JPH0785792B2 - Method for producing cured polyimide resin coating - Google Patents
Method for producing cured polyimide resin coatingInfo
- Publication number
- JPH0785792B2 JPH0785792B2 JP61104204A JP10420486A JPH0785792B2 JP H0785792 B2 JPH0785792 B2 JP H0785792B2 JP 61104204 A JP61104204 A JP 61104204A JP 10420486 A JP10420486 A JP 10420486A JP H0785792 B2 JPH0785792 B2 JP H0785792B2
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- polyimide resin
- coating
- structure represented
- substrate
- 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
Links
- 239000011248 coating agent Substances 0.000 title claims description 34
- 238000000576 coating method Methods 0.000 title claims description 34
- 229920001721 polyimide Polymers 0.000 title claims description 29
- 239000009719 polyimide resin Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000758 substrate Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910000881 Cu alloy Inorganic materials 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000005498 polishing Methods 0.000 description 3
- SYRYWPVKZTYAFV-UHFFFAOYSA-N 1-isocyano-4-[(4-isocyanophenyl)methyl]benzene Chemical compound C1=CC([N+]#[C-])=CC=C1CC1=CC=C([N+]#[C-])C=C1 SYRYWPVKZTYAFV-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 2,3,5-benzenetricarboxylic anhydride Chemical class 0.000 description 1
- YKQNDHBJPRVKPY-UHFFFAOYSA-N 2,4-diisocyano-1-methylbenzene Chemical compound CC1=CC=C([N+]#[C-])C=C1[N+]#[C-] YKQNDHBJPRVKPY-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 241001648319 Toronia toru Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning 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
- 229930003836 cresol Natural products 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
- 230000009477 glass transition Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (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
帯状の基板を巻回し、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 winds a strip-shaped substrate wound in a coil shape 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、大型コンピュ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 a shield connector for a large computer, a polyimide layer is coated on a part of a copper alloy plate, and many polyimide layers are coated in a predetermined case. There is a case where 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、モリイミドそのもの
を直接銅合金等の帯状基板に密着せしめる事を鋭意検討
した結果、該基板の表面に適当な粘度の溶媒可溶型ポリ
イミド樹脂の溶媒溶液を塗布し、さらに加熱により溶媒
を蒸発し、該樹脂を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 molyimide itself is directly adhered to a strip-shaped substrate such as a copper alloy, and as a result, a solvent solution of a solvent-soluble polyimide resin having an appropriate viscosity is formed on the surface of the substrate. The present invention was achieved by coating, further evaporating the solvent by heating, and heating and curing the resin.
すなわち、本発明の要旨は帯状基板を移動させながら該
基板の表面に粘度10〜1000ポアズ（測定条件25℃）の下
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Ｔダイ法により塗布し、ついで加熱処理を行って該樹
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 having a viscosity of 10 to 1000 poise (measurement condition: 25 ° C.) to the surface of the substrate while moving the belt-shaped substrate by the T-die method. Then, a heat treatment is performed to cure the resin, and a method for producing a cured polyimide resin coating is characterized.
繰り返し単位の10〜30モル％が式 で表わされる構造を有し、および残り90〜70モル％が式 で表わされる構造を有する共ポリイミド、あるいは、 繰り返し単位の70〜90モル％が式 で表わされる構造を有し、および残り30〜10モル％が式 で表わされる構造を有する共ポリアミドイミド、に存す
る。10 to 30 mol% of the repeating unit is the formula With a structure represented by A copolyimide having a structure represented by, or 70 to 90 mol% of repeating units are represented by the formula And has a structure represented by A copolyamideimide having a structure represented by
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、その表面に溶接可
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. The substrate is moved while applying tension to the substrate to wind the substrate, and a welding-soluble polyimide resin is applied to the surface of the substrate.
本発明において溶媒可溶型ポリイミド樹脂とは、溶媒可
溶型のものであり下記特定の式で表わされる共ポリイミ
ドおよび共ポリアミドイミドをいう。In the present invention, the solvent-soluble polyimide resin is a solvent-soluble polyimide resin and refers to a copolyimide and a copolyamideimide represented by the following specific formula.
（Ａ）繰り返し単位の10〜30モル％が式 で表わされる構造を有し、および残り90〜70モル％が式 で表わされる構造を有する共ポリイミド、あるいは、 で表わされる構造を有し、および残り30〜10モル％が式 で表わされる構造を有する共ポリアミドイミド。(A) 10 to 30 mol% of the repeating unit has the formula With a structure represented by A copolyimide having a structure represented by, or And has a structure represented by A copolyamideimide having a structure represented by:
なお、溶媒可溶型ポリイミド樹脂は、この中に第２成分
としてポリサルホン、ポリエーテルサルホン等の溶媒可
溶型ポリマーを混合したものも含まれる。The solvent-soluble polyimide resin also includes a mixture of a solvent-soluble polymer such as polysulfone or polyether sulfone as the second component.
上記の共ポリイミドは、たとえばベンゾフェノンテトラ
カルボン酸二無水物（BTDA）と２種の芳香族ジイソシア
ナート、すなわち4,4′−ジイソシアノジフェニルメタ
ンおよび2,4−ジイソシアノトルエンを共重合させて合
成することができる。また、上記の共ポリアミドイミド
は、２種の芳香族ポリカルボン酸、すなわち2,3,5−ベ
ンゼントリカルボン酸無水物および2,6−ベンゼンジカ
ルボン酸と4,4′−ジイソシアノジフェニルメタンを共
重合させて合成することができる。The above-mentioned copolyimide is obtained by copolymerizing, for example, benzophenone tetracarboxylic dianhydride (BTDA) and two aromatic diisocyanates, that is, 4,4'-diisocyanodiphenylmethane and 2,4-diisocyanotoluene. Can be synthesized. In addition, the above copolyamide imide has two aromatic polycarboxylic acids, namely, 2,3,5-benzenetricarboxylic anhydride and 2,6-benzenedicarboxylic acid, and 4,4'-diisocyanodiphenylmethane. It can be synthesized by polymerization.
本発明方法においては、溶媒可溶型ポリイミド樹脂の溶
媒溶液として、上記特定の式で表わされる共ポリイミド
または共ポリアミドイミドを、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
の有機溶媒に溶解したものを用いるが、その粘度が所定
範囲に調整されたものであることが重要である。In the method of the present invention, as a solvent solution of a solvent-soluble polyimide resin, copolyimide or copolyamideimide represented by the above specific formula, dimethylformamide,
What is dissolved in an organic solvent such as dimethylacetamide or N-methyl-2-pyrrolidone is used, but it is important that its viscosity is adjusted to a predetermined range.
溶媒可溶型ポリイミド樹脂の溶媒溶液の粘度としては10
〜1,000ポアズ（測定値25℃）、好ましくは20〜500ポア
ズ（測定値25℃）が好適に用いられる。The viscosity of the solvent solution of solvent-soluble polyimide resin is 10
〜1,000 poise (measured value 25 ° C), preferably 20-500 poise (measured value 25 ° C) are suitably used.
上記の粘度に対応する固形分濃度の値は、使用する溶媒
可溶型ポリイミド樹脂の種類と分子量、溶媒の種類等に
よつても異なるが本発明で好適に用いられる前述の共ポ
リイミドであれば、12〜32重量％、好ましくは17〜27重
量％であり、共ポリアミドイミドであれば10〜30重量
％、好ましくは15〜25重量％である。The value of the solid content concentration corresponding to the above-mentioned viscosity is different depending on the type and molecular weight of the solvent-soluble polyimide resin used, the type of solvent, etc. , 12 to 32% by weight, preferably 17 to 27% by weight, and copolyamideimide is 10 to 30% by weight, preferably 15 to 25% by weight.
なお、粘度の測定はＥ型回転粘度計により常法に従つて
行うことができる。The viscosity can be measured by an E-type rotational viscometer according to a conventional method.
上記溶媒溶液を塗布する方法としては、一般的にはスク
リーン印刷法、グラビアロール印刷法、Ｔダイ法等が考
えられるが、本発明方法においてはＴダイ法によって塗
布する。As a method for applying the solvent solution, a screen printing method, a gravure roll printing method, a T-die method and the like are generally considered, but in the method of the present invention, the T-die method is applied.
溶媒可溶型ポリイミド樹脂の溶媒溶液の粘度が10ポアズ
未満であると、Ｔダイ法で塗布する際、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と
未塗布部の境界部分において、該溶液が流動して直線性
を保てなくなつたり、溶媒可溶型ポリイミドの種類によ
つては加熱硬化後の塗膜の表面にゆず肌と呼ばれる平滑
性不良が発生して好ましくない。When the viscosity of the solvent solution of the solvent-soluble polyimide resin is less than 10 poise, when applying by the T-die method, the edge of the coating, especially the entire surface of the substrate is not coated At the boundary between the uncoated part and the uncoated part, the solution flows and loses its linearity, and depending on the type of solvent-soluble polyimide, the surface of the coating film after heating and curing is called smooth skin. It is not preferable because defects occur.
また、溶媒可溶型ポリイミド樹脂の溶媒溶液の粘度が10
00ポアズを超えるとＴダイ吐出部での該溶液の流動抵抗
が大きくなり、動力上不利であり、やはり好ましくな
い。Further, the viscosity of the solvent solution of the solvent-soluble polyimide resin is 10
If it exceeds 00 poise, the flow resistance of the solution at the T-die discharge part becomes large, which is disadvantageous in terms of power and is also not preferable.
Ｔダイ法を用いる本発明方法においては、粘度が上記特
定範囲の塗布液を使用することにより、塗布の膜厚の均
一性および塗膜の端部、特に基板の全面に塗布せず一部
に塗布するときの塗布部と非塗布部との境界部分の直線
性の良好な塗膜を形成することが可能であるが、膜厚の
均一性および境界部分の直線性を一層良好に保つために
は、塗布液の吐出量、帯状基板の移動速度等を精度よく
コントロールする必要がある。In the method of the present invention using the T-die method, by using a coating solution having a viscosity in the above-mentioned specific range, the uniformity of the coating film thickness and the edge portion of the coating film, particularly the entire surface of the substrate without being coated, are partially covered. It is possible to form a coating with good linearity at the boundary between the coated part and the non-coated part at the time of coating, but in order to keep the uniformity of the film thickness and the linearity at the boundary even better. It is necessary to accurately control the discharge amount of the coating liquid, the moving speed of the strip substrate, and the like.
このような塗膜は基板の片側あるいは両側に形成させる
ことができる。またＴダイの形状、寸法に応じて種々の
幅の塗膜、同一表面上に複数の塗膜を形成させることも
当然可能である。Such a coating can be formed on one side or both sides of the substrate. Further, it is naturally possible to form a coating film having various widths according to the shape and size of the T-die, or to form a plurality of coating films on the same surface.
塗布されたあとは、加熱処理によつて溶媒を蒸発除去
し、樹脂を硬化させる。まず50〜120℃程度で溶媒の大
部分を除去した後、徐々に昇温させて250〜450℃、好ま
しくは275〜425℃で加熱硬化させる。After the application, the solvent is evaporated and removed by heat treatment to cure the resin. First, most of the solvent is removed at about 50 to 120 ° C, and then the temperature is gradually raised to heat and 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、膜厚等により異なる
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, film thickness, etc. of the coating solution, 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 溶媒可溶型ポリイミド樹脂としては、繰り返し単位の約
80モル％が式 で表わされる構造を有し、および残りの20モル％が式 で表わされる構造を有する共ポリアミドイミドの22重量
％溶液（溶媒はジメチルホルムアミド）を用いた。Example 1 As a solvent-soluble polyimide resin, about 1
80 mol% is the formula And has a structure represented by A 22% by weight solution of a copolyamideimide having a structure represented by (the solvent was dimethylformamide) was used.
この溶液の粘度はＥ型回転粘度計で測定したところ280
ポアズ（25℃）であつた。The viscosity of this solution is 280 when measured with an E-type rotational viscometer.
It was poise (25 ° C).
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275℃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。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 carried out at 80 ° C. for 30 seconds, and then the temperature was gradually raised to heat cure at 275 ° C. for 2 minutes. The thickness of the formed coating film was 25μ.
この塗膜の端部は直線性がきわめて良好であり、塗膜表
面の平滑性も良好であつた。The edge of the coating film had very good linearity and the surface of the coating film had good smoothness.
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。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 溶媒可溶型ポリイミド樹脂として、繰り返し単位の約20
モル％が式 で表わされる構造を有し、および残り80モル％が式 で表わされる構造を有する共ポリイミドの22重量％溶液
（溶媒はジメチルホルムアミド、溶液粘度270ポアズ（2
5℃））を用いたこと、および300℃で２分間加熱硬化を
行つたこと以外は実施例１と同様にして硬化ポリイミド
樹脂被覆物を得た。Example 2 As a solvent-soluble polyimide resin, about 20 repeating units were used.
Mol% is the formula And has the remaining 80 mol% of the formula A 22% by weight solution of a copolyimide having a structure represented by (solvent is dimethylformamide, solution viscosity is 270 poise (2
A cured polyimide resin coating was obtained in the same manner as in Example 1 except that (5 ° C)) was used and that the resin was heat-cured at 300 ° C for 2 minutes.
形成された塗膜の厚さは25μであつた。The thickness of the formed coating film was 25μ.
この塗膜の端部は直線性がきわめて良好であり、塗装表
面の平滑性も良好であつた。The edge of this coating film had very good linearity and the coating surface had good smoothness.
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。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.
本発明によれば帯状基板の表面に均一な厚さをもち、か
つ端部の直線性の良好な、すなわち寸法精度の良好なポ
リイミド樹脂膜を連続的に形成することができる。According to the present invention, it is possible to continuously form a polyimide resin film having a uniform thickness on the surface of a strip-shaped substrate and having good linearity at the end portion, that is, good dimensional accuracy.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 今奈良 徹 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60−5263（ＪＰ，Ａ) 特開 昭61−257271（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Imanara 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Kogyo Co., Ltd. (56) JP-A-61-257271 (JP, A)
Claims (1)
粘度10〜1000ポアズ（測定条件25℃）の下記式で表わさ
れる溶媒可溶型ポリイミド樹脂の溶媒溶液をＴダイ法に
より塗布し、ついで加熱処理を行って該樹脂を硬化させ
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。 繰り返し単位の10〜30モル％が式 で表わされる構造を有し、および残り90〜70モル％が式 で表わされる構造を有する共ポリイミド、あるいは、 繰り返し単位の70〜90モル％が式 で表わされる構造を有し、および残り30〜10モル％が式 で表わされる構造を有する共ポリアミドイミド。1. A solvent solution of a solvent-soluble polyimide resin represented by the following formula and having a viscosity of 10 to 1000 poise (measurement condition: 25 ° C.) is applied to the surface of the substrate while moving the belt-shaped substrate by a T-die method, Then, a heat treatment is carried out to cure the resin, which is a method for producing a cured polyimide resin coating. 10 to 30 mol% of the repeating unit is the formula With a structure represented by A copolyimide having a structure represented by, or 70 to 90 mol% of repeating units are represented by the formula And has a structure represented by A copolyamideimide having a structure represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61104204A JPH0785792B2 (en) | 1986-05-07 | 1986-05-07 | Method for producing cured polyimide resin coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61104204A JPH0785792B2 (en) | 1986-05-07 | 1986-05-07 | Method for producing cured polyimide resin coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62262780A JPS62262780A (en) | 1987-11-14 |
| JPH0785792B2 true JPH0785792B2 (en) | 1995-09-20 |
Family
ID=14374441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61104204A Expired - Lifetime JPH0785792B2 (en) | 1986-05-07 | 1986-05-07 | Method for producing cured polyimide resin coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0785792B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01171680A (en) * | 1987-12-28 | 1989-07-06 | Taiyo Seiko Kk | Production of precoated galvanized sheet with paint having high nonvolatile matter content |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS605263A (en) * | 1983-06-23 | 1985-01-11 | Hitachi Chem Co Ltd | Preparation of metal substrate with film |
| JPH0741206B2 (en) * | 1985-05-08 | 1995-05-10 | 三菱化学株式会社 | Method for producing cured polyimide resin coating |
-
1986
- 1986-05-07 JP JP61104204A patent/JPH0785792B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62262780A (en) | 1987-11-14 |
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