CN101796218B - 预处理组合物和涂覆金属基材的方法 - Google Patents
预处理组合物和涂覆金属基材的方法 Download PDFInfo
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- CN101796218B CN101796218B CN2008801053352A CN200880105335A CN101796218B CN 101796218 B CN101796218 B CN 101796218B CN 2008801053352 A CN2008801053352 A CN 2008801053352A CN 200880105335 A CN200880105335 A CN 200880105335A CN 101796218 B CN101796218 B CN 101796218B
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- 150000003949 imides Chemical class 0.000 description 1
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- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical class [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- IJZKJRUCRGJGKO-UHFFFAOYSA-N oxalic acid;zirconium Chemical compound [Zr].OC(=O)C(O)=O IJZKJRUCRGJGKO-UHFFFAOYSA-N 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
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- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006009 resin backbone Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 108700004121 sarkosyl Proteins 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 235000013758 sodium copper chlorophyllin Nutrition 0.000 description 1
- 229940079841 sodium copper chlorophyllin Drugs 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003441 suberic acid derivatives Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
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- 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
- C23C22/34—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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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
- C23C22/34—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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- 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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- 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
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- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
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Abstract
披露了处理金属基材，包括含铁基材例如冷轧钢和电镀锌钢的方法。该方法包括使基材与包含以下组分的预处理组合物接触：(a)IIIB和/或IVB族金属；(b)正电性金属；(c)游离氟；(d)由形成具有至少11的pKsp的氟化物盐的金属形成的金属氟化物盐；和(e)水。
Description
发明领域
本发明涉及预处理组合物和涂覆金属基材(包括含铁基材例如冷轧钢和电镀锌钢)的方法。本发明还涉及涂覆的金属基材。
背景信息
在金属基材上使用保护涂层用于改进的耐腐蚀性和涂料附着力是常见的。涂覆这类基材的常规技术包括涉及用磷酸盐转化涂料(phosphate conversion coating)和含铬洗剂预处理金属基材的技术。然而，这类含磷酸盐和/或铬酸盐的组合物的使用会带来环境和健康问题。
因此，已经开发了不含铬酸盐和/或不含磷酸盐的预处理组合物。这类组合物通常基于以某种方式与基材表面反应并且粘结至其上形成保护层的化学混合物。例如，基于IIIB或IVB族金属化合物的预处理组合物近来变得更加盛行。这类组合物常常含有游离氟源，即所述氟与连接在另一元素例如IIIB或IVB族金属上的氟相反，是在预处理组合物中孤立的氟。游离氟可能蚀刻金属基材的表面，由此促进IIIB或IVB族金属涂层的沉积。然而，一般地这些预处理组合物的耐腐蚀能力明显低于常规的含磷酸盐和/或铬的预处理物。
因此，希望提供克服至少一些前述的现有技术的缺陷(包括与使用铬酸盐和/或磷酸盐相关的环境缺陷)的处理金属基材的方法。此外，希望提供在至少一些情形中赋予与通过使用磷酸盐转化涂料赋予的耐腐蚀性能相当或者甚至更优异的耐腐蚀性能的处理金属基材的方法。还希望提供相关的涂覆的金属基材。
发明概述
在某些方面中，本发明涉及用于处理金属基材的组合物。这些组合物包含：(a)IIIB和/或IVB族金属；(b)正电性金属；(c)百万分之0.1-300(“ppm”)游离氟；(d)由形成具有至少11的pKsp的氟化物盐的金属形成的金属氟化物盐；和(e)水。在某些实施方案中，该组合物基本上不含重金属磷酸盐例如磷酸锌和铬酸盐。
在另一些方面中，本发明涉及处理金属基材的方法，其包括使基材与包含以下组分的预处理组合物接触：(a)IIIB和/或IVB族金属；(b)正电性金属；(c)游离氟；(d)由形成具有至少11的pKsp的氟化物盐的金属形成的金属氟化物盐；和(e)水，其中以足以将组合物中游离氟的含量保持至不小于0.1ppm并且不大于300ppm的量提供形成具有至少11的pKsp的金属氟化物盐的金属。
在另一些方面中，本发明涉及用于处理金属基材的组合物，其包含：(a)IIIB和/或IVB族金属；(b)0.1-300ppm游离氟；(c)由形成具有至少11的pKsp的氟化物盐的金属形成的金属氟化物盐；和(d)水。本发明的这些组合物基本上不含磷酸根离子和铬酸盐。
本发明还涉及由此处理的基材。
发明详述
出于以下详述的目的，应理解本发明可以采取各种备选变换方式和步骤顺序，除了在相反明确说明的情况下。此外，除了在任何操作实施例中或者在另外说明的情况下之外，在说明书和权利要求书中使用的表示例如组分量的所有数值应被理解为在所有情形中由术语“约”修饰。因此，除非相反地说明，在以下说明书和附属的权利要求书中描述的数值参数是近似值，其可以根据将通过本发明获得的所希望的性能而变化。至少地并且不试图限制等同原则应用于权利要求书的范围，每一数值参数应该至少根据具有所报导的有效数位的数值并且通过采用一般舍入技术来理解。
尽管描述本发明的宽范围的数值范围和参数是近似值，但描述于具体实施例中的数值被尽可能准确地报导。然而，任何数值固有地含有由在它们各自的试验测量中发现的标准偏差必然引起的一定误差。
另外，应该理解的是本文中列出的所有数值范围意在包括其中包含的所有子范围。例如，范围“1-10”意在包括在所列出的最小值1与所列出的最大值10之间(并且包括端值)的所有子范围，即具有等于或大于1的最小值和等于或小于10的最大值的所有子范围。
在本申请中，单数的使用包括复数并且复数包括单数，除非另外特别地说明。另外在本申请中，“或”的使用是指“和/或”，除非另外特别地说明，尽管在某些情形中可能明确地使用“和/或”。
如前所述，本发明的某些实施方案涉及涂覆金属基材的方法。用于本发明的合适的金属基材包括通常用于汽车车身的组件、汽车部件和其它制品(例如小金属部件，包括紧固件，即螺母、螺栓、螺杆、销、钉、夹具、按钮等)中的那些。合适的金属基材的具体实例包括，但不限于，冷轧钢、热轧钢、镀锌金属、锌化合物或锌合金的钢例如电镀锌钢、热浸镀锌钢、合金化热镀锌钢(galvanealed steel)、和镀锌合金钢(steelplated with zinc alloy)。还可以使用铝合金、镀铝钢和镀铝合金钢基材。其它合适的非含铁金属包括铜和镁，以及这些材料的合金。另外，通过本发明的方法涂覆的金属基材可以是在其表面的剩余部分之上被另外处理和/或涂覆的基材的切割边缘。根据本发明的方法涂覆的金属基材可以为例如金属片材或预制件(fabricated part)的形式。
可以首先将待根据本发明的方法涂覆的基材清洁以除去油脂、污垢或其它外来物质。这通常通过使用温和或强的碱性清洁剂来进行，所述温和或强的碱性清洁剂例如有可商购获得的和常规地用于金属预处理工艺中的那些。适用于本发明的碱性清洁剂的实例包括Chemkleen 163、Chemkleen 177和Chemkleen 490MX，其分别可从PPG Industries，Inc.商购获得。所述清洁剂通常在水洗之前和/或之后施用。
如前所述，本发明的某些实施方案涉及处理金属基材的方法，其包括使金属基材与包含IIIB和/或IVB族金属的预处理组合物接触。本文中使用的术语“预处理组合物”是指当与基材接触时，与基材表面反应并且化学地改变基材表面以及粘结至其上形成保护层的组合物。
通常，预处理组合物包含载体，通常是水性介质，以使得组合物为IIIB或IVB族金属化合物在载体中的溶液或分散体的形式。在这些实施方案中，可以通过各种已知技术的任一种，例如浸入或浸渍、喷射、间歇喷射、浸入之后喷射、喷射之后浸入、刷涂或辊涂使该溶液或分散体与基材接触。在某些实施方案中，当施涂于金属基材上时，该溶液或分散体处于60-150°F(15-65℃)温度下。接触时间通常为10秒至5分钟，例如30秒至2分钟。
本文中使用的术语“IIIB和/或IVB族金属”是指例如在Handbookof Chemistry and Physics，第63版(1983)中所示的，CAS元素周期表的IIIB族或IVB族中的元素。在适用的情况下，可以使用金属本身。在某些实施方案中，使用IIIB和/或IVB族金属化合物。本文中使用的术语“IIIB和/或IVB族金属化合物”是指包括CAS元素周期表的IIIB族或IVB族中的至少一种元素的化合物。
在某些实施方案中，用于预处理组合物中的IIIB族和/或IVB族金属化合物是锆、钛、铪、钇、铈的化合物、或其混合物。合适的锆化合物包括，但不限于，六氟锆酸、其碱金属盐和铵盐、碳酸锆铵、硝酸氧锆、锆羧酸盐和锆羟基羧酸盐例如氢氟锆酸(hydrofluorozirconicacid)、乙酸锆、草酸锆、羟基乙酸锆铵、乳酸锆铵、柠檬酸锆铵，和其混合物。合适的钛化合物包括，但不限于，氟钛酸和其盐。合适的铪化合物包括，但不限于硝酸铪。合适的钇化合物包括，但不限于硝酸钇。合适的铈化合物包括，但不限于硝酸铈。
在某些实施方案中，IIIB和/或IVB族金属化合物以至少10ppm金属，例如至少100ppm金属，或在一些情形中至少150ppm金属(按照元素金属测量)的量存在于预处理组合物中。在某些实施方案中，IIIB和/或IVB族金属化合物以不大于5000ppm金属，例如不大于300ppm金属，或在一些情形中不大于250ppm金属(按照元素金属测量)的量存在于预处理组合物中。预处理组合物中IIIB和/或IVB族金属的量可以在所列出的数值的任意组合之间，包括所列出的数值在内。
在某些实施方案中，预处理组合物还包含正电性金属。本文中使用的术语“正电性金属”是指比金属基材更加正电性的金属。这是指出于本发明的目的，术语“正电性金属”包括与被处理的金属基材的金属相比，不容易被氧化的金属。正如将被本领域那些技术人员理解的，金属被氧化的趋势被称为氧化电势、以伏特表示并且相对于被任意地指定为0氧化电势的标准氢电极测量。在下表中描述了若干元素的氧化电势。如果在下表中其具有比被比较的元素更大的电压值E+，则该元素与另一元素相比不容易被氧化。
| 元素 | 半电池反应 | 电压，E* |
| 钾 | K++e→K | -2.93 |
| 钙 | Ca2++2e→Ca | -2.87 |
| 钠 | Na++e→Na | -2.71 |
| 镁 | Mg2++2e→Mg | -2.37 |
| 铝 | Al3++3e→Al | -1.66 |
| 锌 | Zn2++2e→Zn | -0.76 |
| 铁 | Fe2++2e→Fe | -0.44 |
| 镍 | Ni2++2e→Ni | -0.25 |
| 锡 | Sn2++2e→Sn | -0.14 |
| 铅 | Pb2++2e→Pb | -0.13 |
| 氢 | 2H++2e→H2 | -0.00 |
| 铜 | Cu2++2e→Cu | 0.34 |
| 汞 | Hg2 2++2e→2Hg | 0.79 |
| 铝 | Ag++e→Ag | 0.80 |
| 金 | Au3++3e→Au | 1.50 |
因此，显然的是，当金属基材包含先前列出的材料例如冷轧钢、热轧钢、镀锌金属、锌化合物或锌合金的钢、热浸镀锌钢、合金化热镀锌钢(galvanealed steel)、和镀锌合金钢(steel plated with zincalloy)、铝合金、镀铝钢、镀铝合金钢、镁和镁合金中的一种时，用于包含在预处理组合物中的合适的正电性金属包括例如镍、铜、银和金，以及其混合物。
在某些实施方案中，预处理组合物中的正电性金属的来源是水溶性金属盐。在本发明的某些实施方案中，水溶性金属盐是水溶性铜化合物。适用于本发明的水溶性铜化合物的具体实例包括，但不限于，氰化铜、氰化铜钾、硫酸铜、硝酸铜、焦磷酸铜、硫氰酸铜、乙二胺四乙酸二钠铜四水合物、溴化铜、氧化铜、氢氧化铜、氯化铜、氟化铜、葡糖酸铜、柠檬酸铜、月桂酰肌氨酸铜、甲酸铜、乙酸铜、丙酸铜、丁酸铜、乳酸铜、草酸铜、肌醇六磷酸铜、酒石酸铜、苹果酸铜、琥珀酸铜、丙二酸铜、马来酸铜、苯甲酸铜、水杨酸铜、天冬氨酸铜、谷氨酸铜、富马酸铜、甘油磷酸铜、叶绿酸铜钠、氟硅酸铜、氟硼酸铜和碘酸铜，以及甲酸到癸酸的同系物系列中的羧酸的铜盐、草酸到辛二酸系列中的多元酸的铜盐，和羟基羧酸(包括羟基乙酸、乳酸、酒石酸、苹果酸和柠檬酸)的铜盐。
当由该水溶性铜化合物提供的铜离子作为硫酸铜、氧化铜等形式的杂质沉淀时，可以优选加入抑制铜离子沉淀的络合剂，由此使它们作为铜络合物稳定在溶液中。
在某些实施方案中，铜化合物作为铜络合物盐例如K3Cu(CN)4或Cu-EDTA加入，这些盐可以独立地稳定地存在于组合物中，但是也可以通过将络合剂与难以独立地溶解的化合物合并而形成可以稳定地存在于组合物中的铜络合物。其实例包括由CuCN和KCN的组合或者CuSCN和KSCN或KCN的组合形成的氰化铜络合物，和由CuSO4和EDTA·2Na的组合形成的Cu-EDTA络合物。
关于络合剂，可以使用能够与铜离子形成络合物的化合物；其实例包括无机化合物，例如氰化物化合物和硫氰酸盐化合物，以及多元羧酸，并且其具体实例包括乙二胺四乙酸、乙二胺四乙酸盐例如乙二胺四乙酸二氢二钠二水合物，氨基羧酸例如次氨基三乙酸和亚氨基二乙酸，羟基羧酸(oxycarboxylic acid)例如柠檬酸和酒石酸、琥珀酸、草酸，乙二胺四亚甲基膦酸，和甘油。
在某些实施方案中，正电性金属例如铜以至少1ppm，例如至少5ppm，或在一些情形中至少10ppm的总金属(按照元素金属测量)的量包含在预处理组合物中。在某些实施方案中，正电性金属以不大于500ppm，例如不大于100ppm，或在一些情形中不大于50ppm的总金属(按照元素金属测量)的量包含在该预处理组合物中。预处理组合物中正电性金属的量可以在所列出的数值的任意组合之间，包含所列出的数值在内。
本发明的预处理组合物还包含游离氟。正如将被理解的，本发明的预处理组合物中游离氟的来源可以变化。例如在一些情形中，游离氟可以源自于在预处理组合物中使用的IIIB和/或IVB族金属化合物，例如六氟锆酸的情形。当在预处理过程期间IIIB和/或IVB族金属沉积在金属基材上时，六氟锆酸中的氟将变成游离氟并且正如将被理解的，当用本发明预处理组合物预处理金属时，预处理组合物中游离氟的含量，如果未经检验，将随着时间增加。
另外，本发明预处理组合物中游离氟的来源可以包括不同于IIIB和/或IVB族金属化合物的化合物。这些来源的非限定实例包括HF、NH4F、NH4HF2、NaF和NaHF2。
如本文中使用的术语“游离氟”是指孤立的氟离子，并且其在本发明预处理组合物中的浓度可以通过用具有氟离子电极的测量仪测量预处理组合物来确定。本文中的实施例阐述了测量用于本发明目的的组合物中游离氟浓度的合适方法。
本发明的预处理组合物还包含由形成具有至少11，在一些情形中至少15，或在另一些情形中至少20的pKsp的氟化物盐的金属形成的金属氟化物盐。正如将被理解的，pKsp是指化合物的溶解度乘积常数的反对数。在本发明中，提供其中金属被选择为使得其形成具有至少11的pKsp的氟化物盐的含金属的化合物。出于本发明的目的，金属氟化物盐的pKsp值是指在Lange’s Handbook of Chemistry，第15版，McGraw-Hill，1999，表8.6中报导的pKsp值。在本发明的某些实施方案中，形成具有至少11的pKsp的氟化物盐的金属选自铈(CeF3的pKsp为15.1)、镧(LaF3的pKsp为16.2)、钪(ScF3的pKsp为23.24)、钇(YF3的pKsp为20.06)、或其混合物。
此外，在本发明的组合物中，这样选择被提供以形成具有至少11的pKsp的氟化物盐的含金属的化合物的量：使得组合物中游离氟的含量不小于0.1ppm，在一些情形中不小于20ppm，并且不大于300ppm，在一些情形中不大于100ppm。正如将被理解的并且如前所述，当用其预处理金属时，本发明预处理组合物中游离氟的含量将随着时间增加。在本发明中，将如上所述的含金属的化合物根据需要提供到预处理组合物中以将预处理组合物的游离氟含量保持在不小于0.1ppm并且不大于300ppm。
根据本发明，可以在其形成时相对即刻从本发明组合物中除去由形成具有至少11的pKsp的氟化物盐的金属形成的金属氟化物盐，或者如果被选择，可以使氟化物盐保留在组合物中一段时间。出于本发明的目的，重要的是该氟化物盐形成并且存在于组合物中，尽管只是短暂的。
因此，在本发明的某些实施方案中，将含钇的化合物提供到预处理组合物中。特别地，加入本发明预处理组合物中的钇的来源导致通过与组合物中的游离氟反应而形成钇氟化物，例如YF3。在某些实施方案中，预处理组合物中的钇来源是水溶性钇盐例如乙酸钇、氯化钇、甲酸钇、碳酸钇、氨基磺酸钇、乳酸钇和硝酸钇。当钇将作为水溶液加入预处理组合物中时，硝酸钇-一种容易获得的钇化合物是合适的钇来源。适用于本发明预处理组合物中的其它钇化合物是有机和无机钇化合物，例如氧化钇、溴化钇、氢氧化钇、钼酸钇、硫酸钇、硅酸钇和草酸钇。也可以使用有机钇络合物和钇金属。合适的铈化合物包括，但不限于，六水合硝酸铈。合适的镧化合物包括，但不限于硝酸镧水合物。
已经发现，通过选择包含形成具有至少11的pKsp的金属氟化物盐的金属的含金属的化合物，该含金属的化合物在从组合物中除去游离氟方面比其中使用包含形成具有小于11的pKsp的金属氟化物盐的金属的含金属的化合物的情形更有效，由此使得更容易控制组合物中游离氟的含量。另外，例如其中使用含钇的化合物的本发明实施方案，所得的含金属氟化物盐YF3的泥渣被认为是环境友好的，因为钇不被认为是重金属。因此，本发明的组合物避免了在一些现有技术金属预处理组合物中存在的环境缺陷。
在某些实施方案中，预处理组合物的pH为2.0-7.0，例如3.5-5.5。根据需要，可以使用例如任何酸或碱调节预处理组合物的pH。在某些实施方案中，通过包含碱性物质来保持溶液的pH，所述碱性物质包括水溶性和/或水分散性碱，例如氢氧化钠、碳酸钠、氢氧化钾、氢氧化铵、氨和/或胺例如三乙胺、甲基乙基胺或其混合物。
在某些实施方案中，该预处理组合物还包含树脂基料(resinousbinder)。合适的树脂包括一种或多种烷醇胺和含至少两个环氧基的环氧官能物质的反应产物，例如披露于美国专利No.5,653,823中的那些。在一些情形中，这类树脂包含通过在树脂的制备中使用二羟甲基丙酸、邻苯二甲酰亚胺或硫代甘油(mercaptoglycerine)作为附加反应物而引入的β羟基酯、酰亚胺或硫化物官能团。作为选择，反应产物是双酚A的二缩水甘油醚(可作为EPON 880从Shell Chemical Company商购获得)、二羟甲基丙酸和二乙醇胺以0.6-5.0∶0.05-5.5∶1摩尔比的反应产物。其它合适的树脂基料包括披露于美国专利No s.3,912,548和5,328,525中的水溶性和水分散性聚丙烯酸类；描述于美国专利No.5,662,746中的酚醛树脂；水溶性聚酰胺例如描述于WO95/33869中的那些；描述于加拿大专利申请2,087,352中的马来酸或丙烯酸与烯丙基醚的共聚物；以及水溶性和水分散性树脂，包括环氧树脂、氨基塑料、酚醛树脂、丹宁酸类物质和聚乙烯基苯酚，如论述于美国专利No.5,449,415中的。
在本发明的这些实施方案中，基于组合物中组分的总重量，树脂基料以0.005-30重量％，例如0.5-3重量％的量存在于预处理组合物中。
然而在另一些实施方案中，预处理组合物基本上不含或者在一些情形中完全不含任何树脂基料。当关于预处理组合物中不存在树脂基料而使用时，本文中使用的术语“基本上不含”是指任何树脂基料以小于0.005重量％的量存在于预处理组合物中。本文中使用的术语“完全不含”是指预处理组合物中根本没有树脂基料。
该预处理组合物可以任选地含有常规用于预处理领域中的其它物质例如非离子表面活性剂和助剂。在水性介质中，可以存在水分散性有机溶剂例如具有至多约8个碳原子的醇，例如甲醇、异丙醇等；或者二醇醚例如乙二醇、二甘醇或丙二醇的单烷基醚等。当存在时，基于水性介质的总体积，水分散性有机溶剂典型地以至多约10体积％的量使用。
其它任选的物质包括充当消泡剂或基材润湿剂的表面活性剂。
在某些实施方案中，预处理组合物还包含反应促进剂，例如亚硝酸根离子、硝酸根离子、含硝基的化合物、羟胺硫酸盐、过硫酸根离子、亚硫酸根离子、硫代硫酸根离子、过氧化物、铁(III)离子、柠檬酸铁化合物、溴酸根离子、全氯化物离子(perchlorinate ion)、氯酸根离子、亚氯酸根离子以及抗坏血酸、柠檬酸、酒石酸、丙二酸、琥珀酸和其盐。合适的物质的具体实例和它们的量描述于美国专利申请公开No.2004/0163736A1的[0032]-[0041]中，该引用部分通过引用并入本文。
在某些实施方案中，预处理组合物还包含填料，例如硅质填料。合适的填料的非限定实例包括二氧化硅、云母、蒙脱石、高岭石、石棉、滑石、硅藻土、蛭石、天然和合成沸石、水泥、硅酸钙、硅酸铝、硅酸钠铝、聚硅酸铝、氧化铝二氧化硅凝胶和玻璃颗粒。除了硅质填料之外，也可以使用其它细粒状、基本上不溶于水的填料。这类任选填料的实例包括炭黑、木炭、石墨、氧化钛、氧化铁、氧化铜、氧化锌、氧化锑、氧化锆、氧化镁、氧化铝、二硫化钼、硫化锌、硫酸钡、硫酸锶、碳酸钙和碳酸镁。
在某些实施方案中，预处理组合物包含磷酸根离子。在某些实施方案中，磷酸根离子以10-500ppm磷酸根离子，例如25-200ppm磷酸根离子的量存在。例举性磷酸根离子来源包括H3PO4、NaH2PO4和/或(NH4)2H2PO4。然而在某些实施方案中，本发明的预处理组合物基本上不含或在一些情形中完全不含磷酸盐离子。当关于预处理组合物中不存在磷酸根离子而使用时，本文中使用的术语“基本上不含”是指磷酸根离子以小于10ppm的量存在于组合物中。当关于不存在磷酸根离子而使用时，本文中使用的术语“完全不含”是指组合物中根本没有磷酸根离子。
在某些实施方案中，预处理组合物基本上不含或在一些情形中完全不含铬酸盐和/或重金属磷酸盐，例如磷酸锌。当关于预处理组合物中不存在铬酸盐和/或重金属磷酸盐而使用时，如本文中使用的术语“基本上不含”是指这些物质不以使得它们造成环境负担的程度存在于组合物中。即，它们基本上不被使用并且在使用基于磷酸锌的处理剂的情形中形成的泥渣例如磷酸锌的形成得以消除。当关于不存在重金属磷酸盐和/或铬酸盐而使用时，如本文中使用的术语“完全不含”是指组合物中根本没有重金属磷酸盐和/或铬酸盐。
此外在某些实施方案中，预处理组合物基本上不含或在一些情形中完全不含任何有机物质。当关于组合物中不存在有机物质而使用时，如本文中使用的术语“基本上不含”是指如果有的话，任何有机物质作为附带的杂质存在于组合物中。换句话说，任何有机物质的存在不影响组合物的性能。当关于不存在有机物质而使用时，如本文中使用的术语“完全不含”是指组合物中根本没有有机物质。
在某些实施方案中，该预处理涂料组合物的残余物的膜覆盖率通常为1-1000毫克/平方米(mg/m2)，例如10-400mg/m2。该预处理涂料的厚度可以变化，但其通常非常薄，常常具有小于1微米的厚度，在一些情形中其为1-500纳米，在另一些情形中其为10-300纳米。
在与预处理溶液接触后，可用水漂洗基材并干燥。
在本发明方法的某些实施方案中，在基材与预处理组合物接触后，然后使其与包含成膜树脂的涂料组合物接触。任何合适的技术可用于使基材与该涂料组合物接触，包括例如刷涂、浸涂、流涂、喷涂等。然而在下面更详细描述的某些实施方案中，该接触包括其中通过电沉积使可电沉积的组合物沉积在金属基材上的电涂步骤。
如本文中使用的术语“成膜树脂”是指当除去存在于组合物中的任何稀释剂或载体时或者当在环境或升高的温度下固化时，可以在基材的至少水平面上形成自支承的连续膜的树脂。可以使用的常规成膜树脂包括，但不限于，通常用于汽车OEM涂料组合物、汽车修补涂料组合物、工业涂料组合物、农业涂料组合物、卷材涂料组合物和航空航天涂料组合物中的那些。
在某些实施方案中，涂料组合物包含热固性成膜树脂。如本文中使用的术语“热固性”是指当固化或交联时不可逆地“固定”的树脂，其中聚合物组分的聚合物链通过共价键连接在一起。该性能通常与常常例如通过热或辐射诱导的组合物组分的交联反应相关。固化或交联反应也可以在环境条件下进行。一旦固化或交联，热固性树脂在施加热时将不会熔融并且不可溶于溶剂中。在另一些实施方案中，涂料组合物包含热塑性成膜树脂。如本文中使用的术语“热塑性”是指包含不通过共价键连接的聚合物组分并因此当加热时可能经历液体流动以及可溶于溶剂中的树脂。
如前所述，在某些实施方案中，通过电涂步骤使基材与包含成膜树脂的涂料组合物接触，在该步骤中通过电沉积使可电沉积的组合物沉积在金属基材上。在电沉积过程中，使充当电极的被处理的金属基材和导电性反电极与离子型可电沉积的组合物接触。当在它们与可电沉积的组合物接触的同时电流在电极与反电极之间通过时，可电沉积的组合物的附着膜将以基本上连续的方式沉积在金属基材上。
电沉积通常在1伏特至数千伏特、典型地50-500伏特的恒定电压下进行。电流密度通常为1.0安培/平方英尺-15安培/平方英尺(10.8-161.5安培/平方米)并且在电沉积过程期间趋向于迅速降低，这表明连续自绝缘膜的形成。
用于本发明某些实施方案中的可电沉积的组合物通常包含分散在水性介质中的树脂相，其中该树脂相包含：(a)含活性氢基团的离子型可电沉积树脂，和(b)具有对(a)的活性氢基团呈反应性的官能团的固化剂。
在某些实施方案中，用于本发明的某些实施方案中的可电沉积的组合物包含作为主要成膜聚合物的含活性氢的离子型、常常阳离子型可电沉积树脂。广泛种类的可电沉积成膜树脂是已知的并且可用于本发明中，只要该聚合物是“水分散性”的，即适于在水中溶解、分散或乳化。水分散性聚合物本质上是离子型的，即该聚合物将含有阴离子官能团以赋予负电荷，或者通常优选的是含有阳离子官能团以赋予正电荷。
适用于阴离子型可电沉积的组合物中的成膜树脂的实例是碱溶解的含羧酸的聚合物，例如干性油或半干性脂肪酸酯与二羧酸或酐的反应产物或加合物；和脂肪酸酯、不饱和酸或酐和任何另外的进一步与多元醇反应的不饱和改性物质的反应产物。另外合适的是不饱和羧酸的羟基-烷基酯、不饱和羧酸和至少一种其它烯属不饱和单体的至少部分中和的互聚物。另一种合适的可电沉积成膜树脂包括醇酸-氨基塑料载体，即含有醇酸树脂和胺-醛树脂的载体。另一种阴离子型可电沉积的树脂组合物包含树脂多元醇的混合酯，例如描述于美国专利No.3,749,657，9栏1-75行和10栏1-13行中的，该引用部分通过引用并入本文。也可以使用其它酸官能聚合物，例如本领域那些技术人员公知的磷酸盐化聚环氧化物(phosphatized polyepoxide)或磷酸盐化丙烯酸类聚合物。
如前所述，通常希望含活性氢的离子型可电沉积树脂(a)是阳离子型的并且能够沉积在阴极上。这类阳离子型成膜树脂的实例包括含胺盐基团的树脂，例如聚环氧化物和伯胺或仲胺的被酸溶解的反应产物，例如描述于美国专利Nos.3,663,389；3,984,299；3,947,338和3,947,339中的那些。通常，这些含胺盐基团的树脂与封端异氰酸酯固化剂组合使用。异氰酸酯可以被完全封端，如美国专利No.3,984,299中所述的，或者异氰酸酯可以被部分封端并且与树脂主链反应，例如在美国专利No.3,947,338中所述的。另外可以使用如描述于美国专利No.4,134,866和DE-OS No.2,707,405中的单组分组合物作为成膜树脂。除了环氧-胺反应产物之外，成膜树脂也可以选自阳离子型丙烯酸类树脂，例如描述于美国专利Nos.3,455,806和3,928,157中的那些。
除了含胺盐基团的树脂之外，也可以使用含季铵盐基团的树脂，例如由有机聚环氧化物与叔胺盐反应形成的那些，如描述于美国专利Nos.3,962,165；3,975,346；和4,001,101中的。其它阳离子型树脂的实例是含叔锍盐基团的树脂和含季鏻盐基团的树脂，例如分别描述于美国专利Nos.3,793,278和3,984,922中的那些。还可以使用通过酯交换固化的成膜树脂，例如在欧洲申请No.12463中描述的。另外，可以使用由曼尼希碱制备的阳离子组合物，例如在美国专利No.4,134,932中描述的。
在某些实施方案中，存在于可电沉积的组合物中的树脂是含有伯胺基和/或仲胺基的带正电荷的树脂，例如描述于美国专利Nos.3,663,389；3,947,339；和4,116,900中的。在美国专利No.3,947,339中，使多胺例如二亚乙基三胺或三亚乙基四胺的聚酮亚胺衍生物与聚环氧化物反应。当将反应产物用酸中和并且分散在水中时，生成游离的伯胺基。另外，当使聚环氧化物与过量的多胺例如二亚乙基三胺和三亚乙基四胺反应并且将过量的多胺从反应混合物中真空气提时形成等价产物，如描述于美国专利Nos.3,663,389和4,116,900中的。
在某些实施方案中，基于电沉积浴的总重量，含活性氢的离子型可电沉积树脂以1-60重量％，例如5-25重量％的量存在于可电沉积的组合物中。
如所述的那样，可电沉积的组合物的树脂相通常进一步包含适于与离子型可电沉积树脂的活性氢基团反应的固化剂。例如，封端有机多异氰酸酯和氨基塑料固化剂均适用于本发明，尽管封端异氰酸酯通常在这里优选用于阴极电沉积(cathodic electrodeposition)。
通常作为用于阴离子电沉积(anionic electrodeposition)的优选固化剂的氨基塑料树脂是胺或酰胺与醛的缩合产物。合适的胺或酰胺的实例是三聚氰胺、苯并胍胺、脲和类似的化合物。一般而言，使用的醛是甲醛，尽管产物可由其它醛例如乙醛和糠醛制得。根据使用的特定醛，缩合产物包含羟甲基或类似的羟烷基。通常，这些羟甲基通过与醇，例如含有1-4个碳原子的一元醇例如甲醇、乙醇、异丙醇和正丁醇反应而醚化。氨基塑料树脂可以以商标CYMEL从American Cyanamid Co.和以商标RESIMENE从Monsanto Chemical Co.商购获得。
氨基塑料固化剂通常以5-60重量％，例如20-40重量％的量与含活性氢的阴离子型可电沉积树脂组合使用，该百分比基于可电沉积的组合物中树脂固体的总重量。
如所述的，封端有机多异氰酸酯通常被用作阴极电沉积组合物中的固化剂。多异氰酸酯可被完全封端，如美国专利No.3,984,299，1栏1-68行，2栏和3栏1-15行中描述的，或者多异氰酸酯可以被部分封端并且与聚合物主链反应，如美国专利No.3,947,338，2栏65-68行，3栏和4栏1-30行中描述的，它们的引用部分通过引用并入本文。“封端”是指异氰酸酯基团已经与化合物反应，使得所得的封端异氰酸酯基团在环境温度下对活性氢稳定但在通常90℃-200℃的升高的温度下对成膜聚合物中的活性氢呈反应性。
合适的多异氰酸酯包括芳族和脂族多异氰酸酯，包括脂环族多异氰酸酯，并且代表性实例包括二苯基甲烷-4，4’-二异氰酸酯(MDI)、2，4-或2，6-甲苯二异氰酸酯(TDI)，包括其混合物，对-亚苯基二异氰酸酯、四亚甲基二异氰酸酯和六亚甲基二异氰酸酯、二环己基甲烷-4，4’-二异氰酸酯、异佛尔酮二异氰酸酯、苯基甲烷-4，4’-二异氰酸酯和多亚甲基多苯基异氰酸酯的混合物。可以使用高级多异氰酸酯例如三异氰酸酯。一个实例将包括三苯基甲烷-4，4’，4”-三异氰酸酯。也可以使用与多元醇例如新戊二醇和三羟甲基丙烷、和与聚合物多元醇例如聚己内酯二醇和三醇(NCO/OH当量比大于1)的异氰酸酯预聚物。
多异氰酸酯固化剂典型地以5-60wt％，例如20-50wt％的量与含活性氢的阳离子型可电沉积树脂组合使用，该百分比基于可电沉积的组合物中树脂固体的总重量。
在某些实施方案中，该包含成膜树脂的涂料组合物还包含钇。在某些实施方案中，钇以10-10,000ppm，例如不大于5,000ppm，在一些情形中不大于1,000ppm的总量钇(按照元素钇测量)的量存在于该组合物中。
可溶性和不溶性钇化合物均可以充当钇来源。适用于不含铅的可电沉积涂料组合物中的钇来源的实例是可溶性有机和无机钇盐例如乙酸钇、氯化钇、甲酸钇、碳酸钇、氨基磺酸钇、乳酸钇和硝酸钇。当钇将作为水溶液加入电涂浴中时，硝酸钇一一种容易获得的钇化合物是一种优选的钇来源。适用于可电沉积组合物的其它钇化合物是有机和无机钇化合物，例如氧化钇、溴化钇、氢氧化钇、钼酸钇、硫酸钇、硅酸钇和草酸钇。也可以使用有机钇络合物和钇金属。当钇将作为颜料糊中的组分引入电涂浴中时，氧化钇通常是一种优选的钇来源。
本文中描述的可电沉积的组合物为水性分散体的形式。术语“分散体”被认为是其中树脂处于分散相中并且水处于连续相中的两相透明、半透明或不透明的树脂体系。树脂相的平均粒径一般小于1.0微米、通常小于0.5微米，常常小于0.15微米。
基于水性分散体的总重量，水性介质中树脂相的浓度常常为至少1wt％，例如2-60wt％。当该组合物为树脂浓缩物的形式时，基于水性分散体的重量，它们一般具有20-60wt％的树脂固体含量。
本文中描述的可电沉积的组合物常常作为两组分提供：(1)透明树脂进料，其通常包括所述含活性氢的离子型可电沉积树脂，即主要成膜聚合物、固化剂和任何另外的水分散性非着色组分；和(2)颜料糊，其通常包括一种或多种着色剂(下文有述)、可与主要成膜聚合物相同或不同的水分散性研磨树脂、和任选地，添加剂例如润湿或分散助剂。电沉积浴组分(1)和(2)被分散在包含水和通常地，聚结溶剂(coalescing solvent)的水性介质中。
如前所述，除了水之外，水性介质可以含有聚结溶剂。可用的聚结溶剂常常是烃类、醇类、酯类、醚类和酮类。优选的聚结溶剂常常为醇类、多元醇类和酮类。具体的聚结溶剂包括异丙醇、丁醇、2-乙基己醇、异佛尔酮、2-甲氧基戊酮、乙二醇和丙二醇，以及乙二醇的单乙醚基、单丁基醚和单己基醚。基于水性介质的总重量，聚结溶剂的量通常为0.01-25wt％，例如0.05-5wt％。
另外，着色剂和如果需要，各种添加剂例如表面活性剂、润湿剂或催化剂可以包含在含有成膜树脂的涂料组合物中。如本文中使用的术语“着色剂”是指将颜色和/或其它不透明性和/或其它视觉效果赋予组合物的任何物质。着色剂可以任何合适的形式，例如离散颗粒、分散体、溶液和/或薄片加入到组合物中。可以使用单一着色剂或者两种或更多种着色剂的混合物。
着色剂的实例包括颜料、染料和调色料(tints)，例如在涂料工业中使用和/或在Dry Color Manufacturers Association(DCMA)中列出的那些，以及特殊效果组合物。着色剂可以包括例如在使用条件下不可溶但可润湿的细粒状固体粉末。着色剂可以是有机或无机的并且可以是聚集或非聚集的。可以通过利用研磨载体例如丙烯酸类研磨载体引入着色剂，所述研磨载体的使用是本领域技术人员熟知的。
颜料和/或颜料组合物的实例包括，但不限于，咔唑二噁嗪粗颜料、偶氮、单偶氮、双偶氮、萘酚AS、盐型(色淀)、苯并咪唑酮、缩合物、金属络合物、异二氢吲哚酮、异二氢吲哚和多环酞菁、喹吖啶酮、苝、紫环酮、二酮吡咯并吡咯、硫靛、蒽醌、靛蒽醌、蒽嘧啶、黄烷士酮、皮蒽酮、蒽嵌蒽醌、二噁嗪、三芳基碳鎓、喹酞酮颜料、二酮吡咯并吡咯红(“DPPBO红”)、二氧化钛、炭黑和它们的混合物。术语“颜料”和“着色填料”可互换地使用。
染料的实例包括，但不限于，溶剂和/或水基的那些例如酞氰绿或酞氰蓝、氧化铁、钒酸铋、蒽醌、苝、铝和喹吖啶酮。
调色料的实例包括，但不限于，分散在水基或可水混溶的载体中的颜料例如可从Degussa，Inc.，CHARISMA COLORANTS商购获得的AQUA-CHEM 896和可从Accurate Dispersions division of EastmanChemical，Inc.商购获得的CHARISMA COLORANTS和MAXITONERINDUSTRIAL COLORANTS。
如上所述，着色剂可以呈分散体形式，包括但不限于呈纳米颗粒分散体形式。纳米颗粒分散体可以包括一种或多种高度分散的纳米颗粒着色剂和/或着色剂颗粒，其产生所需的可见颜色和/或不透明性和/或视觉效果。纳米颗粒分散体可以包括粒径小于150nm例如小于70nm或小于30nm的着色剂例如颜料或染料。可以通过将原料有机或无机颜料与粒径小于0.5mm的研磨介质一起碾磨而产生纳米颗粒。纳米颗粒分散体实例和它们的制造方法在美国专利号6,875,800B2中进行了描述，该文献通过引用并入本文。纳米颗粒分散体也可以通过结晶、沉淀、气相冷凝和化学磨损(即，部分溶解)产生。为了使纳米颗粒在涂料中的再聚集最小化，可以使用树脂涂覆的纳米颗粒的分散体。本文所使用的“树脂涂覆的纳米颗粒的分散体”是指其中分散了离散“复合微粒”的连续相，该“复合微粒”包含纳米颗粒和在该纳米颗粒上的树脂涂层。树脂涂覆的纳米颗粒的分散体实例和它们的制造方法在2004年6月24目提交的美国专利申请公开2005-0287348A1和2003年6月24日提交的美国临时申请号60/482,167以及2006年1月20日提交的美国专利申请号11/337,062中进行了描述，所述文献通过引用并入本文。
可以使用的特殊效果组合物的实例包括产生一种或多种外观效应例如反射、珠光、金属光泽、磷光、荧光、光致变色、感光性、热致变色、随角异色(goniochromism)和/或颜色变化的颜料和/或组合物。另外的特殊效果组合物可以提供其它的可察觉性能例如不透明性或纹理。在某些实施方案中，特殊效果组合物可以产生色移，以致当在不同角度观察涂层时涂层的颜色改变。颜色效果组合物的实例描述于美国专利No.6,894,086中，其通过引用并入本文。另外的颜色效果组合物可以包括透明涂覆的云母和/或合成云母、涂覆的二氧化硅、涂覆的氧化铝、透明液晶颜料、液晶涂料和/或其中干涉由材料内的折射指数差异引起而不归因于材料表面和空气之间的折射指数差异的任何组合物。
在某些实施方案中，可以使用当暴露于一种或多种光源时可逆地改变其颜色的光敏组合物和/或光致变色组合物。可以通过暴露于特定波长的辐射而使光致变色和/或光敏组合物活化。当组合物受到激发时，分子结构被改变并且该改变的结构显示与该组合物的原始颜色不同的新颜色。当除去对辐射的暴露时，该光致变色和/或光敏组合物可以恢复到静态，其中恢复组合物的原始颜色。在某些实施方案中，光致变色和/或光敏组合物可以在非激发态下是无色的而在激发态下显示颜色。完全的变色可以在数毫秒至若干分钟内出现，例如20秒至60秒。光致变色和/或光敏组合物的实例包括光致变色染料。
在某些实施方案中，可以使光敏组合物和/或光致变色组合物与聚合物和/或可聚合组分的聚合材料关联和/或至少部分地结合，例如通过共价键合。与其中光敏组合物可能迁移出涂料并且结晶到基材中的一些涂料相反，根据本发明的某些实施方案与聚合物和/或可聚合组分关联和/或至少部分地结合的光敏组合物和/或光致变色组合物具有最小程度的迁移出涂料的作用。光敏组合物和/或光致变色组合物的实例及其制备方法描述于2004年7月16日提交的美国申请No.10/892,919中，其通过引用并入本文。
一般而言，着色剂可以以足以赋予所希望的视觉和/或颜色效果的任何量存在于涂料组合物中。着色剂可以占1-65重量％，例如3-40重量％或5-35重量％，该重量百分比基于组合物的总重量。
在沉积后，通常将涂料加热以固化沉积的组合物。加热或固化操作通常在120-250℃，例如120-190℃温度下进行10-60分钟时间。在某些实施方案中，所得膜的厚度为10-50微米。
正如将通过上述说明书理解的，本发明涉及用于处理金属基材的组合物。这些组合物包含：(a)IIIB和/或IVB族金属；(b)正电性金属；(c)百万分之0.1-300(“ppm”)的游离氟；(d)由形成具有至少11的pKsp的氟化物盐的金属形成的金属氟化物盐；和(e)水。在某些实施方案中，该组合物基本上不含重金属磷酸盐例如磷酸锌，和铬酸盐。
在另一些方面中，本发明涉及用于处理金属基材的组合物，其包含：(a)IIIB和/或IVB族金属；(b)0.1-300ppm的游离氟；(c)由形成具有至少11的pKsp的氟化物盐的金属形成的金属氟化物盐；和(d)水。本发明的这些组合物基本上不含磷酸根离子和铬酸盐。
正如贯穿前述说明书所述的，在某些实施方案中本发明的方法和涂覆的基材包括结晶磷酸盐例如磷酸锌或铬酸盐的沉积。因此，可以避免与这些物质相关的环境缺陷。然而，本发明的方法已经表明以与其中使用这些物质的方法相当或者在一些情形中甚至更优异的水平提供了在至少一些情形中耐腐蚀的涂覆的基材。这是本发明的令人惊奇并且出人意料的发现，并且满足了现有技术中的长期感到的需要。
以下实施例解释本发明，这些实施例不应被看作是将本发明限于它们的细节。实施例以及贯穿说明书中的所有份和百分比以重量计，除非另外说明。
实施例
可以采用本领域那些技术人员熟知的各种方法测量氟离子浓度，包括游离的和全部的氟离子。通常，使用离子选择电极(“ISE”)，例如由VWR International提供的氟离子选择组合电极或者类似的电极测量氟离子浓度。通过将电极浸入具有已知氟离子浓度的溶液中并且记录以毫伏计的读数；然后将这些毫伏读数绘制成对数曲线而将氟离子ISE标准化。然后可以将未知样品的毫伏读数与该校正曲线比较，并且确定氟离子浓度。作为选择，氟离子ISE可与将内部进行校正计算的仪表一起使用，并且因此在校正后可以直接读出未知样品的浓度。
氟离子是具有高电荷密度的小的负离子，因此在水溶液中其通常与具有高正电荷密度的金属离子例如锆或钛，或者与氢离子络合。由此络合的氟离子不能用氟离子ISE测量，除非它们所处的溶液与从这些络合物中释放氟离子的离子强度调节缓冲剂混合存在。在该点处，氟离子可通过氟离子ISE测量，并且该测量值被称为“全部的氟离子”。不使用该试剂进行的氟离子测量值被称为“游离的氟离子”，因为只有氟离子不与氢离子连接或者处于金属络合物中。
出于下面的实施例的目的，如下测量氟离子：通过将2mL各自分别含有100ppm、300ppm和1000ppm氯离子的标准溶液加入到50mL由在去离子水中10重量％二水合柠檬酸钠(可从Aldrich Chemical，Milwaukee，WI获得)组成的离子强度调节缓冲剂中制备校正标准。然后用氟离子ISE测量这些标准各自的毫伏读数并且用于构造如上所述的校正曲线。对于总的氟离子值，将2mL未知的溶液与50mL柠檬酸钠缓冲剂混合并且将该溶液的氟离子ISE的毫伏读数与生成的校正曲线比较以确定总的氟离子。通过直接读出样品溶液的毫伏数并且与校正曲线比较，并且然后将该数值除以26来确定游离的氟离子(该除法是必要的，因为由于离子强度调节缓冲剂而将标准稀释26倍，并且游离的氟离子样品不被稀释)。
实施例1
如下制备12L锆预处理浴：将10.5g 45％六氟锆酸(可从HoneywellSpecialty Chemicals，Morristown，NJ商购获得)和17.57g 5％w/w硝酸铜2/5水合物溶液(可从Fisher Scientific，Fair Lawn，NJ商购获得)加入到约12升自来水中。用Chemfil缓冲剂(可从PPGIndustries，Euclid，OH商购获得的温和碱性缓冲剂)将溶液中和至pH 4.5。如上所述用ISE测量游离的氟离子并且获得22ppm游离氟离子的值。
在该溶液中在80°F下伴随着适度混合将清洁的冷轧钢(CRS)板处理2分钟。该板具有青铜色外观，伴有一些蓝色虹彩，并且使用便携式X-射线荧光仪器(XRF)在约43nm处测量涂层厚度。
然后向锆预处理溶液中加入16.8g Chemfos AFL(可从PPGIndustries，Euclid，OH获得的液体游离氟离子添加剂)。该加入造成pH轻微地降至3.8。用Chemfil缓冲剂将溶液的pH调节回到4.5。如前测量游离氟离子并且发现为170ppm。然后与前述的板相同，通过该浴处理清洁的CRS板。该板具有浅青铜色外观，并且通过XRF测量的估计涂层厚度为20nm。因此较高含量的游离氟离子的存在使得涂层厚度降低大于50％。
在该点处，将3.02g六水合硝酸钇(可从Acros Organics-FisherScientific的子公司获得)加入到锆预处理溶液中。这造成pH轻微地降至pH 4.3。用Chemfil缓冲剂将其调节回到4.5。如上测量游离氟离子并且确定为115ppm。如上处理的清洁的CRS板具有中等青铜色，伴有一些蓝色虹彩，并且通过XRF测量的涂层厚度约为31nm。预处理浴稍微混浊，大概表明氟化钇化合物沉淀。
将另外3.06g六水合硝酸钇加入锆预处理浴中，这造成pH轻微地降至4.2。加入Chemfil缓冲剂使pH返回到4.5。如上测量的游离氟离子为61ppm，并且预处理浴具有另外的沉淀物。如上通过预处理浴处理的清洁的CRS板具有与先前的板类似的外观。通过XRF测量涂层厚度约为45nm。
将另外的2.98g六水合硝酸钇加入锆预处理浴中。该浴的pH轻微地降至4.2；加入足够的Chemfil缓冲剂使pH返回到4.5。如上测量游离氟离子并且发现为24ppm，这与起始值接近。如上处理清洁的CRS板。板为蓝色外观，伴有一些虹彩。用XRF测量的涂层厚度约为61nm。
实施例2
如下制备4升锆预处理浴：将3.5g 45％六氟锆酸和5.84g 5％w/w硝酸铜2/5水合物溶液加入到约4升自来水中，得到具有175ppm Zr和20ppm Cu的溶液。用Chemfil缓冲剂将溶液中和至pH 4.5。该溶液的游离氟离子测量为22ppm。溶液温度为82°F。取出2升该溶液并且用于预处理清洁的CRS板2分钟。板具有中等青铜色外观，并且使用便携式XRF仪器发现涂层厚度约为28nm。
向该2升浴液中加入6g Chemfos AFL。pH轻微地降至3.8。滴加Chemfil缓冲剂使溶液返回到pH 4.5。现在测量游离氟离子为320ppm。通过该浴处理2分钟的清洁的CRS板具有实际上不可见的预处理；使用XRF测量厚度为4nm。
向该溶液中加入硝酸镧水合物(可从Aldrich Chemical，Milwaukee，WI商购获得；32％La)。这时轻微混浊的溶液立即变模糊。用Chemfil缓冲剂将当加入硝酸镧时降至3.3的pH调节回到4.5。测量游离氟离子为31ppm。通过该浴处理2分钟的清洁的CRS板为青铜色，伴有蓝色虹彩，并且通过XRF测量具有25nm的涂层厚度。
实施例3
将初始的4L浴的余下2升部分用于处理清洁的CRS板2分钟。该板具有中等青铜色并且测量锆预处理涂层约为27nm厚。向该浴中加入6g Chemfos AFL。pH轻微地降至3.7，并且滴加Chemfil缓冲剂使其调节回到4.5。该浴的游离氟离子现在测量为316ppm。通过该浴处理2分钟的清洁的CRS板具有极少可见的预处理；使用XRF，测量厚度为5nm。
向该溶液中加入六水合硝酸铈(可从Alfa Aesar，Ward Hill，MA商购获得)。这时轻微混浊的溶液立即变模糊。用Chemfil缓冲剂将当加入硝酸铈时降至3.3的pH调节回到4.5。测量游离氟离子为28ppm。通过该浴处理2分钟的清洁的CRS板为青铜色，伴有蓝色虹彩，并且通过XRF测量具有29nm的涂层厚度。
本领域那些技术人员将理解的是可以对上述实施方案作出改变，只要不偏离其广泛发明思想。因此理解的是本发明不限于披露的特定实施方案，但其意在覆盖处于由附属的权利要求书定义的处于本发明的精神和范围内的变换方式。
Claims (20)
1.一种处理金属基材的方法，其包括：
使所述基材与包含以下组分的预处理组合物接触：
IIIB和/或IVB族金属；
正电性金属；
游离氟；和
水，
向预处理组合物提供可溶性金属盐，该盐形成具有至少11的pKsp的不溶性金属氟化物；
其中以足以将组合物中游离氟的含量保持至不小于0.1ppm并且不大于300ppm的量提供形成具有至少11的pKsp的金属氟化物盐的金属。
2.权利要求1的方法，其中金属基材包括冷轧钢、热轧钢、热浸镀锌钢、合金化热镀锌钢和/或镀锌合金钢。
3.权利要求1的方法，其中IIIB和/或IVB族金属包括锆。
4.权利要求1的方法，其中IIIB和/或IVB族金属以至少100ppm金属的量存在于预处理组合物中。
5.权利要求1的方法，其中正电性金属包括镍、铜、银和/或金。
6.权利要求1的方法，其中正电性金属以按照元素金属测量的至少10ppm总金属的量包含在预处理组合物中。
7.权利要求1的方法，其中游离氟源自于六氟锆酸。
8.权利要求1的方法，其中由形成具有至少11的pKsp的氟化物盐的金属形成的金属氟化物盐包含钇。
9.权利要求1的方法，其中以足以将组合物中游离氟的含量保持至不小于0.1ppm并且不大于100ppm的量提供形成具有至少11的pKsp的金属氟化物盐的金属。
10.权利要求1的方法，其中预处理组合物基本上不含磷酸根离子。
11.权利要求1的方法，其中预处理组合物基本上不含铬酸盐和/或磷酸锌。
12.权利要求1的方法，其进一步包括使所述基材与包含成膜树脂的涂料组合物接触，其中接触包括电涂步骤，在该步骤中通过电沉积使可电沉积的组合物沉积在金属基材上。
13.一种用于处理金属基材的预处理组合物，其包含：
IIIB和/或IVB族金属；
正电性金属；
0.1-300ppm的游离氟；
由形成具有至少11的pKsp的不溶性金属氟化物的金属形成的不溶性金属氟化物，所述金属包含钇、镧、钪及其组合；和
水；
其中以足以将组合物中游离氟的含量保持至不小于0.1ppm并且不大于300ppm的量提供形成具有至少11的pKsp的不溶性金属氟化物的金属。
14.权利要求13的预处理组合物，其中游离氟以不小于0.1ppm并且不大于100ppm的量存在于组合物中。
15.权利要求13的预处理组合物，其中IIIB和/或IVB族金属包括锆。
16.权利要求13的预处理组合物，其中IIIB和/或IVB族金属以至少100ppm金属的量存在于预处理组合物中。
17.权利要求13的预处理组合物，其中正电性金属包括镍、铜、银和/或金。
18.权利要求13的预处理组合物，其中正电性金属以按照元素金属测量的至少10ppm总金属的量包含在预处理组合物中。
19.权利要求13的预处理组合物，其中预处理组合物基本上不含磷酸根离子。
20.一种用于处理金属基材的预处理组合物，其包含：
(a)IIIB和/或IVB族金属；
(b)0.1-300ppm的游离氟；
(c)由形成具有至少11的pKsp的氟化物盐的金属形成的金属氟化物盐；和
(d)水，
其中该组合物基本上不含磷酸根离子和铬酸盐。
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- 2008-07-29 RU RU2010107612/02A patent/RU2447193C2/ru active
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- 2008-08-01 AR ARP080103353A patent/AR067777A1/es unknown
- 2008-08-01 TW TW097129375A patent/TWI440740B/zh not_active IP Right Cessation
- 2008-08-01 PE PE2008001298A patent/PE20090660A1/es not_active Application Discontinuation
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| Publication number | Publication date |
|---|---|
| EP2188414A2 (en) | 2010-05-26 |
| TWI440740B (zh) | 2014-06-11 |
| PE20090660A1 (es) | 2009-06-18 |
| UA100522C2 (ru) | 2013-01-10 |
| CN101796218A (zh) | 2010-08-04 |
| UY31270A1 (es) | 2009-03-02 |
| ES2769262T3 (es) | 2020-06-25 |
| BRPI0813047B1 (pt) | 2019-05-07 |
| US8673091B2 (en) | 2014-03-18 |
| HK1141841A1 (en) | 2010-11-19 |
| BRPI0813047A2 (pt) | 2014-12-16 |
| WO2009020794A3 (en) | 2009-03-26 |
| WO2009020794A2 (en) | 2009-02-12 |
| MX2010001213A (es) | 2010-03-01 |
| RU2010107612A (ru) | 2011-09-10 |
| EP2188414B1 (en) | 2019-12-18 |
| TW200912042A (en) | 2009-03-16 |
| KR20100050541A (ko) | 2010-05-13 |
| AR067777A1 (es) | 2009-10-21 |
| CA2694515A1 (en) | 2009-02-12 |
| KR101201648B1 (ko) | 2012-11-15 |
| RU2447193C2 (ru) | 2012-04-10 |
| US20090032144A1 (en) | 2009-02-05 |
| CA2694515C (en) | 2015-06-23 |
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