JPH0741206B2 - Method for producing cured polyimide resin coating - Google Patents
Method for producing cured polyimide resin coatingInfo
- Publication number
- JPH0741206B2 JPH0741206B2 JP60096972A JP9697285A JPH0741206B2 JP H0741206 B2 JPH0741206 B2 JP H0741206B2 JP 60096972 A JP60096972 A JP 60096972A JP 9697285 A JP9697285 A JP 9697285A JP H0741206 B2 JPH0741206 B2 JP H0741206B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide resin
- formula
- solvent
- coating
- copper alloy
- 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 - Lifetime
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- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は硬化ポリイミド樹脂被覆物の製造方法に関する
ものである。詳しくは本発明は、コイル状に巻回された
帯状の基板を巻出し、巻取り装置にて移動させながら、
該基板の少なくとも一部に溶媒可溶型ポリイミド樹脂を
塗布して被覆物を得る方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a method for producing a cured polyimide resin coating. More specifically, the present invention unwinds a strip-shaped substrate wound in a coil and moves it by a winding device,
The present invention relates to a method for applying a solvent-soluble polyimide resin to at least a part of the substrate to obtain a coating.
従来、電子材料用の部品等の精密塗布の要求される分
野、たとえば、大型のコンピユータ用のシールドコネク
タでは銅合金板の一部にポリイミド層がコーテイングさ
れており、これを所定のケースに何枚も嵌合してコネク
タの一部が構成されているものがあるが、このようなポ
リイミド層の付いた銅合金板は、従来、接着剤付ポリイ
ミドフイルムを貼り付けて製造したものであつた。しか
し、このような方法で製造されたものは、コネクタ製造
工程中におけるNaOH等による洗浄工程においてポリイミ
ドとは異る化学構造を持つ接着剤が溶解して密着性が低
下する等という問題点があつた。Conventionally, in fields where precision coating of parts for electronic materials is required, for example, in shielded connectors for large computers, a polyimide layer is coated on a part of a copper alloy plate. There is also a connector in which a part of the connector is formed by fitting, but such a copper alloy plate with a polyimide layer has been conventionally manufactured by adhering a polyimide film with an adhesive. However, the product manufactured by such a method has a problem that the adhesive having a chemical structure different from that of polyimide is dissolved in the cleaning process with NaOH or the like in the connector manufacturing process to lower the adhesion. It was
本発明者達はこれらの事情に鑑み、ポリイミドそのもの
を直接銅合金に密着せしめる事を鋭意検討した結果、銅
合金板の一部表面に溶媒可溶型ポリイミド樹脂を塗布
し、適当な条件で熱処理後、加熱硬化させることにより
本発明に到達した。In view of these circumstances, the present inventors have diligently studied that the polyimide itself is directly adhered to the copper alloy, and a solvent-soluble polyimide resin is applied to a part of the surface of the copper alloy plate, which is heat-treated under appropriate conditions. After that, the present invention was reached by heating and curing.
すなわち、本発明の要旨は帯状基板を移動させながら該
基板の一部表面に下記式で表わされる溶媒可溶型ポリイ
ミド樹脂の溶媒溶液を塗布し、まず、温度50〜120℃で
５〜120秒加熱処理を行ない、次いで、更に温度250〜45
0℃で15秒〜６分加熱することによりポリイミド樹脂を
硬化させることを特徴とする硬化ポリイミド樹脂被覆物
の製造方法。That is, the gist of the present invention is to apply a solvent solution of a solvent-soluble polyimide resin represented by the following formula on a partial surface of the substrate while moving the strip-shaped substrate, and first, at a temperature of 50 to 120 ° C. for 5 to 120 seconds. Heat treatment, then temperature 250 ~ 45
A method for producing a cured polyimide resin coating, which comprises curing the polyimide resin by heating at 0 ° C for 15 seconds to 6 minutes.
約20％の式 の繰り返し単位、および残り約80％の式 の繰り返し単位を有するポリイミド、あるいは、 約80％の式 の繰り返し単位、および残り約20％の式 の繰り返し単位を有する共ポリアミドイミドに存する。About 20% formula Repeat unit, and the formula of about 80% remaining With a repeating unit of, or about 80% of the formula Repeating unit, and the formula with about 20% remaining A copolyamideimide having a repeating unit of
以下に本発明を詳しく説明する。The present invention will be described in detail below.
本発明で基板とは通常コイル状に巻き取れるもので耐熱
性の高いもの、例えば金属薄板、プラスチツクシート等
が挙げられる。中でも銅薄板、ステンレス薄板等の金属
薄板が良好に用いられる。このような基板を張力をかけ
て巻き取りながら該基板を移動させ、その表面に溶媒可
溶型ポリイミド樹脂を塗布する。In the present invention, the substrate is usually one that can be wound into a coil and has high heat resistance, such as a thin metal plate and a plastic sheet. Among them, metal thin plates such as copper thin plates and stainless thin plates are preferably used. Such a substrate is moved while applying tension to the substrate, and the solvent-soluble polyimide resin is applied to the surface of the substrate.
樹脂としては溶媒溶液となし得る合成樹脂であれば何ん
でもよいが電気的絶縁性、耐熱性からポリイミドが好適
である。Any resin may be used as long as it is a synthetic resin that can be formed into a solvent solution, but polyimide is preferable in terms of electrical insulation and heat resistance.
本発明においてポリイミドとは、溶媒可溶型のものであ
り、約20％の式 の繰り返し単位、および残り約80％の式 の繰り返し単位を有するポリイミド、あるいは、 約80％の式 の繰り返し単位、および残り約20％の式 の繰り返し単位を有する共ポリアミドイミド等が挙げら
れる。In the present invention, the polyimide is a solvent-soluble type, the formula of about 20% Repeat unit, and the formula of about 80% remaining With a repeating unit of, or about 80% of the formula Repeating unit, and the formula with about 20% remaining And a copolyamideimide having a repeating unit of
本発明でポリイミド溶液とは、上記の共ポリイミドある
いは共ポリアミドイミドを、溶媒としてジメチルホルム
アミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロ
リドン等に溶解したもの等が挙げられる。Examples of the polyimide solution in the present invention include the above copolyimide or copolyamideimide dissolved in dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone or the like as a solvent.
塗布の方法としては、スクリーン印刷法、グラビアロー
ル印刷法、Ｔダイ法等が挙げられるが、これらの塗膜の
端部、特に基板の全面に塗布せず、一部に塗布した場合
の塗布部と未塗布部の境界部分は塗布直後には中央部と
比べて盛り上る傾向がある。この状態のまま乾燥させる
と両端の盛り上つた塗膜が形成されることになり電子部
品として組み立てるに当り不都合を生ずることとなる。
そこで、本発明においては、たとえばＴダイ等で塗布
後、50〜120℃、好ましくは60〜90℃で、５〜120秒間、
好ましくは20〜60秒間加熱処理を行なう。こうすること
により塗布面端部の盛り上りを消滅させるとともに、塗
膜全体の平面性を向上させることができる。Examples of the coating method include screen printing method, gravure roll printing method, T-die method, etc. Immediately after coating, the boundary between the uncoated area and the uncoated area tends to be higher than the central area. If it is dried in this state, a coating film having raised both ends is formed, which causes inconvenience in assembling as an electronic component.
Therefore, in the present invention, for example, after coating with a T-die or the like, at 50 to 120 ° C., preferably 60 to 90 ° C. for 5 to 120 seconds,
The heat treatment is preferably performed for 20 to 60 seconds. By doing so, it is possible to eliminate the swelling at the end of the coating surface and improve the flatness of the entire coating film.
この後、温度を徐々に上昇させながら250〜450℃、好ま
しくは275〜425℃で加熱硬化させる。Then, the temperature is gradually raised to heat-cure at 250 to 450 ° C, preferably 275 to 425 ° C.
加熱温度は、樹脂のガラス転移点付近あるいはそれ以上
であればよい。たとえばポリイミドであれば250〜450℃
程度、好ましくは300〜400℃程度、ポリアミドイミドで
あれば250〜375℃程度、好ましくは275〜350℃程度であ
る。The heating temperature may be near the glass transition point of the resin or higher. For example, in the case of polyimide 250-450 ℃
The temperature is preferably about 300 to 400 ° C, and the temperature is about 250 to 375 ° C, preferably about 275 to 350 ° C for polyamideimide.
加熱時間は塗布液の種類、濃度、濃厚等により異なる
が、溶媒がジメチルホルムアミド、溶液中の固形分濃度
20〜25wt（重量）％、膜厚10〜40μ（乾燥時換算）の場
合、加熱硬化温度が275〜350℃程度であれば１〜６分、
350〜400℃程度であれば30秒〜４分、400〜450℃程度で
あれば15秒〜２分が適当である。The heating time varies depending on the type, concentration, and concentration of the coating liquid, but the solvent is dimethylformamide, and the solid content concentration in the solution.
20 to 25 wt% and a film thickness of 10 to 40 μ (converted to dry time), 1 to 6 minutes if the heat curing temperature is about 275 to 350 ° C.
30 seconds to 4 minutes is suitable for 350 to 400 ° C, and 15 seconds to 2 minutes is suitable for 400 to 450 ° C.
溶媒としては、ジメチルホルムアミドの他、ジメチルア
セトアミド、Ｎ−メチル−２−ピロリドン、クレゾール
等が用いられるが、沸点のちがいにより、ベーキング温
度、時間に影響するので、上述のジメチルホルムアミド
の場合に準じて用いればよい。As the solvent, in addition to dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, cresol and the like are used, but the difference in boiling point affects the baking temperature and time. Therefore, according to the case of dimethylformamide described above. You can use it.
このようにして得られた塗膜は基板に直接的に接着して
おり、耐NaOH性が格段に改良されている。例えばコネク
タ用の部品等の電子材料用材料としてきわめて好適であ
る。なお、銅合金は圧延したままで塗布してもよいが、
ブラシ研摩、バフ研摩、スクラブ研摩等の物理的表面処
理、塩化第二鉄溶液等による化学的表面処理により表面
を微小に粗化することにより、ポリイミド塗膜との密着
性が一層向上する。The coating film thus obtained is directly adhered to the substrate, and the NaOH resistance is remarkably improved. For example, it is extremely suitable as a material for electronic materials such as parts for connectors. The copper alloy may be applied as rolled,
By finely roughening the surface by physical surface treatment such as brush polishing, buff polishing, scrub polishing, or chemical surface treatment with ferric chloride solution, the adhesion with the polyimide coating film is further improved.
上述の塗膜は基板の一方の面だけに形成させてもよい
し、両方の面に形成させてもよい。The above-mentioned coating film may be formed on only one surface of the substrate, or may be formed on both surfaces.
以下に実施例を挙げて本発明を更に詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１ ポリイミド樹脂としては 約80％の式 の繰返し単位、および残りの20％式 の繰返し単位を有する共ポリアミドイミドの22wt％溶液
（溶媒はジメチルホルムアミド）を用いた。Example 1 As a polyimide resin, a formula of about 80% is used. Repeating unit of, and the remaining 20% formula A 22 wt% solution of a copolyamideimide having a repeating unit of (the solvent was dimethylformamide) was used.
銅合金としてはCu−9Ni−2.3Sn系のものであり、幅15ミ
リメートル、厚さ0.35ミリメートル、長さ200メートル
のコイル状に巻回された薄板状のものを用いた。The copper alloy is of Cu- 9 Ni- 2.3 Sn system, using the width 15 mm 0.35 millimeters thick, those lengths 200 m lamellar wound in coiled.
このような銅合金の薄板を巻出し、巻取機、Ｔダイ（幅
10ミリ）、をそなえた連続塗布装置により銅合金の中央
部に幅10ミリの塗布幅で上記共ポリアミドイミド溶液を
塗布した。この後、80℃で30秒間加熱処理を行つたあ
と、温度を徐々に昇温させ300℃で２分間加熱硬化させ
た。形成された塗膜の厚さは25μであつた。この銅合金
の一部を切りとつて、塗膜上にカツターナイフで五盤目
状に傷をつけたあと80℃で50g/のNaOH水溶液に５分間
浸漬した。このあと水洗して、銅合金と塗膜との接着部
分を観察したが、剥離現象はみられなかつた。Unwind such a thin plate of copper alloy, winder, T-die (width
10 mm), the above copolyamideimide solution was applied to the central portion of the copper alloy with a coating width of 10 mm. After that, heat treatment was performed at 80 ° C. for 30 seconds, and then the temperature was gradually raised to heat cure at 300 ° C. for 2 minutes. The thickness of the formed coating film was 25μ. A part of this copper alloy was cut off, and the coating film was scratched in a fifth plate shape with a cutter knife and then immersed at 50 ° C. in a 50 g / NaOH aqueous solution for 5 minutes. After that, it was washed with water and the adhesion portion between the copper alloy and the coating film was observed, but no peeling phenomenon was observed.
実施例２ ポリイミド樹脂としては 約20％の式 の繰り返し単位、および残りの80％の式 の繰り返し単位を有する共ポリイミドの22wt％溶液（溶
媒はジメチルホルムアミド））を用いた。Example 2 About 20% of the formula for polyimide resin Repeating units, and the remaining 80% formula A 22 wt% solution of a copolyimide having a repeating unit of (a solvent is dimethylformamide) was used.
銅合金としてはCu−qNi−2.3Sn系のものであり、幅15ミ
リメートル、厚さ0.35ミリメートル、長さ200メートル
のコイル状に巻回された薄板状のものを用いた。As the copper alloy, a Cu-qNi-2.3Sn-based copper alloy having a width of 15 mm, a thickness of 0.35 mm, and a length of 200 m, which was wound into a coil, was used.
このような銅合金の薄板を巻出し、巻取機、Ｔダイ（幅
10ミリ）をそなえた連続塗布装置により銅合金の中央部
に幅10ミリの塗布幅で上記共ポリイミド溶液を塗布し
た。この後、80℃で30秒間加熱処理を行つたあと、温度
を徐々に昇温させ320℃で２分間加熱硬化させた。形成
された塗膜の厚さは25μであつた。この銅合金の一部を
切りとって、塗膜上にカッターナイフで五盤目状に傷を
つけたあと80℃で50g/のNaOH水溶液に５分間浸漬し
た。このあと水洗して、銅合金と塗膜との接着部分を観
察したが、剥離現象はみられなかつた。Unwind such a thin plate of copper alloy, winder, T-die (width
The above-mentioned copolyimide solution was applied to the central portion of the copper alloy with a coating width of 10 mm by a continuous coating device equipped with 10 mm). After that, heat treatment was performed at 80 ° C. for 30 seconds, and then the temperature was gradually raised to heat cure at 320 ° C. for 2 minutes. The thickness of the formed coating film was 25μ. A part of this copper alloy was cut off, the coating film was scratched in a fifth pattern with a cutter knife, and then immersed at 50 ° C. in a 50 g / NaOH aqueous solution for 5 minutes. After that, it was washed with water and the adhesion portion between the copper alloy and the coating film was observed, but no peeling phenomenon was observed.
本発明の方法によれば基板の表面に均一な厚さのポリイ
ミド樹脂膜を連続的に形成することができ、コネクター
等の部品として使用し得る被覆物が容易に得られる。According to the method of the present invention, a polyimide resin film having a uniform thickness can be continuously formed on the surface of a substrate, and a coating that can be used as a component such as a connector can be easily obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 酒井 静枝 神奈川県横浜市緑区鴨志田町1000番地 三 菱化成工業株式会社総合研究所内 (56)参考文献 特開 昭56−103257（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shizue Sakai 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Co., Ltd. (56) Reference JP-A-56-103257 (JP, A)
Claims (1)
面に下記式で表わされる溶媒可溶型ポリイミド樹脂の溶
媒溶液を連続的に塗布し、まず、温度50〜120℃で５〜1
20秒加熱処理を行ない、次いで、更に温度250〜450℃で
15秒〜６分加熱することによりポリイミド樹脂を硬化さ
せることを特徴とする硬化ポリイミド樹脂被覆物の製造
方法。 約20％の式 の繰り返し単位、および残り約80％の式 の繰り返し単位を有する共ポリイミド、あるいは、 約80％の式 の繰り返し単位、および残り約20％の式 の繰り返し単位を有する共ポリアミドイミド。1. A moving solution of a belt-shaped substrate is continuously coated with a solvent solution of a solvent-soluble polyimide resin represented by the following formula on a partial surface of the substrate, and first, at a temperature of 50 to 120 ° C. for 5 to 1
Heat treatment for 20 seconds, then at a temperature of 250-450 ℃
A method for producing a cured polyimide resin coating, which comprises curing the polyimide resin by heating for 15 seconds to 6 minutes. About 20% formula Repeat unit, and the formula of about 80% remaining Co-polyimide with repeating units of about 80% Repeating unit, and the formula with about 20% remaining A copolyamideimide having a repeating unit of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096972A JPH0741206B2 (en) | 1985-05-08 | 1985-05-08 | Method for producing cured polyimide resin coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096972A JPH0741206B2 (en) | 1985-05-08 | 1985-05-08 | Method for producing cured polyimide resin coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61257271A JPS61257271A (en) | 1986-11-14 |
| JPH0741206B2 true JPH0741206B2 (en) | 1995-05-10 |
Family
ID=14179133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60096972A Expired - Lifetime JPH0741206B2 (en) | 1985-05-08 | 1985-05-08 | Method for producing cured polyimide resin coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0741206B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0785792B2 (en) * | 1986-05-07 | 1995-09-20 | 三菱化学株式会社 | Method for producing cured polyimide resin coating |
| JPH0649185B2 (en) * | 1988-12-29 | 1994-06-29 | 新日鐵化学株式会社 | Flexible printed wiring board manufacturing method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56103257A (en) * | 1980-01-21 | 1981-08-18 | Daikin Ind Ltd | Undercoating composition for fluororesin coating |
-
1985
- 1985-05-08 JP JP60096972A patent/JPH0741206B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61257271A (en) | 1986-11-14 |
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