (a) 5-15% by weight of epoxy resin, (b) 40-60% by weight of polyvinyl butyral resin, (c) 1-10% by weight of polyisocyanate resin, (d) 20-40% by weight of etherified melamine resin, (e) and 1 x 10^ per 100g of epoxy resin
An adhesive for metal foil for laminated plates, characterized in that it contains a carboxylic acid in an amount ranging from -^3 to 1 x 10^-^1 mol.
とする請求項１記載の積層板用金属箔の接着剤。(2) The adhesive for a metal foil for a laminate according to claim 1, wherein the carboxylic acid is fumaric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2282937A JPH04154885A (en) | 1990-10-19 | 1990-10-19 | Adhesive of metallic foil for laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2282937A JPH04154885A (en) | 1990-10-19 | 1990-10-19 | Adhesive of metallic foil for laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04154885A true JPH04154885A (en) | 1992-05-27 |
Family
ID=17659047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2282937A Pending JPH04154885A (en) | 1990-10-19 | 1990-10-19 | Adhesive of metallic foil for laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04154885A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006137838A (en) * | 2004-11-11 | 2006-06-01 | Fujikura Ltd | Epoxy-based resin composition, epoxy resin-based adhesive composition, cover lay for flexible printed circuit board, copper-clad laminated board for flexible printed circuit board, the resultant flexible printed circuit board, prepreg, copper-clad laminated board, photosensitive dry film, photosensitive liquid resist, and printed wiring board |
| WO2023195481A1 (en) * | 2022-04-05 | 2023-10-12 | 住友ベークライト株式会社 | Adhesive composition for wet friction material, and wet friction plate |
-
1990
- 1990-10-19 JP JP2282937A patent/JPH04154885A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006137838A (en) * | 2004-11-11 | 2006-06-01 | Fujikura Ltd | Epoxy-based resin composition, epoxy resin-based adhesive composition, cover lay for flexible printed circuit board, copper-clad laminated board for flexible printed circuit board, the resultant flexible printed circuit board, prepreg, copper-clad laminated board, photosensitive dry film, photosensitive liquid resist, and printed wiring board |
| JP4707998B2 (en) * | 2004-11-11 | 2011-06-22 | 株式会社フジクラ | Epoxy resin adhesive composition for flexible printed circuit board, coverlay for flexible printed circuit board, copper-clad laminate for flexible printed circuit board, and flexible printed circuit board |
| WO2023195481A1 (en) * | 2022-04-05 | 2023-10-12 | 住友ベークライト株式会社 | Adhesive composition for wet friction material, and wet friction plate |
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