CN1363724A - 底面接着用金属表面处理药剂及处理方法 - Google Patents
底面接着用金属表面处理药剂及处理方法 Download PDFInfo
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- CN1363724A CN1363724A CN01143418A CN01143418A CN1363724A CN 1363724 A CN1363724 A CN 1363724A CN 01143418 A CN01143418 A CN 01143418A CN 01143418 A CN01143418 A CN 01143418A CN 1363724 A CN1363724 A CN 1363724A
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- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
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- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
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- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 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
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
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- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
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- WCSBABHZOSWARI-UHFFFAOYSA-L nickel(2+);selenate Chemical compound [Ni+2].[O-][Se]([O-])(=O)=O WCSBABHZOSWARI-UHFFFAOYSA-L 0.000 description 1
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 235000018716 sodium selenate Nutrition 0.000 description 1
- 239000011655 sodium selenate Substances 0.000 description 1
- 229960001881 sodium selenate Drugs 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- RIAJLMJRHLGNMZ-UHFFFAOYSA-N triazanium;trioxomolybdenum;phosphate Chemical compound [NH4+].[NH4+].[NH4+].O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.[O-]P([O-])([O-])=O RIAJLMJRHLGNMZ-UHFFFAOYSA-N 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
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- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
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Abstract
本发明提供一种可提高金属材料与薄膜间的层间密着性,同时也提高耐蚀性、耐溶剂性,使涂装品的接着性随着提高的金属表面处理药剂及其处理方法。为一种胺化苯酚聚合体及、含有由钛、锆、铪、钼、钨、硒、铈、铁、铜、锌、钒及三价铬选出至少一种金属化合物,且pH值在1.5～6.0范围内的金属表面处理药剂;在上述金属表面处理药剂中,也可并用胺化苯酚聚合体及丙烯系聚合体;还是一种在金属表面处理药剂与金属表面接触后,无须水洗,在80℃～300℃的温度范围使其干燥的处理方法。
Description
技术领域
本发明是有关于一种可提高金属材料与薄膜层压塑料或涂膜间的层间密着性，再者，为提高在层压或涂装薄膜后，金属材料的耐蚀性及耐溶剂性的底面接着用金属表面处理药剂及处理方法；更详细地说明，是一种对铝、镁、铜、钢或其合金等金属材料，将薄膜层压后经深拉加工、挤压加工及拉伸加工等严密成形加工后，赋予薄膜不剥离的高密着性，再者，可使物品(成形加工品)具有非常优越的耐蚀性、耐溶剂性的底面接着用金属表面处理药剂及其处理方法；还是一种有关于可使涂装品接着性大幅提高的底面接着用金属表面处理药剂及其处理方法。
背景技术
公知多使用铝、镁、钢、铜或其合金等多种金属材料，经各种加工后涂装，利用于汽车、家电制品、建筑、饮用容器等制造上，一般来说，该涂料主要是使用溶剂系或水系树脂涂料，涂装于金属材料经加热干燥后形成涂膜，以发挥涂料的作用；在汽车、建筑材料的涂装中，采用粉体涂料，以喷涂枪喷涂于被涂物进行涂装，涂装过程中，涂料废弃物或废溶剂等产业废弃物大量排出，又由于涂料是以高温烧结，于是挥散的有机溶剂或碳酸瓦斯等排出至大气中，且形成涂膜也需要很长的时间。
近年来，为减低废弃瓦斯或废器物的排出，以保护地球环境为目的环保规定更趋严格，工业中所使用的六价铬、铅等有害物质，由于其对人体或环境会产生不良影响，而环境规约于全球中又更为严格，在此背景下，有关薄膜层压技术、不使用有害物质表面处理剂的开发及表面处理技术则受到注目，于众多领域中得以实用化；薄膜层压由于直接贴合于金属上，而不会造成原料的浪费，且成品率高，再者，由于废弃瓦斯产生量少有益于环境保护，与由涂装形成的涂膜相比，其气孔(缺陷部)少，质量也较优良。
迄今，有关薄膜层压的技术，有以层压薄膜的金属材料经加工形成物品的制造技术、薄膜制造技术、金属材料的表面处理技术等多数提案，例如特开平10-46101公报中，提出以含有特定苯酚化合物，甚或磷酸系化合物、有机硅化合物的水系组成物，于金属材料表面被覆处理的被覆金属材料及其制造方法；特开平11-140691公报中，提出表面处理方法、表面处理钢钣、及使用表面处理钢钣作为热可塑性树脂被覆钢钣，并以含六价铬的药剂实施电解铬酸处理，再作为提高密着性的表面处理，而使用有机硅烷偶和剂作硅烷处理的技术。
上述技术是在经特定表面处理的金属材料上，将聚酯系薄膜层压后，经深拉加工、拉伸加工、挤压加工，该成形加工后所得物品在蒸馏杀菌处理时的耐久密着性、盐水浸渍的耐蚀性皆良好，但其耐久密着性若于严苛环境下，则耐蚀性、耐溶剂性皆不充分，因此，有关薄膜层压基底用金属材料，以适用于不含六价铬表面处理剂的被覆金属材料，得到密着性、耐蚀性及耐溶剂性皆优越的技术仍不存在于现状。
发明内容
本发明为解决公知技术中所存在的问题点，具体来说，本发明是以提供一种提高金属材料与薄膜间的层间密着性、或金属材料与涂装膜间的层间密着性，更甚者为使薄膜经层压或涂装后，该金属材料的耐蚀性、耐溶剂性提高的金属表面处理药剂及其处理方法。
本发明者为达成前述目的，经深入研究，发现以含有胺化苯酚聚合体及特定的金属化合物，或含有胺化苯酚聚合体及丙烯系聚合体及特定的金属化合物，且pH值在1.5～6.0范围内的金属表面处理药剂，于金属材料表面以特定方法处理后，将薄膜层压后的材料经成形加工，能产生优良的层间密着性，且耐蚀性及耐溶剂性皆优越，又以上述方法处理后，涂装的材料与涂膜间也具有优越的层间密着性，且耐蚀性及耐溶剂性皆优良，于是完成本发明。
即，本发明是一种以含有胺化苯酚聚合体，及由钛、锆、铪、钼、钨、硒、铈、铁、铜、锌、钒及三价铬中选出至少一种金属化合物，且pH值在1.5～6.0范围内为特征的金属表面处理药剂；前述胺化苯酚聚合体于形成皮膜时，会增加金属表面与薄膜间的层间密着性，对严密的成形加工可发现其随动性；而前述金属化合物于形成皮膜时，由胺化苯酚聚合体与金属交联形成致密的皮膜，且耐蚀性或耐溶剂性皆优良；本发明的金属表面处理药剂pH值在1.5～6.0范围内，使表面处理药剂可安定地存在。
本发明金属表面处理药剂所含有的胺化苯酚聚合体，以下述一般式(I)所示的构造为理想。
〔但，式中X1独立表示氢原子或下述式(II)的Z1基；(式中R1及R2互为独立，表示氢原子、C1～C10的烷基或C1～C10的羟烷基)
Y1为氢原子、羟基、C1～C5的烷基、C1～C5的羟烷基、C1～C12的芳基、苄基或下述式(III)
〔式中R3及R4互为独立，表示氢原子、C1～C10的烷基或C1～C10的羟烷基，又X2为于式(I)中表示各自构成单位中独立的氢原子或下述式(IV)中的Z2基〕
(式中R5及R6互为独立，表示氢原子、C1～C10的烷基或C1～C10的羟烷基)
Y2表示氢原子，当其存在于Y1邻接位置时，由于其包含Y1与Y2间的结合，而以一体的稠苯环来表示；
n为整数；
其中，Z1基+Z2基的导入率相对于1个苯环为0.2～1.0个)
本发明也可含有丙烯系聚合体，由并用丙烯系聚合体，可使金属材料与薄膜或涂膜间的层间密着性、耐蚀性、耐溶剂性更加提高；胺化苯酚聚合体/丙烯系聚合体的比例，以固形分换算比例较理想为100/1～1/20，前述丙烯系聚合体以含有自下述一般式(V)及(VI)所选出至少一种单体单位的聚合体为理想。
-(CH2-CHCOR7)- (V)
-(CHCH3-CHCOR8)- (VI)〔但，式中R7及R8是表示羟基、胺基或C1～C5的羟烷基〕
本发明是一种在金属表面处理药剂与金属表面接触后，不需水洗，以80℃～300℃范围内的温度使其干燥，以此为特征的处理方法；再者，由前述金属表面处理方法所形成的金属表面皮膜，其胺化苯酚聚合体、或胺化苯酚聚合体及丙烯系聚合体合计后的干燥后附着量以1～100mg/m2，且由钛、锆、铪、钼、钨、硒、铈、铁、铜、锌、钒及三价铬中选出至少一种金属化合物，其干燥后附着量的金属附着量合计为1～100mg/m2为理想。
具体实施方式
以下对本发明的内容作一详细叙述。
本发明被覆金属材料所使用的金属材料，可列举出铝、镁、铜、钢或其合金等，而金属材料的形状虽无特别限定，但为层压薄膜用则以板为宜，该板为片状、盘状皆无妨。
本发明金属表面处理药剂中所含的胺化苯酚聚合体，于式(I)中，X1如前所述，于各自构成单位中独自表示氢原子或式(II)的Z1基；式(II)中，R1、R2互为独立，各自表示氢原子、C1～C10的烷基或C1～C10的羟烷基，但在C11以上的烷基或羟烷基中，微性多孔部位增加，而无法形成致密的被膜，导致耐蚀性劣化；再者，由于烷基部分较长疏水性增大，与薄膜间的密着性减弱。
式(I)中，Y1如前所述，是表示氢原子、羟基C1～C5的烷基、C1～C5的羟烷基、C1～C12的芳基、苄基或下述式(III)的基，或表示Y2及Y1与Y2间结合为一体的稠苯环，而C6以上的烷基或羟烷基或C13以上的芳基、苄基以前述的相同理由，其耐蚀性与密着性皆差。
如前所述，胺化苯酚聚合体的构造中，Z1基+Z2基的导入率相当于一个苯环则为0.2～1.0个，例如，前述式(I)中表示的构造单位是由100个结合而成的聚合体，即Z1基+Z2基在导入100个时，其导入率当Y1不为式(III)中的基时为1.0，当Y1为式(III)中的基时为0.5；Z1基+Z2基的导入率，是将聚合体中Z1基+Z2基的合计数除以一般式(I)中苯环及式(III)中苯环合计数所得的数，当Z1基+Z2基的导入率不满0.2时，胺化苯酚聚合体与金属表面间的密着性不足，在加工时容易造成薄膜剥离的问题，而当Z1基+Z2基的导入率超过1.0时，由于极性增大容易引入水而导致耐蚀性变差。
本发明金属表面处理药剂所含的胺化苯酚聚合体依常法即可制造而成，例如，苯酚化合物、萘酚化合物或双酚类(双酚A、F等)与甲醛缩聚，再使用甲醛及胺基导入官能基X1及X2所制得；甲醛通常使用甲醛水，胺化苯酚聚合体为使其水溶化也可加入酸，可使用有机酸、无机酸、配位氟化物，例如醋酸、柠檬酸、乳酸、苹果酸、丁二酸、己二酸、硫酸、硝酸、硅酸、氟硅酸、氟酸、磷酸、锆氢氟酸、钛氢氟酸等；有关胺化苯酚聚合体的分子量并无特别限定，但以1000～1000000左右为较适当。
本发明金属表面处理药剂所含的由钛、锆、铪、钼、钨、硒、铈、铁、铜、锌、钒及三价铬选出至少一种金属化合物，有提高经薄膜层压或涂装后金属材料的耐蚀性的作用，金属化合物有金属氧化物、氢化物、配位化合物、有机酸盐、无机酸盐等，可使用以下所列举的种类，例如锆氢氟酸、锆氟化铵、醋酸锆、硝酸锆、硫酸锆、碳酸锆铵、钛氢氟酸、钛氟化铵、硫酸氧钛、乳酸钛、二异丙氧基二乙醯醋酮酸钛、偏钒酸、偏钒酸铵、偏钒酸钠、五氧化钒、硫酸氧钒、氧钒乙醯醋酸盐、钒乙醯醋酸盐、乙醯醋酮酸铈、硝酸铈、硫酸铈、氟化铈、二氧化硒、硫化硒、硒酸钠、硒酸镍、钼酸铵、钼酸钠、12磷钼酸、磷钼酸铵、磷钼酸钠、钨铵、钨酸钠、六羰基钨、12磷钨酸、磷钨酸铵、磷钨酸钠、硅钨酸、乙醯醋酮酸铁、柠檬酸铁、柠檬酸铁铵、草酸铁、草酸铁铵、硫酸铁(II)铵、硫酸铁(III)铵、氟化铁、乳酸铁(II)、硝酸铁(III)、醋酸亚铅、乙醯醋酮酸亚铅、碳酸亚铅、柠檬酸亚铅、氟化亚铅、氟化硅酸亚铅、乳酸亚铅、硝酸亚铅、硫酸铬、硝酸铬、氟化铬、草酸铬、醋酸铬等。
本发明金属表面处理药剂的溶媒是以水为主体，以调整表面张力低下、低温干燥性等液物性为目的，也可并用乙醇等有机溶剂；本发明的金属表面处理药剂，其pH必须维持于1.5～6.0范围内，一离开该范围则会产生下述问题，当pH不满1.5时则有产生装置腐蚀等设备性问题，又当pH超过6.0，胺化苯酚聚合体则析出无法安定存在；在调整pH时可使用有机酸、无机酸，例如醋酸、柠檬酸、乳酸、苹果酸、丁二酸、己二酸、硫酸、硝酸、硅酸、氟硅酸、氟酸、磷酸等。
为使层间密着性、耐蚀性、耐溶剂性更为提高，金属表面处理药剂所含的丙烯系聚合体，并无特别限定可广泛使用，但以使用由一般式(V)及一般式(VI)所选出至少一种单体单位的聚合体为理想，例如，将式(V)的R7限定于一种类的丙烯单独聚合体、或式(V)的R7为使用两种类以上的丙烯聚合体；又以将式(VI)的R8限定于一种类的甲基丙烯单独聚合体、或式(VI)的R8为使用两种类以上的甲基丙烯共聚体为宜；也可为将式(V)与式(VI)共同使用的丙烯一甲基丙烯共聚体；再者，也可为混合(掺合)前述单独聚合体及共聚体两种类以上者；也可为以由一般式(V)及一般式(VI)选出至少一种单体单位为主体的其它乙烯基系单体单位的共聚体；当R7及R8为羟烷基时，烷基锁以C1～C5的范围为宜，特别以C1、C2为理想；C6以上由于疏水性增高，会引起液安定性的劣化或与薄膜间密着性的劣化，丙烯系聚合体的分子量以数平均分子量5000～100万左右为适当，理想为1万～20万。
以下就本发明的金属表面处理方法作一叙述。
首先，作为底面用薄膜层压，在本发明的金属表面处理药剂与金属材料表面接触以前，必须将金属材料表面清洗干净，即，工业使用的金属材料表面多有防锈油、压延油等附着于上，因此需先将其去除，除去的方法并无特别限定，可列举出溶剂脱脂、碱系脱脂或酸系脱脂等，在脱脂处理后，为除去残留于金属表面的脱脂剂并以水置换，因此还须经过水洗。
本发明的金属表面处理药剂是在于金属表面涂布后，不需经水洗而直接将其加热干燥的方法，即一般归类于涂布型处理方法，有关涂布方法并无特别限定，可列举出辊涂法、喷涂法、浸渍法、旋涂法、等；涂布时金属表面处理药剂的温度虽无特别限定，但通常为10～40℃，较理想为15～25℃的范围。
在金属材料表面上涂布本发明的金属表面处理药剂后，为得到干燥皮膜而必需进行加热干燥处理，由此能在水分等溶媒挥发的同时，使胺化苯酚聚合体不溶化，进而发生与金属化合物的交联反应，此时，加热干燥温度在80～300℃的范围，理想为100～250℃的范围，加热干燥温度若不满80℃，则(II)式及(VI)式中的Z1及Z2基会在干燥皮膜上大量残留，而容易引入水分导致耐蚀性劣化，若加热干燥温度超过300℃，则易使胺化苯酚聚合体变质(劣化)而导致耐蚀性降低、或导致热源的能源性问题，于经济性为不理想。
在金属材料表面形成的干燥皮膜，其胺化苯酚聚合体、或胺化苯酚聚合体与丙烯系聚合体合计后的干燥后附着量必须于1～100mg/m2范围内，若附着量未满1mg/m2，则无法得到满足薄膜层压后加工密着性的性能，若附着量超过100mg/m2，则其性能呈稳定状态，从经济观点来看并不理想；由钛、锆、铪、钼、钨、硒、铈、铁、铜、锌、钒及三价铬选出至少一种金属化合物，其金属附着量合计需于1～100mg/m2范围内，若附着量未满1mg/m2，则其耐蚀性或耐溶剂性皆呈现劣化，若附着量超过100mg/m2，则干燥皮膜脆弱使加工密着性劣化。
于使用本发明金属表面处理药剂形成干燥皮膜的金属材料，层压上薄膜，层压的薄膜具有接着性、气体隔绝性、导电性或设计性等依用途可多样变化，而无特别限定，例如可列举出聚酯、对苯二甲酸乙烯、聚乙烯、聚丙烯、聚碳酸酯、聚乙烯乙醇、聚乙烯乙醇、聚酉先胺、聚醋酸乙烯、或其共聚体，又为赋予机能性，也可使用配合导电填料、着色剂等的薄膜；将金属材料与薄膜层压的方法可列举出接着加热软化薄膜的“热层压”、将接着剂做为底层涂料使用的“干层压”、又将溶融后的树脂以T形塑膜挤出的“挤出层压”等；本发明除用于底面用薄膜层压外，也适用于底面涂装，该涂装涂料并无特别限定，可使用丙烯环氧系水性涂料或聚氯乙烯系溶剂涂料等。
以下有关本发明的金属表面处理药剂列举出几个实施例，并将其作用与比较例作一对比表示出来。
〔金属材料〕
1.铝合金板
于铝合金板(JIS A3004、板厚0.26mm)，以finecleaner4377K(日本巴卡莱近沽股份有限公司制的碱性脱脂剂)的2％水溶液在50℃喷雾脱脂10秒钟，再利用水洗将表面洗净，接着为使铝合金表面水分蒸发，以80℃加热干燥1分钟。
2.钢板
在冷延钢板(JIS SPCC、板厚0.26mm)上，以finecleaner4328K(日本巴卡莱近沽股份有限公司制的碱性脱脂剂)的2％水溶液于60℃喷雾脱脂20秒钟，再利用水洗将表面洗净，接着为使铝合金表面水分蒸发，以80℃加热干燥1分钟。〔表面处理药剂〕
实施例及比较例中所使用表面处理药剂的成分如以下所示，在调整表面处理药剂时则使用去离子水、pH调整剂。
表面处理药剂1
下述胺化苯酚聚合体I：10g/L
锆氢氟酸：5.0g/L
pH：4.0(以氨水调整)
胺化苯酚聚合体I
为一般式(I)中所示的胺化苯酚聚合体，且X1于式(I)中所示的各别构成单位中独立，为氢原子或Z1＝-CH2-N(CH3)2，Y1及Y2为氢原子，Z1基导入率为0.5，MW为5000的聚合体。
表面处理药剂2
下述胺化苯酚聚合体II：10g/L
锆氢氟酸：5.0g/L
pH：4.0(以氨水调整)
胺化苯酚聚合体II
为一般式(I)中所示的胺化苯酚聚合体，且X1于式(I)所示的各别构成单位中独立，为氢原子或Z1＝-CH2-N(CH3)2，Y1为(III)式中所示的基〔但式中，R3及R4为CH3、X2于式(I)所示的各别构成单位中独立，为氢原子或Z1＝-CH2-N(CH3)2〕，Y2为氢原子，Z1+Z2基的导入率为1.0，MW为2000的聚合体。
表面处理药剂3
下述胺化苯酚聚合体III：10g/L
锆氢氟酸：5.0g/L
pH：4.0(以氨水调整)
胺化苯酚聚合体III
为一般式(I)中所示的胺化苯酚聚合体，且X1于式(I)所示的各别构成单位中独立，为氢原子或Z1＝-CH2-N(CH2CH2OH)2，Y1为(III)式中所示的基〔但，式中，R3及R4为CH3、X2于式(I)所示的各别构成单位中独立，为氢原子或Z2＝-CH2-N(CH2CH2OH)2〕，Y2为氢原子，Z1+Z2基的导入率为0.7，MW为5000的聚合体。
表面处理药剂4
前述胺化苯酚聚合体I：10g/L
钼酸：3.0g/L
pH：1.5(以氟酸调整)
表面处理药剂5
前述胺化苯酚聚合体I：10g/L
硝酸铈：8.0g/L
pH：3.0(以氟酸调整)
表面处理药剂6
前述胺化苯酚聚合体I：10g/L
硝酸铬：10g/L
pH：3.0(以氟酸调整)
表面处理药剂7
前述胺化苯酚聚合体I：0.02g/L
锆氢氟酸：0.5g/L
pH：4.0(以氨水调整)
表面处理药剂8
前述胺化苯酚聚合体I：5g/L
锆氢氟酸：5.0g/L
下述丙烯系聚合体I：5g/L
pH：4.0(以氨水调整)
丙烯系聚合体I
为一般式(V)中所示单体单位组成的丙烯系聚合体，且式中的R7为胺基，MW为30000的聚合体。
表面处理药剂9
前述胺化苯酚聚合体I：5g/L
锆氢氟酸：5.0g/L
下述丙烯系聚合体I：5g/L
pH：4.0(以氨水调整)
丙烯系聚合体II
为一般式(V)中所示单体单位与一般式(VI)中单体单位组成的共聚体，其共聚比例为一般式(V)中单体单位：一般式(VI)中单体单位＝8∶2(莫耳比)，且其式中的R7为羟乙基，R8为羟基，MW为50000的共聚体。
表面处理药剂10(比较用药剂；特开平10-46101)
前述胺化苯酚聚合体I：10g/L
pH：4.0(以正磷酸调整)
表面处理药剂11(比较用药剂；特开平10-46101)
前述胺化苯酚聚合体I：10g/L
正磷酸：4.0g/L
γ—缩水甘油丙烷基三甲氧基硅烷：0.05g/L
pH：5.0(以氨水调整)
表面处理药剂12(比较用药剂)
下述丙烯系聚合体III：16g/L
硝酸铬：15g/L
pH：2.5
丙烯系聚合体III
为一般式(V)中所示单体单位组成的丙烯系聚合体，且式中的R7为胺基，MW为10000的聚合体。〔表面处理方法〕
表面处理药剂的处理方法，是将依上述调整后的表面处理药剂于金属板表面以辊涂方法涂布(复印)，形成重量5g/m2，再于设定为200℃的热风加热炉内烧结干燥30秒(以到达板温200℃)，由此制成具一定附着量的被覆金属板。〔薄膜层压〕
在上述经表面处理的被覆金属材料上，将聚酯系薄膜(膜厚16μm)以250℃5秒钟(到达板温180℃)，进行热层压使其面压为50kg/cm2。〔成形加工〕
对经薄膜层压的被覆金属板实施挤压加工实验，将冲切为直径160mm的被覆金属板进行挤压加工(1)，制成直径100mm的杯膜(cup)，将该杯膜再度挤压加工(2)为直径75mm，进而实施直径65mm的挤压加工(3)制成罐，作为供试材；其中，各加工工程(1)、(2)、(3)的膜化(薄壁化分)率各以(1)5％、(2)15％、(3)15％进行。〔经薄膜层压被覆金属材料的性能评价〕1.初期密着性
实施成形加工后，以下示的内容进行初期密着性评价○：可制成罐，且薄膜完全不剥离△：虽可制成罐，但有一部份薄膜剥离×：破裂而无法制成罐2.耐久密着性
有关实施成形加工后的供试材，于加热加压蒸气的环境下进行蒸馏实验，条件为于125℃中进行1小时，使用市贩的灭菌装置。○：薄膜完全不剥离△：薄膜部分剥离×：薄膜完全剥离3.耐蚀性
就耐蚀性而言，由于金属材料种类不同而无法作一概比较，以铝合金板为代表进行实验，在挤压加工制成的罐内，装满实验液〔柠檬酸一水合物∶氯化钠∶去离子水＝5∶5∶990(重量部)〕，以60℃经过120小时，以目测确认罐内面的外观。○：外观无变化△：部分发生薄膜剥离(浮脱)×：薄膜剥离(浮脱)，且于薄膜下发生腐蚀4.耐溶剂性
将成形加工后的供试材，于20％乙醇水溶液中以60℃浸渍120小时，观察薄膜外观。○：外观无变化△：薄膜部分剥离或膨润×：薄膜剥离或膨润
表1为实施例1～12及比较例1～3，记录有金属表面处理药剂、处理条件及于金属材料上形成的皮膜附着量，表2为进行实验后评价判定结果，由表2的结果可清楚得知，实施例1～12的初期密着性、耐久密着性、耐蚀性及耐溶剂性皆优良，另一方面，除去本发明必须成分的金属化合物而仅含胺化苯酚聚合体的比较例1、除去金属化合物而含有正磷酸即有机硅化合物的比较例2、除去胺化苯酚聚合体而使用聚丙烯酸再配合三价铬化合物的比较例3，其初期密着性、耐久密着性、耐蚀性及耐溶剂性皆不足。〔涂装〕
于使用实施例1的金属表面处理药剂及实施例11的金属表面处理药剂，且依前述的表面处理方法进行处理所得的被覆金属材料上，以丙烯环氧系水性涂料及聚氯乙烯系溶剂涂料辊涂涂布，以到达板温250℃加热干燥得到实验片，利用电磁膜厚计测定干燥后的膜厚各为10μm，又，以finecleaner4377K(日本巴卡莱近沽股份有限公司制的碱性脱脂剂)的2％水溶液于50℃喷雾脱脂10秒钟，再利用水洗将表面洗净，再连续以AM-K702(日本巴卡莱近沽公司制的磷酸铬酸盐合成处理剂)于50℃下喷雾处理5秒钟，进行水洗除去未反应的药剂以80℃加热干燥1分钟，得到实验片(铬附着量为20mg/m2)。
有关上述所得的实验片，进行前述实验，依照评价基准不作判定，得到如表3所示的评价结果，由表3的结果可明显得知，将本发明的金属表面处理药剂用于底面涂装处理时，也具有优越的性能。表1 金属表面处理药剂的处理条件及干燥皮膜的附着量
表2评价结果
表3
| 材料 | 金属表面处理药剂 | 干燥温度 | 胺化苯酚聚合体附着量 | 金属化合物金属种类金属附着量 | 丙烯系聚合体附着量 | ||
| 实施例1 | 铝合金板 | 表面处理剂1 | 200℃ | 50 | Zr | 11 | - |
| 实施例2 | 钢板 | 表面处理剂1 | 200℃ | 50 | Zr | 11 | - |
| 实施例3 | 铝合金板 | 表面处理剂2 | 200℃ | 50 | Zr | 11 | - |
| 实施例4 | 表面处理剂3 | 200℃ | 50 | Zr | 11 | - | |
| 实施例5 | 表面处理剂4 | 200℃ | 50 | Mo | 10 | - | |
| 实施例6 | 表面处理剂5 | 200℃ | 50 | Ce | 17 | - | |
| 实施例7 | 表面处理剂6 | 200℃ | 50 | Cr(3价) | 11 | - | |
| 实施例8 | 表面处理剂1 | 80℃ | 50 | Zr | 11 | - | |
| 实施例9 | 表面处理剂1 | 300℃ | 50 | Zr | 11 | - | |
| 实施例10 | 表面处理剂7 | 200℃ | 1 | Zr | 1 | - | |
| 实施例11 | 表面处理剂8 | 200℃ | 25 | Zr | 11 | 25 | |
| 实施例12 | 表面处理剂9 | 200℃ | 25 | Zr | 11 | 25 | |
| 比较例1 | 表面处理剂10 | 200℃ | 50 | - | - | 50 | |
| 比较例2 | 表面处理剂11 | 200℃ | 50 | - | - | 50 | |
| 比较例3 | 表面处理剂12 | 200℃ | 30 | Cr(3价) | 17 | 80 | |
| 初期密着性 | 耐久密着性 | 耐蚀性 | 耐溶剂性 | |
| 实施例1 | ○ | ○ | ○ | ○ |
| 实施例2 | ○ | ○ | 未实施 | ○ |
| 实施例3 | ○ | ○ | ○ | ○ |
| 实施例4 | ○ | ○ | ○ | ○ |
| 实施例5 | ○ | ○ | ○ | ○ |
| 实施例6 | ○ | ○ | ○ | ○ |
| 实施例7 | ○ | ○ | ○ | ○ |
| 实施例8 | ○ | ○ | ○ | ○ |
| 实施例9 | ○ | ○ | ○ | ○ |
| 实施例10 | ○ | ○ | ○ | ○ |
| 实施例11 | ○ | ○ | ○ | ○ |
| 实施例12 | ○ | ○ | ○ | ○ |
| 比较例1 | ○ | △ | × | △ |
| 比较例2 | ○ | ○ | × | △ |
| 比较例3 | △ | × | × | × |
| 涂装 | 底面处理 | 耐久密着性 | 耐蚀性 | 耐溶剂性 |
| 溶剂系 | 实施例1 | ○ | ○ | ○ |
| 实施例11 | ○ | ○ | ○ | |
| 磷酸铬酸盐 | ○ | △ | ○ | |
| 水性 | 实施例1 | ○ | ○ | ○ |
| 实施例11 | ○ | ○ | ○ | |
| 磷酸铬酸盐 | ○ | △ | ○ |
含于胺化苯酚聚合体的羟基，由式(II)、式(IV)的胺基等官能基与金属化合物产生金属交联，提高其气体隔绝性而得到耐蚀性及耐溶剂性，再利用残留的羟基与金属表面强力接着，如此一来，即可提高与层压薄膜或涂膜间的层间密着性，进而发现由于金属化合物所带有的防蚀作用，在成形加工后即使将金属材料置于腐蚀环境中仍然具有优越耐蚀性；由并用丙烯酸系聚合体，可更提高层间密着性、耐蚀性、耐溶剂性。
因此，使用本发明的金属表面处理药剂于金属材料表面形成底面皮膜，由薄膜层压或涂装，可形成层间密着性良好、初期密着性、耐久密着性优越的夹层或涂膜，再者，经层压薄膜后的金属材料或经涂装后的金属材料，其耐溶剂性也优良。
Claims (6)
1.一种底面接着用金属表面处理药剂，其特征在于：其含有胺化苯酚聚合体、及由钛、锆、铪、钼、钨、硒、铈、铁、铜、锌、钒及三价铬中选出的至少一种金属化合物，且pH在1.5～6.0的范围内。
2.如权利要求1所述的底面接着用金属表面处理药剂，其特征在于：其中的胺化苯酚聚合体为如下记一般式(I)中所示的聚合体。
〔但，式中X1独立表示氢原子或下述式(II)的Z1基；
(式中R1及R2互为独立，表示氢原子、C1～C10的烷基或C1～C10的羟烷基)
Y1为氢原子、羟基、C1～C5的烷基、C1～C5的羟烷基、C1～C12的芳基、苄基或表示下述式(III)；
〔式中R3及R4互为独立，表示氢原子、C1～C10的烷基或C1～C10的羟烷基，又X2为于式(I)中于各自构成单位中独立的氢原子或下述式(IV)中的Z2基〕(式中R5及R6互为独立，表示氢原子、C1～C10的烷基或C1～C10的羟烷基)
Y2表示氢原子，当其存在于Y1邻接位置时，由于其包含Y1与Y2间的结合，而以一体的稠苯环来表示；
n为整数；
其中，Z1基+Z2基的导入率相对于1个苯环为0.2～1.0个〕
3.如权利要求1或2所述的底面接着用金属表面处理药剂，其特征在于：其含有丙烯系聚合体，且胺化苯酚聚合体/丙烯系聚合体的比例以固形分换算下为100/1～1/20。
4.如权利要求3所述的底面接着用金属表面处理药剂，其特征在于：其中的丙烯系聚合体，为含有由下述一般式(V)及(VI)中选出至少一种单体单位的聚合体。
-(CH2-CHCOR7)- (V)
-(CHCH3-CHCOR8)- (VI)〔但，式中R7及R8表示羟基、胺基或C1～C5的羟烷基〕
5.一种处理方法，其特征在于：将如权利要求1至4中任何一项中所述的底面接着用金属表面处理药剂，与金属表面接触，再于80℃～300℃的温度范围内使其干燥。
6.一种处理方法，其特征在于：如权利要求5所述的处理方法中，胺化苯酚聚合体及丙烯系聚合体合计后的干燥后附着量为1～100mg/m2，且由钛、锆、铪、钼、钨、硒、铈、铁、铜、锌、钒及三价铬中选出的至少一种金属化合物，其干燥后附着量的金属附着量合计为1～100mg/m2。
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