JPH0322410B2 - - Google Patents
Info
- Publication number
- JPH0322410B2 JPH0322410B2 JP2756789A JP2756789A JPH0322410B2 JP H0322410 B2 JPH0322410 B2 JP H0322410B2 JP 2756789 A JP2756789 A JP 2756789A JP 2756789 A JP2756789 A JP 2756789A JP H0322410 B2 JPH0322410 B2 JP H0322410B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- adhesive
- clad laminate
- manufacturing
- copper foil
- 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
Links
- 239000000853 adhesive Substances 0.000 claims description 27
- 230000001070 adhesive effect Effects 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000011889 copper foil Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 206010034133 Pathogen resistance Diseases 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 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 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- VCRZAKVGPJFABU-UHFFFAOYSA-N 10-phenoxarsinin-10-yloxyphenoxarsinine Chemical compound C12=CC=CC=C2OC2=CC=CC=C2[As]1O[As]1C2=CC=CC=C2OC2=CC=CC=C21 VCRZAKVGPJFABU-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
［発明の目的］
（産業上の利用分野）
本発明は、銅張積層板の製造方法に関し、特に
耐菌性と、電気絶縁材料としての特性、印刷配線
板としての特性とを、併せ有する銅張積層板の製
造方法に関するものである。
（従来技術）
印刷配線板に用いられる、エポキシ樹脂、シリ
コーン樹脂、ポリイミド樹脂、ポリウレタン樹
脂、ポリエステル樹脂などの銅張積層板は、高温
度高湿度下にさらされると、菌（カビ、バクテリ
ア等）が発育しやすい。そのような銅張積層板に
菌が発育すると、電気絶縁性の極端な低下、回路
の浸食、外観の変化等、大きな被害が起こる。最
近は、回路が精密になつたこともあり、わずかな
回路の浸食も許さない、信頼性の高い銅張積層板
が要求されている。
このために、銅張積層板自体に耐菌性を付与で
きれば希ましいが、銅張積層板は高温の乾燥工程
や成形工程を経るなどして製造されるものであ
り、また、エツチング工程やメツキ工程では激し
く化学薬品にさらされて加工されるものである。
したがつて、耐菌性、電気絶縁性、印刷配線加工
性を同時に満足できる製造方法を見いだすことは
容易になしえぬことであつた。
一般的に行われている銅張積層板の製造方法を
工程順に説明する。
使用目的に合わせ、エポキシ樹脂、ポリイミ
ド樹脂、シリコーン樹脂等の熱硬化性樹脂を溶
剤に溶かし、プリプレグ用ワニスとする。この
ワニスに、さらに溶剤を加えて、含浸のための
適当な粘度とし、これをガラスクロス、紙等の
基材に含浸乾燥してプリプレグとする。
使用目的に合わせ、フエノール樹脂、エポキ
シ樹脂、ビニルブチラール樹脂等の接着性樹脂
液を、銅箔の片面に塗布し、120〜150℃のオー
ブンで５〜20分間加熱乾燥して、接着性樹脂液
の揮発分が２〜８重量％程度になるようにし
て、接着剤銅箔を得る。
プリプレグを数枚重ね、次に接着剤付銅箔
を、接着剤面をプリプレグ側にして重ねて、
150〜180℃に加熱したプレス熱盤間にはさみ10
〜150Kg／cm2の圧力下で、60〜180分間加熱加圧
して銅張積層板を得る。
［発明の構成］
（課題を解決するための手段と作用）
本発明は、銅張積層板に、耐菌性と、電気絶縁
材料としての特性、印刷配線板としての特性と
を、併せ付与する製造方法を種々検討した結果、
以下に示す方法を発明したものである。
すなわち、本発明は、銅箔と積層板との接合
に、接着剤を塗布乾燥し、加熱加圧して銅張積層
板を製造する際に、10，10′−オキシビスフエノ
キサアルシンを、接着剤中の樹脂固形分に対して
0.02重量％〜0.2重量％の割合で、添加混合した
接着剤を用いることを特徴とする、耐菌性を有す
る銅張積層板の製造方法である。
本発明に用いる除菌剤は、次の構造を有する
10，10′−オキシビスフエノキサアルシン［10，
10′−oxybisphenoxarsine］である。
この防菌剤は、前記した銅張積層板の製造工程
と加工工程によつて特性の失われない防菌剤であ
る。
そして防菌剤は、接着剤に添加混合して使用す
る。接着剤中に含有させることにより、菌の回路
への浸食を最もよく防止することができ、防菌剤
の使用量を最少にすることができる。しかも、片
面銅張積層板の積層板面でさえ菌の成育を防止す
ることができる。
防菌剤の添加量について検したが、接着剤中の
樹脂固形分に対して、10，10′−オキシビスフエ
ノキサアルシンは0.02重量％〜0.2重量％の割合
で、添加するのがよい。下限未満の添加量では十
分な耐菌性がえられない。また上限を超えた添加
量を加えると、はんだ耐熱性、耐薬品性、引きは
がし強さ及び電気的特性に悪影響があらわれはじ
め、実用上支障となるばかりでなく、耐菌性も逆
に低下する。
防菌剤を接着剤に添加混合するには、メチルエ
チルケトン等の溶剤に溶解して加えるのがよい。
銅箔と積層板とを接着させるには、前記したよう
に接着剤付銅箔を用いたプリプレグの成形と同時
に接着させてもよく、合成樹脂シートに重ねて接
着剤のために加熱加圧して接着させてもよい。フ
イルムに銅箔を接着させればフレキシブル銅張板
が得られる。
本発明によれば、銅箔の接着剤に防菌剤を添加
混合する工程を加えただけで、簡単に耐菌性を有
する銅張積層板を得ることができる。得られた銅
張積層板は、耐菌性と同時に、電気的特性と印刷
配線用特性とを満足するものであり、菌による回
路の浸食を防止するのに、極めて少量で有効であ
る。
（実施例）
以下実施例を示すが、本発明はこれら例示によ
つて限定されるものではない。部、％とあるの
は、夫々重量部、重量％を意味する。
実施例 １
接着剤：アルカリ触媒を使用した液状フエノー
ル樹脂４５部、エポキシ樹脂（アラルダイト
ECN−1280、チバ社商品名）５部、ポリビニル
ブチラール50部とエチルアルコールとメチルエチ
ルケトンの１：１混合溶剤を用いて溶解し、濃度
20％の接着剤を調製した。
防菌剤の添加：防菌剤として10，10′−オキシ
ビスフエノキサアルシンをメチルエチルケトンに
溶解して２％溶液とし、接着剤固形分100部に防
菌剤0.025重量部を添加し、室温で十分均一にな
るまで撹拌混合した。
接着剤付銅箔：防菌剤入接着剤を35μｍ厚の銅
箔の片面に塗布して風乾後、120℃で10分間乾燥
して、接着剤付銅箔とした。
銅張積層板：接着剤付銅箔を、セルロース紙基
材エポキシ樹脂含浸プリプレグに重畳して、150
℃、120Kg／cm2、90分の加熱加圧条件で成形して
銅張積層板（1.6mm厚）を得た。
実施例２〜３
第１表に示した組成の接着剤に、10，10′−オ
キシビスフエノキサアルシンを第１表に示した添
加量によつて防菌剤入接着剤を調製し、他は実施
例１と同様にして、紙基材エポキシ樹脂銅張積層
板（実施例２）及びガラス布基材エポキシ樹脂銅
張積層板（実施例３）を得た。
[Purpose of the invention] (Industrial application field) The present invention relates to a method for manufacturing a copper-clad laminate, and particularly relates to a method for manufacturing a copper-clad laminate, and particularly relates to a method for manufacturing a copper-clad laminate, and particularly relates to a method for manufacturing a copper-clad laminate, and particularly relates to a method for manufacturing a copper-clad laminate, and in particular, the invention relates to a method for manufacturing a copper-clad laminate. The present invention relates to a method for manufacturing a stretched laminate. (Prior art) Copper-clad laminates made of epoxy resins, silicone resins, polyimide resins, polyurethane resins, polyester resins, etc., used for printed wiring boards, are susceptible to mold (mold, bacteria, etc.) when exposed to high temperatures and high humidity. is easy to grow. When bacteria grow on such copper-clad laminates, major damage occurs, such as an extreme drop in electrical insulation, erosion of circuits, and changes in appearance. Recently, as circuits have become more precise, there is a demand for highly reliable copper-clad laminates that do not allow even the slightest erosion of the circuits. For this reason, it would be desirable if the copper-clad laminates themselves could be made resistant to bacteria, but copper-clad laminates are manufactured through a high-temperature drying process or a molding process, and they also require an etching process or an etching process. The plating process involves intense exposure to chemicals.
Therefore, it has not been easy to find a manufacturing method that can simultaneously satisfy the requirements of bactericidal resistance, electrical insulation, and printed wiring processability. A commonly used method for manufacturing copper-clad laminates will be explained step by step. Depending on the purpose of use, thermosetting resins such as epoxy resins, polyimide resins, and silicone resins are dissolved in a solvent to create prepreg varnishes. A solvent is further added to this varnish to obtain a suitable viscosity for impregnation, and this is impregnated into a base material such as glass cloth or paper and dried to form a prepreg. Depending on the purpose of use, apply an adhesive resin liquid such as phenol resin, epoxy resin, vinyl butyral resin, etc. to one side of the copper foil, heat dry it in an oven at 120 to 150°C for 5 to 20 minutes, and then apply the adhesive resin liquid to one side of the copper foil. An adhesive copper foil is obtained by adjusting the volatile content of the adhesive to be about 2 to 8% by weight. Layer several sheets of prepreg, then layer copper foil with adhesive, with the adhesive side facing the prepreg.
Scissors between press heating plates heated to 150-180℃10
A copper clad laminate is obtained by heating and pressing for 60 to 180 minutes under a pressure of ~150 Kg/ cm2 . [Structure of the invention] (Means and effects for solving the problems) The present invention provides a copper-clad laminate with germ resistance, properties as an electrical insulating material, and properties as a printed wiring board. As a result of considering various manufacturing methods,
The method described below was invented. That is, the present invention applies 10,10'-oxybisphenoxaarsine when manufacturing a copper-clad laminate by applying an adhesive to the bond between the copper foil and the laminate, drying it, heating and pressing it, Based on the resin solid content in the adhesive
This is a method for manufacturing a copper-clad laminate having germ resistance, characterized by using an adhesive added and mixed in a proportion of 0.02% to 0.2% by weight. The disinfectant used in the present invention has the following structure.
10,10′-oxybisphenoxaarsine [10,
10'-oxybisphenoxarsine]. This antibacterial agent is an antibacterial agent that does not lose its properties during the manufacturing and processing steps of the copper-clad laminate described above. The antibacterial agent is used by being added to the adhesive. By including it in the adhesive, the invasion of bacteria into the circuit can be best prevented and the amount of antibacterial agent used can be minimized. Moreover, the growth of bacteria can be prevented even on the laminate surface of a single-sided copper-clad laminate. We examined the amount of antibacterial agent added and found that it is recommended to add 10,10'-oxybisphenoxaarsine at a rate of 0.02% to 0.2% by weight based on the resin solid content in the adhesive. . If the amount added is less than the lower limit, sufficient bacterial resistance cannot be obtained. Furthermore, if the amount added exceeds the upper limit, it will begin to have an adverse effect on solder heat resistance, chemical resistance, peel strength, and electrical properties, which will not only be a practical hindrance, but also cause a decrease in bacterial resistance. . When adding and mixing the antibacterial agent to the adhesive, it is preferable to dissolve it in a solvent such as methyl ethyl ketone and then add it.
To bond the copper foil and the laminate, as described above, the adhesive may be bonded at the same time as the prepreg is formed using the copper foil, or the copper foil may be layered on a synthetic resin sheet and heated and pressed for the adhesive. It may also be glued. By adhering copper foil to a film, a flexible copper-clad board can be obtained. According to the present invention, a copper-clad laminate having antibacterial properties can be easily obtained by simply adding a step of adding and mixing an antibacterial agent to an adhesive for copper foil. The obtained copper-clad laminate satisfies not only germ resistance but also electrical properties and properties for printed wiring, and is effective in preventing corrosion of circuits by bacteria in a very small amount. (Examples) Examples will be shown below, but the present invention is not limited to these examples. Parts and % mean parts by weight and % by weight, respectively. Example 1 Adhesive: 45 parts of liquid phenolic resin using an alkali catalyst, epoxy resin (Araldite
Dissolve 5 parts of ECN-1280 (Ciba brand name), 50 parts of polyvinyl butyral in a 1:1 mixed solvent of ethyl alcohol and methyl ethyl ketone, and
A 20% adhesive was prepared. Addition of antibacterial agent: Dissolve 10,10'-oxybisphenoxaarsine in methyl ethyl ketone to make a 2% solution as an antibacterial agent, add 0.025 parts by weight of the antibacterial agent to 100 parts of adhesive solids, and leave at room temperature. The mixture was stirred and mixed until the mixture was sufficiently homogeneous. Adhesive-coated copper foil: An antibacterial agent-containing adhesive was applied to one side of a 35 μm thick copper foil, air-dried, and then dried at 120° C. for 10 minutes to obtain an adhesive-coated copper foil. Copper-clad laminate: adhesive-coated copper foil is superimposed on cellulose paper-based epoxy resin-impregnated prepreg.
A copper-clad laminate (1.6 mm thick) was obtained by molding under heating and pressing conditions of 120 Kg/cm 2 at 120 Kg/cm 2 for 90 minutes. Examples 2 to 3 Antibacterial agent-containing adhesives were prepared by adding 10,10'-oxybisphenoxaarsine in the amounts shown in Table 1 to the adhesives having the compositions shown in Table 1. Otherwise, a paper-based epoxy resin copper-clad laminate (Example 2) and a glass cloth-based epoxy resin copper-clad laminate (Example 3) were obtained in the same manner as in Example 1.
【表】
比較例１〜３
第２表に示した組成の接着剤を用い、防菌剤を
添加せずに、他は実施例１と同様にして、紙基材
エポキシ樹脂銅張積層板を得た。[Table] Comparative Examples 1 to 3 Paper-based epoxy resin copper-clad laminates were prepared in the same manner as in Example 1, using adhesives with compositions shown in Table 2 and without adding antibacterial agents. Obtained.
【表】
実施例と比較例の耐菌性、はんだ耐熱性、接着
性、電気的特性、耐薬品性などを測定して、第３
表に対照したように実施例のものはすぐれた成績
を示した。[Table] Bacterial resistance, soldering heat resistance, adhesion, electrical properties, chemical resistance, etc. of Examples and Comparative Examples were measured.
As compared to the table, the examples showed excellent results.
【表】【table】
Claims (1)
し、加熱加圧して銅張積層板を製造する際に、
10，10′−オキシビスフエノキサアルシンを、接
着剤中の樹脂固形分に対して0.02重量％〜0.2重
量％の割合で、添加混合した接着剤を用いること
を特徴とする、耐菌性を有する銅張積層板の製造
方法。1. When manufacturing a copper-clad laminate by applying an adhesive to the bond between the copper foil and the laminate, drying it, and applying heat and pressure,
Bacterial resistance characterized by using an adhesive in which 10,10′-oxybisphenoxaarsine is added and mixed in a proportion of 0.02% to 0.2% by weight based on the resin solid content in the adhesive. A method for manufacturing a copper-clad laminate having the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2756789A JPH01232033A (en) | 1989-02-08 | 1989-02-08 | Manufacture of copper-clad laminates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2756789A JPH01232033A (en) | 1989-02-08 | 1989-02-08 | Manufacture of copper-clad laminates |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11649880A Division JPS5741950A (en) | 1980-08-26 | 1980-08-26 | Manufacture of copper lined laminated plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01232033A JPH01232033A (en) | 1989-09-18 |
| JPH0322410B2 true JPH0322410B2 (en) | 1991-03-26 |
Family
ID=12224603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2756789A Granted JPH01232033A (en) | 1989-02-08 | 1989-02-08 | Manufacture of copper-clad laminates |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01232033A (en) |
-
1989
- 1989-02-08 JP JP2756789A patent/JPH01232033A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01232033A (en) | 1989-09-18 |
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