JPH0215383B2 - - Google Patents
Info
- Publication number
- JPH0215383B2 JPH0215383B2 JP59092997A JP9299784A JPH0215383B2 JP H0215383 B2 JPH0215383 B2 JP H0215383B2 JP 59092997 A JP59092997 A JP 59092997A JP 9299784 A JP9299784 A JP 9299784A JP H0215383 B2 JPH0215383 B2 JP H0215383B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- corrosion
- resins
- ion exchange
- forming
- 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
- 230000007797 corrosion Effects 0.000 claims description 31
- 238000005260 corrosion Methods 0.000 claims description 31
- 239000003456 ion exchange resin Substances 0.000 claims description 25
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 25
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000003973 paint Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 239000007769 metal material Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000010408 film Substances 0.000 description 53
- 238000000034 method Methods 0.000 description 53
- 238000000576 coating method Methods 0.000 description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 229940023913 cation exchange resins Drugs 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- SQKIRAVCIRJCFS-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1C=C SQKIRAVCIRJCFS-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 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 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
Description
【発明の詳細な説明】
本発明は、金属材表面に耐食性が優れている親
水性皮膜を得ることができる耐食親水性皮膜を形
成する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a corrosion-resistant hydrophilic film that can provide a hydrophilic film with excellent corrosion resistance on the surface of a metal material.
金属材は、種々の用途に用いられているが、用
途によつては水によく濡れるいわゆる親水性であ
ることが望まれている。すなわち、熱交換器とく
にそのフイン、あるいは、熱交換器以外でも湿潤
雰囲気内で金属表面の結露を防止したい場合、光
沢を必要とする金属表面の曇り止めをしたい場
合、又は水の濡れ性を高め金属表面から水の蒸発
量を高めたい場合などにおいても当該金属表面に
親水性皮膜を形成することが行なわれている。た
とえば、熱交換器においては、高性能化や小型化
されるに伴なつてフイン間隔を狭くして伝熱性能
を向上させることが行なわれている。しかして熱
交換器は、フイン表面において大気と間に熱交換
が行なわれ、フイン表面に大気中の水分が凝縮す
るが、フイン間隔をたとえば３〜４mm以下のよう
に狭ばめた場合、凝縮した水分がフイン間にブリ
ツジを形成するために通風抵抗が増加して騒音の
発生やエネルギー消費効率を低下させる因となる
ものであつて、親水性を付与してブリツジの形成
を防止することが行なわれている。この親水性を
与える手段としては使用する金属材に応じた手段
がとられているが、たとえば、樹脂塗料に親水付
与剤としてシリカ粉末や界面活性剤を添加したも
のを塗布することが知られている。しかしこれら
は、シリカ粉末を多量に添加する必要があり、そ
のため無機質皮膜の緻密性を低下させ皮膜の耐食
性を低下させ、これを補償するために６価クロム
イオン濃度を高めると生成皮膜から６価クロムイ
オンが溶出したり、皮膜形成後にダイス成形加工
などを施行する場合にダイスの摩耗を生じたり、
あるいは、界面活性剤が経年的に溶出し親水性が
劣化するといつたようなことや、使用環境によつ
ては親水性を高めると金属材の耐食性を低下させ
るといつたような問題があつた。 Metal materials are used for various purposes, and depending on the purpose, they are desired to be so-called hydrophilic, meaning that they can be easily wetted by water. In other words, when you want to prevent dew condensation on a heat exchanger, especially its fins, or on metal surfaces other than heat exchangers in a humid atmosphere, when you want to prevent fogging on metal surfaces that require gloss, or when you want to increase water wettability. Also when it is desired to increase the amount of water evaporated from a metal surface, a hydrophilic film is formed on the metal surface. For example, as heat exchangers become more sophisticated and smaller, the fin spacing is narrowed to improve heat transfer performance. Heat exchangers exchange heat with the atmosphere on the fin surfaces, and moisture in the atmosphere condenses on the fin surfaces. However, if the fin spacing is narrowed to, for example, 3 to 4 mm or less, the condensation This moisture forms bridges between the fins, which increases ventilation resistance and causes noise generation and lowers energy consumption efficiency.The formation of bridges can be prevented by imparting hydrophilicity. It is being done. Methods for imparting this hydrophilicity are taken depending on the metal material used; for example, it is known to apply silica powder or surfactant as a hydrophilic agent to resin paint. There is. However, these require the addition of a large amount of silica powder, which reduces the density of the inorganic film and reduces the corrosion resistance of the film.If the concentration of hexavalent chromium ions is increased to compensate for this, the hexavalent Chromium ions may be eluted, or die wear may occur when die forming is performed after film formation.
There were also problems such as surfactants leaching over time and deterioration of hydrophilicity, and depending on the environment of use, increasing hydrophilicity could reduce the corrosion resistance of metal materials. .
本発明者らは、これらの問題を解決するために
種々研究を重ねた結果、金属材に、あらかじめ耐
食性皮膜を形成させた後、イオン交換樹脂を配合
した親水性皮膜形成剤を塗布することによつて目
的を達し得ることを見出して本発明をなしたもの
である。すなわち、本発明は、金属材に、耐食性
皮膜を形成させた後、該皮膜上にイオン交換樹脂
粉末を含有させた樹脂塗料を塗布することにより
親水性皮膜を形成させることを特徴とする耐食・
親水性皮膜を形成させる方法である。 As a result of various studies to solve these problems, the present inventors decided to form a corrosion-resistant film on the metal material in advance and then apply a hydrophilic film-forming agent containing an ion exchange resin. The present invention was created based on the discovery that the object can be achieved. That is, the present invention is a corrosion-resistant film characterized in that a hydrophilic film is formed by forming a corrosion-resistant film on a metal material and then applying a resin paint containing ion exchange resin powder on the film.
This is a method of forming a hydrophilic film.
本発明において使用する金属材としては、鉄及
びその合金、アルミニウム及びその合金、銅及び
その合金その他の金属材で製作された板や押出型
材のような素形材、又は、熱交換器のような特定
形状品、組立品などがあげられる。 The metal materials used in the present invention include molded materials such as plates and extruded materials made of iron and its alloys, aluminum and its alloys, copper and its alloys, and other metal materials, or materials such as heat exchangers. Examples include products with specific shapes and assembled products.
次に、耐食性下地皮膜の形成方法としては、酸
化皮膜を形成する方法、又は、アルミニウム、亜
鉛、銅、クロムなどによる耐食性金属皮膜を形成
させる方法などがある。 Next, methods for forming the corrosion-resistant base film include a method of forming an oxide film, and a method of forming a corrosion-resistant metal film of aluminum, zinc, copper, chromium, or the like.
しかして、酸化皮膜を形成する方法としては、
化成酸化皮膜法と陽極酸化皮膜法などが常用さ
れ、いずれも適用可能であるが、比較的薄膜で耐
食性にすぐれた皮膜を連続的に安価に得ることが
できるので化成酸化皮膜の方が好ましい。 However, as a method for forming an oxide film,
Chemical oxide coating methods and anodic oxidation coating methods are commonly used, and both are applicable, but chemical oxide coatings are preferable because a relatively thin film with excellent corrosion resistance can be obtained continuously and inexpensively.
化成酸化皮膜法としては、浴成分から、アルカ
リクロメート法と呼ばれるMBV法、EW法、
Pylumin法、Alrock法、及び、酸性クロメート
法と呼ばれるボンデライト法、インダイト法、ア
ロジン法並びにベーマイト処理法、リン酸塩法な
どがある。なお、通常は、クロム酸・フツ化物を
主要浴成分として浴温20〜40℃で５秒〜５分間処
理するクロメート皮膜処理法、クロム酸・フツ
酸・リン酸を主要浴成分として26〜60℃で30秒〜
７分間処理するリン酸クロム皮膜処理法、リン酸
亜鉛・リン酸マンガンなどのリン酸塩を主要浴成
分として浴温60〜100℃で５分間程度処理するリ
ン酸塩皮膜法、及び、熱水飽和水蒸気・トリエタ
ノールアミンなどで処理するベーマイト皮膜法な
どが適用される。 Chemical oxide coating methods include the MBV method (also known as the alkali chromate method), the EW method, and
There are the Pylumin method, the Alrock method, the Bonderite method called the acid chromate method, the Indite method, the Allozin method, the Boehmite treatment method, and the phosphate method. Usually, the chromate film treatment method uses chromic acid/fluoride as the main bath components and processes at a bath temperature of 20 to 40°C for 5 seconds to 5 minutes, and the ~30 seconds at °C
Chromium phosphate film treatment method, which is treated for 7 minutes, phosphate film treatment method, which is treated for about 5 minutes at a bath temperature of 60 to 100℃ using phosphates such as zinc phosphate and manganese phosphate as the main bath components, and hot water treatment. The boehmite coating method, which involves treatment with saturated steam, triethanolamine, etc., is applied.
これらは、浸漬法、スプレー法、ロールコート
法、スチームガン法などによつて施行することが
できる。しかして、これらの方法によつて、
0.005μｍ以上の化成酸化皮膜を形成するものであ
つて、0.005μｍ以下では、耐食性下地皮膜として
の特性が不十分である。たとえば熱交換器用フイ
ンの場合には、0.01〜0.5μｍ程度とすることが好
ましく、皮膜形成後に成形加工する必要がないと
き、あるいは皮膜の熱伝導性を問題としないとき
には、5μｍ以上の皮膜厚とすることもできる。 These can be carried out by a dipping method, a spray method, a roll coating method, a steam gun method, or the like. However, by these methods,
It forms a chemical oxide film with a thickness of 0.005 μm or more, and if it is less than 0.005 μm, the properties as a corrosion-resistant base film are insufficient. For example, in the case of heat exchanger fins, the thickness is preferably about 0.01 to 0.5 μm, and when there is no need for molding after film formation, or when the thermal conductivity of the film is not an issue, the film thickness is 5 μm or more. You can also.
耐食性金属皮膜を形成させる方法としては、金
属材の材質と用途に応じてアルミニウ、亜鉛、
銅、クロムなどの金属を電解メツキ法、蒸着法、
溶射法あるいはクラツド法などの方法があり、適
宜方法が適用される。 As a method for forming a corrosion-resistant metal film, aluminum, zinc,
Metals such as copper and chromium can be electrolytically plated, vapor-deposited,
There are methods such as the thermal spraying method and the cladding method, and the method is applied as appropriate.
すなわち、たとえば、亜鉛被覆の場合には、酸
化亜鉛150〜240ｇ／・水酸化ナトリウム500〜
550ｇ／・シアン化ナトリウム５〜10ｇ／を
主要成分とする浴で電気メツキする方法、硫酸亜
鉛・塩化亜鉛・ホウフツ化亜鉛を用いる酸性亜鉛
電気メツキ浴法、酸化亜鉛・水酸化ナトリウムを
主要成分とするシンジケート電解メツキ浴法、塩
化亜鉛にオキシ酸などのキレート剤を添加した中
性亜鉛電解メツキ浴法及びピロリン酸塩浴法な
ど、あるいは、塩化アンモニウム・塩化亜鉛アン
モニウムのフラツクス前処理を経て溶融金属亜鉛
浴中に浸漬する溶融亜鉛メツキ法、亜鋭溶射法、
クラツド法などによつて亜鉛皮膜を形成するもの
である。又、アルミニウム被覆法としては、たと
えば塩化カリウム・塩化ナトリウムからなる塩化
物系や氷晶石・フツ化アルミニウムからなるフツ
化物系のフラツクス浴中に浸漬後、溶融アルミニ
ウム浴中に浸漬する溶融アルミニウムメツキ法、
プラズマ溶射法、真空蒸着法及びクラツド法など
があげられる。 That is, for example, in the case of zinc coating, 150 to 240 g of zinc oxide/500 to 240 g of sodium hydroxide
A method of electroplating in a bath containing 550g/・sodium cyanide 5 to 10g/ as the main components, an acid zinc electroplating bath method using zinc sulfate, zinc chloride, and zinc borofluoride, and a method of electroplating with a bath containing 550g/・sodium cyanide/5 to 10g/ as the main components, an acid zinc electroplating bath method using zinc oxide and sodium hydroxide as the main components Syndicate electrolytic plating bath method, neutral zinc electrolytic plating bath method in which a chelating agent such as oxyacid is added to zinc chloride, pyrophosphate bath method, etc., or molten metal after flux pretreatment with ammonium chloride/zinc ammonium chloride. Hot-dip galvanizing method by immersing in zinc bath, sub-sharp thermal spraying method,
A zinc film is formed by a method such as a cladding method. In addition, as an aluminum coating method, for example, molten aluminum plating is immersed in a chloride-based flux bath consisting of potassium chloride and sodium chloride or a fluoride-based flux bath consisting of cryolite and aluminum fluoride, and then immersed in a molten aluminum bath. law,
Examples include plasma spraying, vacuum evaporation, and cladding.
これらの方法によつて皮膜厚が3μｍ以上の耐
食性金属皮膜を形成するものであつ、3μｍ以下
では耐食性下地皮膜としての特性が不十分であ
る。皮膜厚は使用目的によつて異なり、たとえば
熱交換器用フインの場合には、５〜10μｍ程度が
好ましいが、皮膜形成後に成形加工する必要がな
いとき、あるいは皮膜の熱伝導性を問題としない
ときには、10μｍ以上の適宜な皮膜厚とすること
ができる。 By these methods, a corrosion-resistant metal film having a thickness of 3 μm or more is formed, and if the thickness is less than 3 μm, the properties as a corrosion-resistant base film are insufficient. The thickness of the coating varies depending on the purpose of use, and for example, in the case of heat exchanger fins, it is preferably about 5 to 10 μm, but when there is no need to process the coating after forming the coating, or when the thermal conductivity of the coating is not an issue. , an appropriate film thickness of 10 μm or more can be achieved.
しかして、これらの方法のうち耐食性下地皮膜
の形成方法として実用上は、クロメート処理法が
もつとも好ましく経済性も含めて最良の効果を発
現させ得るものである。 Therefore, among these methods, the chromate treatment method is practically preferable as a method for forming a corrosion-resistant base film, and can exhibit the best effects including economical efficiency.
次に、イオン交換樹脂粉末を含有する親水性皮
膜を形成させる方法としては、イオン交換樹脂粉
末を配合し親水性皮膜形成剤を塗布することによ
るものであつて、イオン交換樹脂粉末を配合した
親水性皮膜形成剤としては、樹脂塗料にイオン交
換樹脂粉末を配合したものである。 Next, a method for forming a hydrophilic film containing ion exchange resin powder is to mix ion exchange resin powder and apply a hydrophilic film forming agent. The adhesive film forming agent is a resin paint mixed with ion exchange resin powder.
樹脂塗料中の塗膜形成樹脂成分としては、樹脂
塗料として使用されている天然樹脂、合成樹脂あ
るいは熱可塑性樹脂、熱硬化性樹脂などの中から
用途に応じて適宜のものを選定して使用し得、た
とえばアルキツド樹脂、アクリル樹脂、ポリビニ
ルアルコール樹脂、酢酸ビニル樹脂、エポキシ樹
脂、フエノール樹脂、ポリエステル樹脂、シリコ
ン系樹脂、フツ素系樹脂、ウレタン樹脂などが列
挙される。 The film-forming resin component in the resin paint is selected from among the natural resins, synthetic resins, thermoplastic resins, thermosetting resins, etc. used in resin paints, depending on the application. For example, alkyd resins, acrylic resins, polyvinyl alcohol resins, vinyl acetate resins, epoxy resins, phenol resins, polyester resins, silicone resins, fluorine resins, urethane resins, etc. are listed.
イオン交換樹脂としては、親水性原子団を有し
非水溶性の界面活性剤として機能し得るものであ
つて、イオン交換樹脂として常用されている樹脂
や、イオン交換膜として使用されている樹脂も使
用可能であり、所望の親水性レベルに応じて適宜
のものを使用し得、総イオン交換容量が0.5〔mg当
量／ｇ・DryR〕以上のもの、より好ましくは、
1.0〔mg当量／ｇ・DryR〕以上のものが望ましい。
すなわち、フエノールスルホン酸系、エチレンイ
ミン−エピクロロヒドリン系、エポキシ系などの
ような縮合系イオン交換樹脂、スチレン−ジビニ
ルベンゼン系、ビニルジビニルベンゼン系、メタ
クリル酸−ジビニルベンゼン系などのような重合
系イオン交換樹脂などが入手可能であり、それら
に親水性原子団としてスルホン酸基、ホスホン酸
基、ホスフイン基あるい第四級アンモニウム、第
一級ないし第三級アミンなどを付加たものが陽イ
オン交換樹脂あるいは陰イオン交換樹脂として入
手可能である。さらに、強塩基性陰イオン交換樹
脂にアクリル酸を重合させた両性イオン交換樹脂
並びに親水性原子団を導入したフツ素樹脂などの
ようなものも市販されており同様に使用可能であ
るが、これらの中、親水性の点で陽イオン交換樹
脂が好適であり、スルホン酸型強酸性陽イオン交
換樹脂が最適である。 Ion exchange resins include resins that have hydrophilic atomic groups and can function as water-insoluble surfactants, and include resins that are commonly used as ion exchange resins and resins that are used as ion exchange membranes. Any suitable material can be used depending on the desired hydrophilicity level, and those with a total ion exchange capacity of 0.5 [mg equivalent/g・DryR] or more, more preferably,
A value of 1.0 [mg equivalent/g・DryR] or more is desirable.
That is, condensation type ion exchange resins such as phenolsulfonic acid type, ethyleneimine-epichlorohydrin type, epoxy type, etc., polymerization such as styrene-divinylbenzene type, vinyldivinylbenzene type, methacrylic acid-divinylbenzene type, etc. ion exchange resins, etc. are available, and those to which hydrophilic atomic groups such as sulfonic acid groups, phosphonic acid groups, phosphine groups, quaternary ammonium, primary or tertiary amines are added are cationic. It is available as an ion exchange resin or an anion exchange resin. Furthermore, amphoteric ion exchange resins made by polymerizing acrylic acid onto strongly basic anion exchange resins, and fluorine resins into which hydrophilic atomic groups are introduced are also commercially available and can be used in the same way. Among them, cation exchange resins are preferred from the viewpoint of hydrophilicity, and sulfonic acid type strongly acidic cation exchange resins are most suitable.
これらのイオン交換樹脂は、所望の親水性レベ
ルに応じて一種類のイオン交換樹脂だけでなく、
強酸性と弱酸性の陽イオン交換樹脂、あるいは、
強塩基性と弱塩基性の陰イオン交換樹脂を適宜の
割合で二種類以上配合して用いることもできる。
また、イオン交換樹脂は、新品だけでなく、他の
プロセスで使用済みの再生品も適用することが出
来る。 These ion exchange resins are not only one type of ion exchange resin depending on the desired level of hydrophilicity.
Strongly acidic and weakly acidic cation exchange resins, or
Two or more types of strongly basic and weakly basic anion exchange resins may be used in combination at an appropriate ratio.
Furthermore, not only new ion exchange resins but also recycled products that have been used in other processes can be used.
それらの粒度としては、皮膜を形成し物品の用
途、所望の皮膜の平滑性などか選定される皮膜厚
に応じて決められるが、たとえば熱交換器用フイ
ンに好適な0.5〜5μｍの厚さの皮膜を形成させる
ときには、平均粒径0.5〜1μｍのものが望ましい。
したがつて、入手可能なものが大粒径である場合
には、振動ボールミル、アトライターなどによる
粉砕処理をした後に使用に供することが好まし
い。 The particle size of these particles is determined depending on the intended use of the article to be coated, the desired smoothness of the coating, etc., and the thickness of the selected coating. When forming such particles, it is desirable to have an average particle size of 0.5 to 1 μm.
Therefore, when available particles have large particle sizes, it is preferable to use them after pulverization using a vibrating ball mill, attritor, or the like.
イオン交換樹脂の配合割合は、固形分として塗
膜成分とイオン交換樹脂の合計中に占めるイオン
交換樹脂の割合が乾燥重量基準で0.1以上、好ま
しくは、0.3〜0.7となるように配合するものであ
つて、0.1以下では、所望の親水性レベルを安定
的に得ることが困難であり、0.7以上添加すると
皮膜の接着性、耐水性が低下するものであり、残
余分を塗膜形成成分を配合するものである。 The blending ratio of the ion exchange resin is such that the ratio of the ion exchange resin in the total of the coating film components and the ion exchange resin as a solid content is 0.1 or more on a dry weight basis, preferably 0.3 to 0.7. If it is less than 0.1, it is difficult to stably obtain the desired hydrophilicity level, and if it is added more than 0.7, the adhesion and water resistance of the film will decrease. It is something to do.
なお、塗膜形成助剤として、水性型塗料の場合
は水が、有機溶媒性塗料の場合には、炭化水素、
アルコール、エステル、ケトン、エーテルなどが
それぞれ常法通り使用され、それら溶媒の添加量
も通常の塗料と同様に、用いる塗布手段に応じた
流動性を発現させるために適宜の範囲に任意に選
定され得るものであるが、通常、イオン交換樹脂
を含む樹脂固形分１に対して１〜９の割合で添加
される。さらに、塗料としての諸属性を付与する
添加剤、たとえば、分散剤、防カビ剤、皮張り防
止剤、スリツプ剤あるいは消泡剤などを所望によ
つて、それぞれ１〜２％程度含有させ得る。又、
皮膜の初期親水性向上剤として、α−オレフイン
スルフオネートのような界面活性剤を0.5〜10％
程度添加することができる。 In addition, as a film forming aid, water is used in the case of water-based paints, and hydrocarbons, etc. are used in the case of organic solvent-based paints.
Alcohols, esters, ketones, ethers, etc. are used in the usual manner, and the amount of these solvents added is arbitrarily selected within an appropriate range in order to develop fluidity depending on the application method used, just like in ordinary paints. However, it is usually added at a ratio of 1 to 9 parts per 1 part of the solid content of the resin containing the ion exchange resin. Furthermore, additives that impart various properties as a coating material, such as a dispersant, a fungicide, an antiskinning agent, a slip agent, or an antifoaming agent, may be contained in an amount of about 1 to 2%, respectively, as desired. or,
0.5-10% surfactant such as α-olefin sulfonate as an initial hydrophilicity improver for the film.
Can be added to some degree.
本発明において使用するイオン交換樹脂粉末を
配合した親水皮膜形成剤は、前記のような各成分
を前記のような割合で配合し、十分に均一に混合
して調製するものである。 The hydrophilic film-forming agent blended with ion exchange resin powder used in the present invention is prepared by blending the above-mentioned components in the above-mentioned proportions and thoroughly and uniformly mixing them.
次に、イオン交換樹脂粉末を含有する親水性皮
膜の形成は、金属材の形状に応じて、ロールコー
ト法、スプレー法、浸漬法、刷毛塗り法、スピン
コート法など適宜の方法によつて、塗布量が１〜
３ｇ／m2（乾燥基準）程度となるように塗布さ
れ、樹脂塗料が常乾性塗料であれば塗布後そのま
ま風乾して皮膜の固定化を行ない、焼付型塗料で
あればイオン交換樹脂の特性を損なわない適宜の
加熱条件下で焼付け処理を行なうことによつてさ
れるものである。 Next, the hydrophilic film containing the ion exchange resin powder is formed by an appropriate method such as a roll coating method, a spray method, a dipping method, a brush coating method, or a spin coating method depending on the shape of the metal material. Application amount is 1~
3g/m 2 (dry standard). If the resin paint is an air-drying paint, it is air-dried after application to fix the film, and if it is a baking-type paint, it is applied to maintain the properties of the ion exchange resin. This is done by performing a baking treatment under appropriate heating conditions that do not damage the material.
本発明は、耐食性下地皮膜の上に、イオン交換
樹脂粉末を配合した親水性皮膜を形成させるよう
にしたので、相互に皮膜の特性を補完し得るの
で、単独に施行するときに較べてそれぞれの皮膜
厚を薄くし得、又、浸漬塗布のような塗膜厚が不
均一になるような方法（たとえば槽から引き上げ
方向によつて3μｍ以上の差があるときがある）
であつても所期の耐食性を発揮し得、上層が可焼
性に富む樹脂層であるために、皮膜形成後の塑性
加工時におけるダイス摩耗や耐食性下地皮膜の割
れによる耐食性劣化などの発生を防止し得、従来
の界面活性剤を使用する親水性皮膜に較べて親水
性の経年劣化が少ないなど多くのすぐれた効果を
認めることができる。 In the present invention, a hydrophilic film containing ion-exchange resin powder is formed on a corrosion-resistant base film, so that the properties of each film can be complemented. Methods such as dip coating that can reduce the film thickness and make the film thickness uneven (for example, there may be a difference of 3 μm or more depending on the direction of pulling from the tank)
Since the upper layer is a highly flammable resin layer, corrosion resistance deterioration due to die wear and cracking of the corrosion-resistant base film during plastic processing after film formation is avoided. Many excellent effects can be recognized, such as less deterioration of hydrophilicity over time compared to hydrophilic coatings using conventional surfactants.
次に、本発明の実施例を述べる。 Next, examples of the present invention will be described.
実施例
弱アルカリ性クリーナ（商品名FC315、日本パ
ーカライジング社製）で脱脂したコイル状アルミ
ニウムフイン材（AA3105合金製、板厚0.12mm）
に、1.3wt％濃度のリン酸クロメート型処理剤
（商品名アロジン401−45、日本ペイント社製）を
35℃に加熱して、スプレー法で塗布し、表面に約
70Åの耐食性下地皮膜を形成させた。Example Coiled aluminum fin material (made of AA3105 alloy, plate thickness 0.12 mm) degreased with a weak alkaline cleaner (product name FC315, manufactured by Nippon Parkerizing Co., Ltd.)
A phosphoric acid chromate type treatment agent (trade name: Allozin 401-45, manufactured by Nippon Paint Co., Ltd.) at a concentration of 1.3 wt% was added to
Heat to 35℃, apply by spraying, and apply to the surface about approx.
A corrosion-resistant base film of 70 Å was formed.
ついで、平均粒径が0.5〜1μｍのスルホン酸型
イオン交換樹脂（商品名Ｒ−120B、オルガノ社
製）を乾燥固形分重量比で40％となるように、触
媒硬化型エポキシエステル系水性塗料（商品名ウ
オーターゾルS346、大日本インキ社製）中に添
加し、よく混合して調製した親水性皮膜形成剤を
ロールコート法で塗布量1.5ｇ／m2（乾燥基準）
となるように耐食性下地皮膜上に塗布した後、温
風乾燥炉にて230℃で30秒間加熱して焼付け固定
化処理を行なつた。 Next, a sulfonic acid type ion exchange resin (trade name R-120B, manufactured by Organo Co., Ltd.) with an average particle size of 0.5 to 1 μm was added to a catalyst-curing epoxy ester water-based paint ( A hydrophilic film-forming agent prepared by adding it to Watersol S346 (trade name, manufactured by Dainippon Ink Co., Ltd.) and mixing well was coated using a roll coating method in an amount of 1.5 g/m 2 (dry basis).
After coating it on a corrosion-resistant base film so as to have the following properties, it was baked and fixed by heating at 230°C for 30 seconds in a hot air drying oven.
皮膜形成処理をして得たコイル材を打抜き加
工、しごき加工してクロスフイン材を製作し、親
水性と耐食性の評価試験を行なつた。 Cross fin materials were manufactured by punching and ironing the coil materials obtained through film formation treatment, and evaluation tests for hydrophilicity and corrosion resistance were conducted.
すなわち、親水性の長期安定性は、相対湿度95
％、温度50℃の雰囲気中において500時間放置し
たときの濡れ面積率によつて評価したが、100％
であつて良好な親水性が得られことが認められ
た。 That is, the long-term stability of hydrophilicity is at a relative humidity of 95
%, evaluated by the wetted area ratio when left for 500 hours in an atmosphere at a temperature of 50°C, but 100%
It was confirmed that good hydrophilicity was obtained.
又、耐食性は、JIS Z2371（1955）による500時
間塩水噴霧試験によつて評価したが、未加工部及
びしごき加工部のいずれにも腐食発生が認められ
ず、耐食性にもすぐれていることが認められ、本
発明によるときは、親水性、耐食性ともにすぐれ
た皮膜が形成し得るとともに、皮膜形成後の機械
加工性にもすぐれていることが認められた。 In addition, corrosion resistance was evaluated by a 500-hour salt spray test according to JIS Z2371 (1955), and no corrosion was observed in either the unprocessed or ironed parts, indicating that the product had excellent corrosion resistance. It was found that when the present invention was used, a film with excellent hydrophilicity and corrosion resistance could be formed, and the machinability after film formation was also excellent.
比較例
実施例におけるリン酸クロメートによる耐食性
下地皮膜形成を行なわず、イオン交換樹粉末を含
有する親水性皮膜を実施例と同様に処理して形成
し、同様に皮膜形成後、機械加工を行なつて、同
様な評価試検を行なつた。Comparative Example A hydrophilic film containing ion exchange resin powder was formed by processing in the same manner as in the example, without forming the corrosion-resistant base film using phosphoric acid chromate as in the example, and after forming the film, machining was performed in the same manner. We conducted a similar evaluation test.
その結果、親水性は、漏れ面積率100％であつ
たが、腐食試検では、未加工部で腐食面積率が平
均５％であり、しごき加工部では、10％であり腐
食の発生が認められた。 As a result, the leakage area ratio was 100% for hydrophilicity, but in the corrosion test, the average corrosion area ratio was 5% in the unprocessed area, and 10% in the ironed area, indicating that corrosion had occurred. It was done.
Claims (1)
皮膜上にイオン交換樹脂粉末を含有させた樹脂塗
料を塗布することにより親水性皮膜を形成せしめ
ることを特徴とする耐食・親水性皮膜を形成させ
る方法。1 Formation of a corrosion-resistant/hydrophilic film characterized by forming a corrosion-resistant base film on a metal material and then forming a hydrophilic film by applying a resin paint containing ion-exchange resin powder onto the film. How to do it.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9299784A JPS60236746A (en) | 1984-05-11 | 1984-05-11 | Method of forming corrosion-resistant and hydrophilic film |
| GB08428144A GB2151641B (en) | 1983-11-11 | 1984-11-07 | Hydrophilic film-forming coating compositions |
| CA000467532A CA1216695A (en) | 1983-11-11 | 1984-11-09 | Hydrophilic-film-forming preparation |
| FR8417347A FR2554824B1 (en) | 1983-11-11 | 1984-11-12 | PREPARATIONS FOR THE FORMATION OF A HYDROPHILIC FILM, PROCESS FOR THEIR IMPLEMENTATION AND ARTICLES THEREOF |
| DE19843441275 DE3441275A1 (en) | 1983-11-11 | 1984-11-12 | MEDIUM FOR PRODUCING HYDROPHILIC FILMS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9299784A JPS60236746A (en) | 1984-05-11 | 1984-05-11 | Method of forming corrosion-resistant and hydrophilic film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60236746A JPS60236746A (en) | 1985-11-25 |
| JPH0215383B2 true JPH0215383B2 (en) | 1990-04-11 |
Family
ID=14070000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9299784A Granted JPS60236746A (en) | 1983-11-11 | 1984-05-11 | Method of forming corrosion-resistant and hydrophilic film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60236746A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5582797A (en) * | 1978-12-14 | 1980-06-21 | Nippon Steel Corp | Preparation of high anticorrosive d and i can |
-
1984
- 1984-05-11 JP JP9299784A patent/JPS60236746A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5582797A (en) * | 1978-12-14 | 1980-06-21 | Nippon Steel Corp | Preparation of high anticorrosive d and i can |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60236746A (en) | 1985-11-25 |
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