JPH03215581A - Method for improving adherence of polyimide coating film - Google Patents
Method for improving adherence of polyimide coating filmInfo
- Publication number
- JPH03215581A JPH03215581A JP1011790A JP1011790A JPH03215581A JP H03215581 A JPH03215581 A JP H03215581A JP 1011790 A JP1011790 A JP 1011790A JP 1011790 A JP1011790 A JP 1011790A JP H03215581 A JPH03215581 A JP H03215581A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- anhydride
- polyamic acid
- polyimide coating
- dianhydride
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 title claims abstract description 17
- 239000004642 Polyimide Substances 0.000 title claims abstract description 14
- 229920001721 polyimide Polymers 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 7
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 15
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 6
- 239000002966 varnish Substances 0.000 claims abstract description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 11
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 abstract description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic tetracarboxylic anhydride Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- XLXVRIOQCHHBTC-UHFFFAOYSA-N 2,2-bis(phenoxycarbonyl)propanedioic acid Chemical compound C=1C=CC=CC=1OC(=O)C(C(O)=O)(C(=O)O)C(=O)OC1=CC=CC=C1 XLXVRIOQCHHBTC-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 1
- VETOZLDSVKEYKO-UHFFFAOYSA-N 4-phenyl-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2C1=CC=CC=C1 VETOZLDSVKEYKO-UHFFFAOYSA-N 0.000 description 1
- TZQVSGOOKNNDFU-UHFFFAOYSA-N 4-phenylsulfanylaniline Chemical compound C1=CC(N)=CC=C1SC1=CC=CC=C1 TZQVSGOOKNNDFU-UHFFFAOYSA-N 0.000 description 1
- YTRAFABYXOZRDF-UHFFFAOYSA-N 5-phenyl-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC=C1 YTRAFABYXOZRDF-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- IDVDAZFXGGNIDQ-UHFFFAOYSA-N benzo[e][2]benzofuran-1,3-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)OC2=O IDVDAZFXGGNIDQ-UHFFFAOYSA-N 0.000 description 1
- IZJDCINIYIMFGX-UHFFFAOYSA-N benzo[f][2]benzofuran-1,3-dione Chemical compound C1=CC=C2C=C3C(=O)OC(=O)C3=CC2=C1 IZJDCINIYIMFGX-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐熱性と密着性に優れた芳香族ポリイミドに
関するものであり、更に詳しくは、耐熱性を損なうこと
なく芳香族ポリイミド塗膜の金属への密着性を向上させ
る方法に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an aromatic polyimide having excellent heat resistance and adhesion. This invention relates to a method for improving adhesion to metal.
従来、各種の有機合成高分子からなる金属被覆材が知ら
れており、比較的耐熱性を有するものとしては、エポキ
シ系、シリコーン系樹脂が知られている。しかし、これ
らの使用許容範囲は通常２００℃内外とされており、よ
り高温での使用には耐えない。Conventionally, metal coating materials made of various organic synthetic polymers are known, and epoxy-based and silicone-based resins are known as those having relatively heat resistance. However, the permissible range for use of these is usually around 200°C, and they cannot withstand use at higher temperatures.
また、より耐熱性のある樹脂としては、芳香族ポリイミ
ドが知られているが、一般的にポリイミドは金属に対す
る密着性に乏しく、高温環境下において剥離を生じると
いう問題点を有する。Aromatic polyimides are known as more heat-resistant resins, but polyimides generally have poor adhesion to metals and have the problem of peeling in high-temperature environments.
本発明の目的は、優れた耐熱性と密着性とを併せ持つ樹
脂を金属に被覆することにより、より優れた耐熱性と耐
腐食性を有する金属材料を開発することにある。An object of the present invention is to develop a metal material that has better heat resistance and corrosion resistance by coating metal with a resin that has both excellent heat resistance and adhesiveness.
本発明者らは、上記問題点を解決すべく鋭意検討した結
果、特定の末端基構造を有するポリイミドにおいては、
金属への密着性が飛躍的に向上することを見出し、本発
明を完成させた。As a result of intensive studies to solve the above problems, the present inventors found that in polyimide having a specific terminal group structure,
It was discovered that the adhesion to metals was dramatically improved, and the present invention was completed.
即ち本発明は、芳香族テトラカルボン酸二無水物と芳香
族ジアミンとジカルボン酸無水物もしくはモノアミンと
を反応させ、得られたポリアミド酸ワニスを金属板上に
塗布して加熱することによりポリイミド塗膜を得ること
を特徴とするポリイミド塗膜の密着性改良方法を提供す
るものである。That is, the present invention produces a polyimide coating film by reacting an aromatic tetracarboxylic dianhydride, an aromatic diamine, and a dicarboxylic acid anhydride or monoamine, and applying the obtained polyamic acid varnish onto a metal plate and heating it. The present invention provides a method for improving the adhesion of a polyimide coating film, which is characterized by obtaining the following properties.
本発明のポリイミドの前駆体であるポリアミド酸は、芳
香族テトラカルボン酸無水物とジアミン及びジカルボン
酸無水物もしくはモノアミンとを、溶媒中で反応させる
などの周知の方法により合成することができる。Polyamic acid, which is a precursor of the polyimide of the present invention, can be synthesized by a well-known method such as reacting an aromatic tetracarboxylic anhydride with a diamine and a dicarboxylic anhydride or a monoamine in a solvent.
芳香族テトラカルボン酸二無水物としては、ピロメリッ
ト酸二無水物、３．３゜， ４． ４’−ベンゾフエノ
ンテトラカルボン酸二無水物、４．４′−オキシジフタ
ル酸二無水物、３． ３’ ， ４． ４’−ビフエニ
ルテトラカルボン酸二無水物、３．３′．４，４゜ジフ
ェニルメタンテトラカルボン酸二無水物、３． ３’
， ４， ４゜−ジフェニルスルフイドテトラカルボン
酸二無水物、３，３“， ４． ４’−ジフエニルスル
ホンテトラカルボン酸二無水物等を使用することができ
、一種又は二種以上のものを併用することもできる。Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3.3°, 4. 4'-Benzophenonetetracarboxylic dianhydride, 4.4'-oxydiphthalic dianhydride, 3. 3', 4. 4'-biphenyltetracarboxylic dianhydride, 3.3'. 4,4° diphenylmethanetetracarboxylic dianhydride, 3. 3'
, 4, 4゜-diphenylsulfone tetracarboxylic dianhydride, 3,3'', 4.4'-diphenylsulfone tetracarboxylic dianhydride, etc. can be used, and one or more types can be used. You can also use them together.
芳香族ジアミンとしては、例えば、ｐ−フエニレンジア
ミン、ｍ−フェニレンジアミン、ベンジジン、４．４′
−オキンジアニリン、３，３゛−オキシジアニリン、３
．４’−オキシジアニリン、４，４゛−ジアミノジフェ
ニルメタン、４．４’−ジアミノジフェニルスルホン、
２．２−ビス（４−（４アミノフェノキン）フェニル〕
フロパン、ｐジアミノキシリレン、２，６−ジアミノト
ルエン、２，４−ジアミノトルエン、１，６−へキサメ
チレンジアミン等を挙げることができ、一種又は二種以
上のものを併用することもできる。Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, benzidine, 4.4'
-Oquindianiline, 3,3゛-oxydianiline, 3
．． 4'-oxydianiline, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone,
2.2-bis(4-(4aminophenoquine)phenyl)
Furopane, p-diaminoxylylene, 2,6-diaminotoluene, 2,4-diaminotoluene, 1,6-hexamethylenediamine, etc. can be mentioned, and one type or two or more types can also be used in combination.
本発明において上記二成分とともに反応せしめられるジ
カルボン酸無水物もしくはモノアミンは塗膜の密着性を
向上させるための必須の成分である。In the present invention, the dicarboxylic acid anhydride or monoamine reacted with the above two components is an essential component for improving the adhesion of the coating film.
本発明において用いられるジカルボン酸無水物としては
、例えば、無水フタル酸、２，３−ペンゾフェノンジカ
ルボン酸無水物、３．４−ペンゾフェノンジカルボン酸
無水物、２．３−シフエニルエーテルジカルボン酸無水
物、３，４−ジフェニルエーテルジカルボン酸無水物、
２，３−ビフェニルジカルボン酸無水物、３．４−ビフ
エニルジカルボン酸無水物、２．３−ジフェニルスルホ
ンジカルボン酸無水物、３．４−ジフエニルスルホンジ
カルボン酸無水物、２．３−ジフエニルスルフィドジカ
ルボン酸無水物、３．４−シフエニルスルフィドジカル
ボン酸無水物、１，２−ナフタレンジカルボン酸無水物
、２，３−ナフタレンジカルボン酸無水物、１，８−ナ
フタレンジカルボン酸無水物及び無水マレイン酸、テト
ラヒド口無水フタル酸等が挙げられ、これらは単独ある
いは２種以上混合して使用してもよい。Examples of the dicarboxylic anhydride used in the present invention include phthalic anhydride, 2,3-penzophenone dicarboxylic anhydride, 3,4-penzophenone dicarboxylic anhydride, and 2,3-cyphenyl ether dicarboxylic anhydride. acid anhydride, 3,4-diphenyl ether dicarboxylic acid anhydride,
2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-diphenylsulfonedicarboxylic anhydride, 3,4-diphenylsulfonedicarboxylic anhydride, 2,3-diphenyl Sulfide dicarboxylic anhydride, 3,4-cyphenylsulfide dicarboxylic anhydride, 1,2-naphthalene dicarboxylic anhydride, 2,3-naphthalene dicarboxylic anhydride, 1,8-naphthalene dicarboxylic anhydride and maleic anhydride Examples include acids, tetrahydrophthalic anhydride, and the like, and these may be used alone or in combination of two or more.
本発明において用いられるモノアミンとしては、例えば
、アルキルアミン、アニリン及びトルイジン、キシリジ
ン、クロロアニリン、プロモアニリン、ニトロアニリン
、アミノベンゾニトリノベアミノベンゾフエノン、アミ
ノジフエニルエーテル、アミンビフェニノベアミノジフ
エニルスルホン、アミノジフエニルスルフイド、ナフチ
ルアミン等の置換位置異性体等が挙げられ、これらは単
独あるいは２種以上混合して使用してもよい。Monoamines used in the present invention include, for example, alkylamines, aniline and toluidine, xylidine, chloroaniline, promoaniline, nitroaniline, aminobenzonitrinobeaminobenzophenone, aminodiphenyl ether, aminebiphenynoveaminodiphenyl sulfone. , aminodiphenyl sulfide, naphthylamine, and other substituted positional isomers, and these may be used alone or in combination of two or more.
本発明の方法において用いられる芳香族テトラカルボン
酸二無水物と芳香族ジアミン及びジカルボン酸無水物も
し《はモノアミンのモル比は、芳香族テトラカルボン酸
二無水物１モル当たり、芳香族ンアミン１．０モル乃至
１．１モル、ジカルボン酸無水物０．００１モル乃至１
．０モルもしくは芳香族テトラカルボン酸二無水物１モ
ル当たり、芳香族ジアミン０．９モル乃至１．０モル、
モノアミン０． ００１モル乃至１．０モルである。The molar ratio of the aromatic tetracarboxylic dianhydride to the aromatic diamine and dicarboxylic anhydride used in the method of the present invention is 1 mole of aromatic tetracarboxylic dianhydride to 1. 0 mol to 1.1 mol, dicarboxylic acid anhydride 0.001 mol to 1 mol
．． 0 mol or 1 mol of aromatic tetracarboxylic dianhydride, 0.9 mol to 1.0 mol of aromatic diamine,
Monoamine 0. 001 mol to 1.0 mol.
本発明においてポリアミド酸を合成する際に用いられる
溶媒としては、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ
−ジメチルホルムアミド、Ｎメチル−２−ピロリドン、
ジメチルスルホキシドなどのような非プロトン性極性溶
媒、又はビス（２−メトキシエチル）エーテル（略称ジ
グライム）、テトラヒド口フラン、１．３−ジオキサン
、１，４−ジオキサン、１，２−ビス（２−メトキシエ
トキシ）エタン等のエーテル系溶媒を使用することがで
きる。In the present invention, the solvent used when synthesizing polyamic acid includes N,N-dimethylacetamide, N,N
-dimethylformamide, N-methyl-2-pyrrolidone,
Aprotic polar solvents such as dimethyl sulfoxide, or bis(2-methoxyethyl) ether (abbreviated as diglyme), tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, 1,2-bis(2- Ether solvents such as methoxyethoxy)ethane can be used.
本発明においてポリアミド酸からポリイミドへの変換は
、周知の方法が適用される。即ち例えば、本発明のポリ
アミド酸ワニスを金属板上に塗布した後、１００℃以上
の温度にて熱処理を行うことにより容易に達成できる。In the present invention, a well-known method is applied to convert polyamic acid into polyimide. That is, for example, this can be easily achieved by applying the polyamic acid varnish of the present invention onto a metal plate and then heat-treating it at a temperature of 100° C. or higher.
以下、実施例及び比較例にて本発明を詳しく説明するが
、本発明はかかる実施例に限定されるものではない。The present invention will be explained in detail below using Examples and Comparative Examples, but the present invention is not limited to these Examples.
実施例１
撹拌機、窒素導入管、温度計を付したフラスコ内に、４
，４“−オキンジアニリン２００． ２ｇ （１． ０
０モル）を仕込み、系内を窒素で百換した後Ｎ，Ｎジメ
チルアセトアミド１， ３００ ｇを入れ４．４′オキ
ンジアニリンを溶解させた。これに、４，４′オキシジ
フタル酸二無水物３０４． ０ｇ（０． ９８モル）及
び無水フタル酸５． ９２ｇ （０． ０４モル）を徐
々に添加した。添加終了後、４，４′−オキシジフタル
酸二無水物が完溶した時点より、７０℃にて２時間攪拌
を行い、２１０ｐＯｉＳｅ／２５℃（固形分２８％）の
溶液粘度を有するポリアミド酸溶液を得た。Example 1 In a flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, 4
,4"-Oquindianiline 200.2g (1.0
After purging the system with nitrogen, 1,300 g of N,N dimethylacetamide was added to dissolve 4.4' oxin dianiline. To this, 4,4' oxydiphthalic dianhydride 304. 0 g (0.98 mol) and phthalic anhydride5. 92 g (0.04 mol) were added gradually. After the addition, from the time when 4,4'-oxydiphthalic dianhydride was completely dissolved, stirring was carried out at 70°C for 2 hours to prepare a polyamic acid solution having a solution viscosity of 210 pOiSe/25°C (solid content 28%). Obtained.
こうして得られたポリアミド酸溶液を、ＪＩＳＧ ３１
４１及びＪＩＳ Ｈ ４０００に規定する冷間圧延鋼板
及びアルミ板上に塗布し、（１２０℃×１０分） ＋
（１８０℃×３０分） ＋（２５０℃×３０分）の熱処
理を行い、膜厚２５μｍの塗膜を得た。The polyamic acid solution obtained in this way was
41 and JIS H 4000 on cold rolled steel plates and aluminum plates, (120°C x 10 minutes) +
A heat treatment of (180° C. x 30 minutes) + (250° C. x 30 minutes) was performed to obtain a coating film with a thickness of 25 μm.
得られた塗膜の剥離強度は、冷間圧延鋼板では５５０−
６５０ｇ／ｃｍであり、アルミ板では７００〜８００ｇ
／Ｃｍてあった。The peel strength of the resulting coating film was 550-
650g/cm, and 700-800g for aluminum plate
/Cm was there.
実施例２
撹拌機、窒素導入管、温度計を付したフラスコ内に４．
４′−オキシジアニリン１９６． ２ｇ（０． ９８モ
ル）及びアニリン３． ７２ｇ （０． ０４モル）を
仕込み、系内を窒素で置換した後Ｎ，Ｎ−ジメチルアセ
トアミド１， ３００ ｇを入れ４，４゛−オキシジア
ニリン及びアニリンを溶解させた。これに、４，４′−
オキンジフタル酸二無水物３１０． ２ｇ（１． ００
モル）を徐々に添加した。添加終了後、４，４′−オキ
シジフタル酸二無水物が完溶した時点より、７０℃にて
２時間攪拌を行い、１８０ｐｏｉｓｅ／２５℃（固形分
２８％）の溶液粘度を有するポリアミド酸溶液を得た。Example 2 4.
4'-oxydianiline 196. 2 g (0.98 mol) and aniline 3. After charging 72 g (0.04 mole) and purging the system with nitrogen, 1,300 g of N,N-dimethylacetamide was added to dissolve 4,4'-oxydianiline and aniline. To this, 4,4'-
Oquine diphthalic dianhydride 310. 2g (1.00
mol) was added gradually. After the addition, from the time when 4,4'-oxydiphthalic dianhydride was completely dissolved, stirring was performed at 70°C for 2 hours to prepare a polyamic acid solution having a solution viscosity of 180 poise/25°C (solid content 28%). Obtained.
こうして得られたポリアミド酸溶液を、ＪＩＳＧ ３１
４１及びＪＩＳ Ｈ ４０００に規定する冷間圧延鋼板
及びアルミ板上に塗布し、（１２０℃×１０分） ＋
（１８０℃×３０分） ＋（２５０℃×３０分）の熱
処理を行い、膜厚２５μｍの塗膜を得た。The polyamic acid solution obtained in this way was
41 and JIS H 4000 on cold rolled steel plates and aluminum plates, (120°C x 10 minutes) +
A heat treatment of (180° C. x 30 minutes) + (250° C. x 30 minutes) was performed to obtain a coating film with a thickness of 25 μm.
得られた塗膜の剥離強度は、冷間圧延鋼板でよ４００
〜５００ｇ／ｃｍであり、アルミ板では６００〜７００
ｇ／ｃｍであった。The peel strength of the resulting coating film was 400
~500g/cm, and 600~700 for aluminum plate
g/cm.
比較例１
撹拌機、窒素導入管、温度計を付したフラスコ内に４，
４゜−オキシジアニリン２００． ２ｇ （１． ００
モル）を仕込み、系内を窒素で置換した後、Ｎ，Ｎジメ
チルアセトアミド１，３００ｇを入れ４，４゛オキンジ
アニリンを溶解させた。これに、４．４′一オキンジフ
タル酸二無水物３０４． ０ｇ （０． ９８モル）を
徐々に添加した。添加終了後、４．４′一オキンジフタ
ル酸二無水物が完溶した時点より、７０℃にて２時間攪
拌を行い、２２０ｐｏｉｓｅ／２５℃（固形分２８％）
の溶液粘度を有するポリアミド酸溶液を得た。Comparative Example 1 In a flask equipped with a stirrer, nitrogen inlet tube, and thermometer, 4,
4°-oxydianiline 200. 2g (1.00
After purging the system with nitrogen, 1,300 g of N,N dimethylacetamide was added to dissolve 4,4゛oxindianiline. To this, 4.4'-monoquine diphthalic dianhydride 304. 0g (0.98 mol) was added slowly. After the addition was complete, stirring was carried out at 70°C for 2 hours at 220poise/25°C (solid content 28%) from the time when the 4.4'-monoquine diphthalic dianhydride was completely dissolved.
A polyamic acid solution having a solution viscosity of .
こうして得られたポリアミド酸溶液を、ＪＩＳＧ ３１
４１及びＪＩＳ Ｈ ４０００に規定する冷間圧延鋼板
及びアルミ板上に塗布し、（１２０℃×１０分） ＋
（１８０℃×３０分） ＋（２５０℃×３０分）の熱処
理を行い、膜厚２５μｍの塗膜を得た。The polyamic acid solution obtained in this way was
41 and JIS H 4000 on cold rolled steel plates and aluminum plates, (120°C x 10 minutes) +
A heat treatment of (180° C. x 30 minutes) + (250° C. x 30 minutes) was performed to obtain a coating film with a thickness of 25 μm.
得られた塗膜の剥離強度は、冷間圧延鋼板では２５Ｃｌ
−３５０ｇ／ｃｍであり、アルミ板では５００〜６ＱＱ
ｇ／ｃｍであった。The peel strength of the obtained coating film is 25Cl for cold rolled steel plate.
-350g/cm, and 500~6QQ for aluminum plate
g/cm.
実施例及び比較例にて明らかなように、本発明にて得ら
れるポリイミド塗膜は、その優れた耐熱性を保持したま
ま金属への密着性が著しく向上しているのが判る。従っ
て、その優れた密着性、耐熱性、及び耐腐食性により、
自動車のマフラー、石油ファンヒーター吹き出し口、オ
ーブントースターの窓枠等の他に、電気・電子分野にお
ける耐熱性絶縁材料、
形設、構造材料、
航空、
宇宙材料など様々な分野において使用が期待される。As is clear from the Examples and Comparative Examples, it can be seen that the polyimide coating film obtained by the present invention has significantly improved adhesion to metal while maintaining its excellent heat resistance. Therefore, due to its excellent adhesion, heat resistance, and corrosion resistance,
In addition to automobile mufflers, kerosene fan heater vents, toaster oven window frames, etc., it is expected to be used in a variety of fields such as heat-resistant insulating materials, molding and structural materials in the electrical and electronic fields, and aviation and space materials. .
Claims (1)
カルボン酸無水物もしくはモノアミンとを反応させ、得
られたポリアミド酸ワニスを金属板上に塗布して加熱す
ることによりポリイミド塗膜を得ることを特徴とするポ
リイミド塗膜の密着性改良方法。Aromatic tetracarboxylic dianhydride, aromatic diamine, and dicarboxylic anhydride or monoamine are reacted, and the resulting polyamic acid varnish is applied onto a metal plate and heated to obtain a polyimide coating film. A method for improving the adhesion of polyimide coatings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1011790A JPH03215581A (en) | 1990-01-19 | 1990-01-19 | Method for improving adherence of polyimide coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1011790A JPH03215581A (en) | 1990-01-19 | 1990-01-19 | Method for improving adherence of polyimide coating film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03215581A true JPH03215581A (en) | 1991-09-20 |
Family
ID=11741359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1011790A Pending JPH03215581A (en) | 1990-01-19 | 1990-01-19 | Method for improving adherence of polyimide coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03215581A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011056634A3 (en) * | 2009-10-27 | 2011-09-22 | E. I. Du Pont De Nemours And Company | Polyimide resins for high temperature wear applications |
| EP2493983A2 (en) * | 2009-10-27 | 2012-09-05 | E. I. du Pont de Nemours and Company | Polyimide resins for high temperature wear applications |
| WO2012173202A1 (en) * | 2011-06-14 | 2012-12-20 | 宇部興産株式会社 | Method for producing polyimide laminate, and polyimide laminate |
| US9161440B2 (en) | 2006-06-26 | 2015-10-13 | Sabic Global Technologies B.V. | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof |
-
1990
- 1990-01-19 JP JP1011790A patent/JPH03215581A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9161440B2 (en) | 2006-06-26 | 2015-10-13 | Sabic Global Technologies B.V. | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof |
| WO2011056634A3 (en) * | 2009-10-27 | 2011-09-22 | E. I. Du Pont De Nemours And Company | Polyimide resins for high temperature wear applications |
| EP2493983A2 (en) * | 2009-10-27 | 2012-09-05 | E. I. du Pont de Nemours and Company | Polyimide resins for high temperature wear applications |
| EP2493983A4 (en) * | 2009-10-27 | 2013-03-13 | Du Pont | Polyimide resins for high temperature wear applications |
| WO2012173202A1 (en) * | 2011-06-14 | 2012-12-20 | 宇部興産株式会社 | Method for producing polyimide laminate, and polyimide laminate |
| JPWO2012173202A1 (en) * | 2011-06-14 | 2015-02-23 | 宇部興産株式会社 | Method for producing polyimide laminate and polyimide laminate |
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