TW201305287A - 四級銨鹽作為油漆和塗料的防蝕添加劑之用途 - Google Patents
四級銨鹽作為油漆和塗料的防蝕添加劑之用途 Download PDFInfo
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- TW201305287A TW201305287A TW101139664A TW101139664A TW201305287A TW 201305287 A TW201305287 A TW 201305287A TW 101139664 A TW101139664 A TW 101139664A TW 101139664 A TW101139664 A TW 101139664A TW 201305287 A TW201305287 A TW 201305287A
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- Prior art keywords
- paint
- anion
- quaternary ammonium
- alkyl
- acid
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- 239000003973 paint Substances 0.000 title claims abstract description 69
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 24
- 238000000576 coating method Methods 0.000 title claims abstract description 23
- 239000000654 additive Substances 0.000 title claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000005260 corrosion Methods 0.000 claims abstract description 15
- -1 halogen anions Chemical class 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 239000004816 latex Substances 0.000 claims description 13
- 229920000126 latex Polymers 0.000 claims description 13
- 125000002015 acyclic group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000004922 lacquer Substances 0.000 claims description 6
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- 229920005989 resin Polymers 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
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- 239000002904 solvent Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 102000014171 Milk Proteins Human genes 0.000 claims description 2
- 108010011756 Milk Proteins Proteins 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005018 casein Substances 0.000 claims description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021240 caseins Nutrition 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 235000021239 milk protein Nutrition 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 238000007739 conversion coating Methods 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 11
- 235000021317 phosphate Nutrition 0.000 abstract description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001099 ammonium carbonate Substances 0.000 abstract description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract description 3
- 235000012501 ammonium carbonate Nutrition 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 47
- 239000010959 steel Substances 0.000 description 47
- 238000012360 testing method Methods 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 13
- 238000009472 formulation Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 239000007921 spray Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- 238000011282 treatment Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- TXOJCSIIFFMREV-UHFFFAOYSA-L didecyl(dimethyl)azanium;carbonate Chemical compound [O-]C([O-])=O.CCCCCCCCCC[N+](C)(C)CCCCCCCCCC.CCCCCCCCCC[N+](C)(C)CCCCCCCCCC TXOJCSIIFFMREV-UHFFFAOYSA-L 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007744 chromate conversion coating Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
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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
- C23C22/68—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 solutions with pH between 6 and 8
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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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- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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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
- C09D5/08—Anti-corrosive paints
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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
- 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
- C23C22/07—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 phosphates
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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
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- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
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- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
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Abstract
所揭示者為作為賦予油漆防蝕性質的轉化塗層或添加劑之包含非鹵素陰離子(例如碳酸根、碳酸氫根、磷酸根和甘醇酸根和混合物)之四級銨鹽。本發明係有關一種藉由施用包含一或多種四級銨碳酸鹽或碳酸氫鹽之組成物來抑制金屬表面的腐蝕之方法。本揭示也有關包含該等化合物的金屬基材用防蝕塗層和有關具有這些防蝕塗層的金屬基材。
Description
本發明係有關包含非鹵素陰離子如碳酸根、碳酸氫根、磷酸根和甘醇酸根之四級銨鹽作為轉化塗層的活性成分和作為油漆和塗料的添加劑之用途。
在其中金屬表面會與水(無論是液態水或潮溼空氣)接觸之方法中，總是有腐蝕的危險。當金屬本身有腐蝕的傾向且沒有被塗佈時，此特別是問題。
有腐蝕傾向之金屬的例子發現於從亞鐵合金製造之衝壓金屬汽車零件、磨損表面如機器製造之鋼零件和從鑄鐵製造之機器構件中。
轉化塗層係用來抑制腐蝕且保證油漆對金屬表面(特別是對鋼)的良好黏著。裸鋼與有機塗料並不形成良好結合。為了改良金屬/有機塗料結合，鉻酸鹽或磷酸鹽轉化塗層與鋼進行化學反應而形成具有金屬-磷酸鹽板體之粗糙表面，其提供有機聚合物對金屬表面的機械和化學聯鎖(黏著)兩者。參見，例如，Watson,J."A refresher：Understanding pretreatment",Powder Coating 1996,7(3)及Ferguson,D.；Monzyk,B.,"Nonpolluting replacement for chromate conversion coating and zinc phosphate in powder coating applications",Powder Coating 2001,72(7)。在此和下文中，應了解轉化塗層表示在金屬基材表面上之保護性阻隔薄膜
或層，其同時具有腐蝕抑制和油漆黏著二者之能力且係由(i)有機薄膜、(ii)從金屬蝕刻和再沈積方法產生之無機氧化物、(iii)從真實沈積方法產生的無機氧化物或(iv)任何來自(i)、(ii)和(iii)之無機和有機材料的混合物所構成。最廣泛使用的轉化塗層為鉻酸鹽處理、磷鉻酸鹽處理和磷酸鋅處理。咸信鉻酸鹽處理產生較好的腐蝕抑制作用，而磷鉻酸鹽處理產生較好的油漆黏著。在塗覆轉化塗層到金屬表面之前，必須清理金屬表面以除去任何在金屬表面上的油脂。轉化塗層然後可藉由浸漬或噴霧塗覆。鉻酸鹽和磷鉻酸鹽轉化塗層是最通常的化學轉化塗層，但是因為健康、安全和環境考量，需要其他類型的轉化塗層。
已發現包含非鹵素陰離子如碳酸氫根、碳酸根、磷酸根和甘醇酸根之四級銨鹽，更特定言之，包含作為陰離子的碳酸氫根、碳酸根、磷酸根和甘醇酸根之二烷基二甲基銨鹽，和其各種組合，具有作為金屬表面且特別是鋼的轉化塗層之適用性。此外，已發現該四級鹽類能夠產生所要的表面轉變，例如所要表面氧化物(也就是磁鐵礦，Fe3O4)在鋼基材上之生長。此氧化物形成產生黏著至金屬基材之獨特微晶區，且預期塗層如油漆對此會顯示改良的黏著性。除此之外，該四級銨鹽可直接地加到油漆以提供油漆對金屬表面的較好黏著和藉此改良耐腐蝕性。
四級銨碳酸鹽和碳酸氫鹽的腐蝕抑制性質已揭示於同
在申請中之美國專利申請案序號10/810279(US 2005/0003978A1)中。此外，已發現在抑制劑薄膜下，經保護的鋼表面生長出所要之表面氧化物(也就是磁鐵礦，Fe3O4)。此氧化物形成造成一些區域，預期有機塗料如油漆對此會顯示改良之黏著性。
發明的詳細說明
令人驚訝地，已經發現某些包含非鹵素陰離子之四級銨鹽，例如二正癸基二甲基碳酸銨，當塗覆至鐵和鐵合金如鋼的表面時，具有在比先前已知者溫和很多的溫度條件下，在鐵和鐵合金如鋼的表面上產生已知的想要轉變之傾向。雖然鋼表面在>110℃之熱誘發轉變在該技藝中為已知的，但產生該轉變需要之高溫至今已經限制它們的商業開發。然而，上述的四級銨鹽顯示能夠在低如室溫之溫度下產生相似的鋼表面轉變。
此外，上述四級銨鹽(純淨或調配物)之獨特性質允許在最後塗層塗覆之前的一步驟金屬表面製備方法。已經發現金屬暴露於其溶液將在最後塗層塗覆之製備中同時地清理、腐蝕抑制和底漆塗佈金屬表面。此表示優於目前以逐步驟方式完成下列獨立功能且具有顯著大量必須丟棄的工業污水之方法之顯著改良：
a)用油鈍化原料金屬以防止薄銹。
b)除去且丟棄鈍化油
c)在塗覆最後塗層之前，金屬表面用轉化塗層溶液(酸性，含重金屬的化學品)處理且硬化。
也已經發現根據本發明處理之鋼表面能抵抗薄銹。薄銹是在新形成之裸鋼表面暴露於水中且反應而形成紅色氫氧化鐵銹層時發生。
根據本發明處理之盤旋鋼板可抵抗在溼氣冷凝在卷板邊緣上時發生之邊緣沾染。目前鋼板在儲存或運輸之前係用輕油噴霧。此油必須在另外的表面處理或塗佈之前先除去。
根據本發明形成之氧化物薄膜具有作為鋼底漆轉化塗層或底漆之可能性。裸鋼與有機塗料並不形成良好的結合。為了改良金屬/有機塗料結合，鉻酸鹽或磷酸鹽轉化塗層係與鋼化學反應而形成具有金屬-磷酸鹽板體之粗糙表面，其提供有機聚合物對金屬表面的機械和化學聯鎖(黏著)兩者。
也已發現本發明之轉化塗層和防蝕漆顯示某些在刮擦時自行復原的性質，其表示甚至在刮痕中之“裸”金屬表面顯示一些鈍化作用，其可能是由於四級銨鹽從周圍塗料的遷移所致。在某些情況中，也觀察到造成刮擦區之長期鈍化之永久氧化物轉變。此為一種類似於在鉻塗佈之金屬表面上所觀察到的自行復原之效果。
特別地，本發明係有關一種將轉化塗層塗覆到金屬基材表面之方法，該方法包含使基材與一種組成物接觸之步驟，該組成物包含
(a)至少一種包含非鹵素陰離子之四級銨鹽，和(b)可選擇地，溶劑。
較佳地，四級銨鹽具有式
其中R1為一種可選擇地經芳基取代之C1-20烷基，及R2為一種可選擇地經芳基取代之C1-20烷基，R3和R4彼此獨立地為C1-4烷基，Xn-為一種選自由氫氧根、碳酸根、碳酸氫根、磷酸根、亞磷酸根、次磷酸根、硝酸根、硫酸根、硼酸根、飽和及不飽和無環C1-20單羧酸之陰離子、飽和及不飽和無環C2-20二羧酸之陰離子和羥基取代之羧酸的陰離子所組成群組之陰離子，和n表示該陰離子之負電荷的適當數目。
在此和下文中，C1-20烷基為具有1到20個碳原子之直鏈或支鏈烷基，包括但不限制於甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、己基、庚基、辛基、壬基、異壬基、癸基、十二烷基、十四烷基、十六烷基、十八烷基和二十烷基。芳基取代之C1-20烷基為任何具有芳基(特別是苯基)作為取代基之上述基。較佳的芳基取代之C1-20烷基的例子為苯甲基、苯乙基和苯丙基。
應了解術語“磷酸根”為包括磷酸之酸和中性鹽兩者，即磷酸二氫根(H2PO4 2-)、磷酸氫根(HPO4 2-)和磷酸根(PO4 3-)，
以及寡和多磷酸之鹽，例如二磷酸鹽(焦磷酸鹽)和三磷酸鹽。
亞磷酸根為包含陰離子H2PO2-及/或HPO32-之亞磷酸的鹽。
硫酸根為硫酸氫根(HSO4 -)和硫酸根(SO4 2-)及二硫酸根(S2O7 2-)和相關陰離子。
硼酸根為任何衍生自硼酸(H3BO3)和各種多硼酸的陰離子。
飽和及不飽和無環C1-20單羧酸特別是烷酸，例如甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸、癸酸、十二酸、十四酸、十六酸、十八酸和二十酸，或烯酸，例如丙烯酸、甲基丙烯酸、油酸和亞麻酸。
飽和及不飽和無環C2-20二羧酸特別是烷二酸，例如草酸、丙二酸、丁二酸、戊二酸和己二酸，或烯二酸，例如反-丁烯二酸或順-丁烯二酸。
羥基取代之羧酸為任何除羧酸基(等)之外具有至少一個羥基的羧酸，例如乙醇酸、蘋果酸、檸檬酸或水楊酸。
顯示上述效果之更佳四級銨鹽為四級銨碳酸鹽、四級銨碳酸氫鹽、四級銨磷酸鹽和四級銨甘醇酸鹽。
仍較佳地，式I的四級銨鹽中的R3和R4為甲基。
在較佳具體實例中，R1為甲基。
在一更佳具體實例中，R2為苯甲基或苯乙基。
在另一較佳具體實例中，R1和R2為相同的C1-20烷基。
在一更佳具體實例中，R1和R2為C10烷基。
在甚至更佳具體實例中，R1和R2為正-C10烷基。
在特佳具體實例中，四級銨鹽為二正癸基二甲基碳酸銨及/或二正癸基二甲基碳酸氫銨。
較佳地，金屬基材為鋼。
更佳地，鋼為盤旋鋼板。
本發明另一標的為一種製造物件，其包含一種根據上述方法或任何其較佳具體實例處理之金屬基材。
再次地，較佳金屬基材為鋼。
本發明又另一標的為一種防蝕漆，其包含(a)至少一種包含非鹵素陰離子之四級銨鹽，(b)黏合劑，(c)可選擇地，溶劑和(d)可選擇地，顏料。
如在上述方法中，防蝕漆中的四級銨鹽較佳具有下式
其中R1為一種可選擇地經芳基取代之C1-20烷基，及R2為一種可選擇地經芳基取代之C1-20烷基，R3和R4彼此獨立地為C1-4烷基，Xn-為一種選自由氫氧根、碳酸根、碳酸氫根、磷酸根、硝酸根、硫酸根、硼酸根、飽和及不飽和無環C1-20單羧酸之陰離子、飽和及不飽和無環C2-20二羧酸之陰離子和羥基取代之羧酸的陰離子所組成群組之陰離子，和n表示該陰離子之負電荷的適當數目。
在上述方法中之四級銨鹽的進一步較佳體實例類似地適用於防蝕漆。
較佳地，黏合劑係選自由丙烯酸樹脂、酪蛋白(乳蛋白質)、乙烯基樹脂、乳膠漆樹脂、乙酸酯樹脂、環氧樹脂和其混合物所組成之群組。
在一較佳具體實例中，防蝕漆為乳膠漆。
在另一較佳具體實例中，防蝕漆為瓷噴漆。
在進一步較佳具體實例中，防蝕漆為E-塗漆。
在另一較佳具體實例中，防蝕漆為丙烯酸漆。
本發明又另一標的為一種製造物件，其包含用上述防蝕漆油漆的金屬基材。全部關於防蝕漆性質、欲包含在該油漆中的銨鹽及金屬基材的較佳具體實例同樣地適用於該製造物件。
本發明又另一標的為一種具有下式的四級銨鹽作為油漆或塗料中之防蝕添加劑之用途，
其中R1為一種可選擇地經芳基取代之C1-20烷基，及R2為一種可選擇地經芳基取代之C1-20烷基，R3和R4彼此獨立地為C1-4烷基，Xn-為一種選自由氫氧根、碳酸根、碳酸氫根、磷酸根、亞磷酸根、次磷酸根、硝酸根、硫酸根、硼酸根、飽和及不飽和無環C1-20單羧酸之陰離子、飽和及不飽和無環C2-20二羧酸之陰離子和羥基取代之羧酸的陰離
子所組成群組之陰離子，和n表示該陰離子之負電荷的適當數目。
上述方法中之四級銨鹽的進一步較佳具體實例類似地適用於作為防蝕添加劑的用途。
下列實施例舉例說明本發明，但不是其限制。所有的份和百分比以重量計，除非另有指示。
實施例1
為了製備鋼板(S-46，購自Q-Panel Lab Products，Cleveland，俄亥俄州)用CarboShield®1000(二正癸基二甲基碳酸氫/碳酸銨)、“Phosphoquat”(二正癸基二甲基磷酸銨)和各種相關控制組的各種水性處理進行轉化塗層研究(參考：NB5751-001至018)。
直徑27.9公分(11”)和高度27.9公分(11”)的塑膠槽用來處理該等鋼板。用9,600克的試驗溶液充滿塑膠槽。位於離最高邊緣6.35毫米(1/4”)處具有直徑6.35毫米(1/4”)的孔之10.16公分x15.24公分x1.59毫米(4”x6”x1/16”)鋼(S-46)板係藉由將塑膠吸量管通過板中的孔來處理。使用相同的吸量管串聯最多三個板。此使該等板站直，且只有板底碰觸槽底。然後將槽放置在70℃烤箱一小時。在一個小時之後，從槽移出該等板，用紙巾弄乾然後包裝在塑膠包裝中且貼標籤。所製備的試驗溶液可發現於下述列表中。所有的濃度以重量百分比給予。CarboShield®和Phosphoquat®之所述濃度為活性化合物之真實濃度：
試驗溶液
去離子水
自來水(Allendale，NJ)
5%鹽(NaCl)水
在去離子水中之0.1%CarboShield®1000＊)
在自來水(Allendale，N.J.)中之0.1%CarboShield®1000
在5%鹽(NaCl)水中之0.1%CarboShield®1000
在去離子水中之0.1%Phosphoquat®＊＊)(pH=2.5)
在去離子水中之0.1%Phosphoquat®(pH=4.0)
在去離子水中之0.1%Phosphoquat®(pH=7.5)
在去離子水中之0.1%Glycoquat＊＊＊)(pH=7.5)
＊)CarboShield®1000為二正癸基二甲基碳酸(氫)銨(90莫耳%碳酸氫鹽，10莫耳%碳酸鹽)之50%水溶液。
＊＊)Phosphoquat®為藉由將獲得所需pH的量之85%磷酸水溶液加到CarboShield®1000而製得的二正癸基二甲基磷酸(氫)銨的溶液。
＊＊＊)Glycoquat為藉由將獲得特定pH所需量的羥基乙酸加到CarboShield®1000而製得的二正癸基二甲基甘醇酸銨的溶液。
在該等鋼板用試驗溶液處理之後，使用三種不同的油漆方法將它們油漆。各種油漆方法油漆二塊鋼板。在油漆方法之一中，使用Rust-Oleum專業高效瓷(Hunter Green)噴漆將該等鋼板噴漆。將四塊鋼板頭尾相連平放且用約18克塗覆至鋼板上表面的油漆噴漆且使其乾燥過夜。次日以相似的方法處理板底。使用Rust-Oleum®’s Painters
Touch®(Hunter Green)乳膠漆油漆第二組鋼板。油漆係用泡沫滾筒塗覆至鋼板。總計二塗層之油漆塗覆至鋼板的每側。使用己知為E-Coating(聚合物基塗料)之商業油漆方法油漆第三組鋼板。這些樣品在Royal E-Coat(Costa Mesa,California)使用專有方法油漆。第四組之鋼板(未處理)也使用其中於0.1%、0.5%或1.0%加入CarboShield® 1000之Rust-Oleum®’s Painters Touch®(Hunter Green)乳膠漆油漆。第五組鋼板(未處理)也使用其中於所示含量加入CarboShield® 1000、phosphoquat®或glycoquat的Rust-Oleum®’s光澤保護噴瓷(Hunter Green)漆油漆。
所有油漆之樣品都送到保証試驗服務(Assured Testing Services)(224 River Rd.,Ridge-way,PA 15853)進行鹽噴試驗(ASTM B117)。一組鋼板於鋼板的中心刻劃“X”。在5個不同位置測量刻劃的X之油漆拉回的數量(毫米)。然後平均該等測量。平均值愈低，處理性能也愈好。在試驗過程期間於不同時間間隔測量該等樣品。第二組邊緣用蠟塗佈以防止邊緣效應。未擾動的鋼板表面週期地評估總可見銹，並從0到100%分級。
轉化塗層/油漆/鹽噴試驗結果：
經噴漆(瓷)之鋼板顯示相對於控制組樣品之油漆黏著的最大改良。對於大部份所評估的試驗樣品，乳膠漆樣品沒有顯示在試驗樣品和對應控制組之間的差異。E-Coat樣品顯示在144小時之後最少量的油漆拉回。試驗樣品和控制之間存在差異的相關結果編輯在下表1和2中。
此數據清楚地証明當試板用CarboShield® 1000和phosphoquat材料預處理時，在商業噴瓷情況中對油漆剝離的顯著改良。
PQ=Phosphoquat；C=CarboShield
®
DI=去離子水。
列在表2之結果也被描述在圖5中。
製備未刻劃油漆板複製組而且進行鹽噴暴露試驗。下表3為試驗樣品和控制之間存在差異的主要結果之概述表。
全體而言，此數據証明CarboShield®1000和
phosphoquat版“轉化塗層”預處理二者在鹽噴試驗中顯著減少商業乳膠漆和瓷噴漆處理之總锈的顯著能力。
此數據顯示當CarboShield® 1000直接地摻入商業油漆調配物內時，油漆剥離的顯著改良。
在另一試驗中，對用摻有各種量的CarboShield® 1000(CS)的乳膠漆油漆之未擾動試驗板表面在鹽噴暴露24到456小時之後測定可見銹的量(%)。該等數據編輯在下表5中且描述於圖6中。
樣品係藉由刷式塗覆製備。
在另外的試驗中，用摻有各種量的CarboShield®
1000(CS)、phosphoquat和glycoquat之光澤保護噴瓷油漆的未擾動試驗板表面在鹽噴暴露24到168小時之後測定可見銹的量(%)。該等數據編輯在下表6中且描述於圖7中。
適用的話，所有的樣品係藉由刷塗製備以便可供摻料。
表5 & 6中的數據顯示當CarboShield®1000或相關phosphoquat或glycoquat材料直接摻入商業油漆調配物中時，耐腐蝕性的顯著改良。
實施例2 &比較例1
根據表7中所列之成分和處理步驟的量和順序調配二種乳膠漆。一種調配物(實施例2)包含CarboShield®1000而另一種(比較例1)包含陰離子表面活性劑(Triton®X-100)和習知腐蝕抑制劑(Canguard® 327)的組合。
Natrosol®250 HBR為Hercules公司(美國Wilmington,Delaware)的水溶性羥乙基纖維素。
Tamol®850為賓夕凡尼亞州費城羅門哈斯(Rohm and Haas)公司之聚丙烯酸鈉。
Triton®X-100為陶氏化學公司(Dow Chemical Company)的辛基酚乙氧化物。
Drewplus® L-493為新澤西州Boonton亞仕蘭特用化學品公司(Ashland Specialty Chemical Company)的消泡劑。
Canguard® 327為陶氏化學公司的子公司恩琪斯化學公司(ANGUS Chemical Company)之以噁唑啶為主的腐蝕抑制劑。
AMP-95TM為包含5%水之2-胺基-2-甲基-1-丙醇，其可得自恩琪斯化學公司。
Ti-Pure® R-931為杜邦鈦科技(Wilmington,Delaware)的金紅石二氧化鈦顏料。
Imsil®-15為Unimin特用礦物公司(Tamms,Illinois)的微晶矽石。
UCAR®123為UCAR乳膠系統(Cary,North Carolina)的高固體苯乙烯-丙烯黏合劑。
Texanol®為伊士曼化學公司(Eastman Chemical Company)(Kingsport,Tennessee)的單異丁酸2,2,4-三甲基-1,3-戊二醇酯。
Aerosol® RM-825為BASF AG(德國Ludwigshafen)的以丙烯酸酯共聚物為主的流變改性劑。
試驗表7調配物之儲存穩定性和黏度以及金屬表面上油漆薄膜的耐擦性和遮蓋力。
實施例2的調配物幾天內是穩定的，甚至優於比較例1，具有較少的分離。調配物也比比較調配物“更濃稠(creamier)”(更令人想要的)。此觀察證實CarboShield®1000可相容於乳膠漆系統。
遮蓋力，其為塗層隱藏黑色斑點的能力，在比較例中為96.8%，在根據本發明之實施例中為97.2%。此表示CarboShield®1000作用勝於界面活性劑Triton®X-100。遮蓋力係藉由使用在標準Leneta(類型2C)卡上的伯爾得棒下降
(bird bar draw down)(76.2微米=3密耳)測量，且以黑和白L-值(LAB彩色系統)之比值表示。
從實施例2調配物製備之油漆薄膜的耐擦性為480循環到不合格，而從比較例1調配物之油漆薄膜者只有370循環到不合格。此為顯著約30%改良。使用標準ASTM D2486方法學測量耐擦性。
光澤測量顯示從兩個調配物製備的塗層之間沒有顯著差異。
實施例2調配物的史托馬(Stormer)黏度顯著高於比較例1者，即83KU對73KU。此允許減少加至調配物的相關增稠劑之量。
圖1為鋼表面在包含0.1%二正癸基二甲基碳酸銨的3.5%NaCl水溶液中浸漬二個星期之後的SEM顯微鏡圖。注意表面上六角板體的形成。
圖2為鋼表面在包含0.1%二正癸基二甲基碳酸銨的3.5%NaCl水溶液中浸漬二個月之後的SEM顯微鏡圖。該表面佈滿板體和球體粒子。這些相之一為鐵磁性(磁鐵礦，Fe3O4)。
圖3為鋼表面在0.1%二正癸基二甲基甘醇酸銨在自來水中的溶液中於70℃浸漬48小時之後的SEM顯微鏡圖。
圖4為鋼表面在自來水中於70℃浸漬1小時之後(控制實驗)的SEM顯微鏡圖。
圖5描述用幾種E-塗佈鋼樣品在鹽噴霧暴露之後油漆剝離試驗的結果。
圖6描述用藉由加入四級銨鹽而防蝕之乳膠漆油漆的鋼樣品之鹽噴霧試驗的結果。
圖7描述用具有各種量的四級銨鹽之光澤保護噴瓷油漆的鋼樣品之鹽噴霧試驗的結果。
Claims (9)
- 一種防蝕漆，其包含(a)至少一種包含非鹵素陰離子之四級銨鹽，(b)黏合劑，(c)可選擇地，溶劑和(d)可選擇地，顏料。
- 根據申請專利範圍第1項之防蝕漆，其中四級銨鹽具有下式：
- 根據申請專利範圍第1或2項之防蝕漆，其中黏合劑係選自由丙烯酸樹脂、酪蛋白(乳蛋白質)、乙烯基樹脂、乳膠漆樹脂、乙酸酯樹脂、環氧樹脂和其混合物所組成之群組。
- 根據申請專利範圍第1或2項之防蝕漆，其為乳膠 漆。
- 根據申請專利範圍第1或2項之防蝕漆，其為瓷噴漆。
- 根據申請專利範圍第1或2項之防蝕漆，其為e-塗漆。
- 根據申請專利範圍第1或2項之防蝕漆，其為丙烯酸漆。
- 一種製造物件，其包含用申請專利範圍第1到7項中任一項之防蝕漆油漆的金屬基材。
- 一種具有下式的四級銨鹽之用途，
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| US63479304P | 2004-12-09 | 2004-12-09 |
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| TW094143497A TWI386519B (zh) | 2004-12-09 | 2005-12-09 | 將防蝕塗層塗覆到金屬基材表面之方法 |
| TW101139664A TWI454541B (zh) | 2004-12-09 | 2005-12-09 | 四級銨鹽作為油漆和塗料的防蝕添加劑之用途 |
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| JP (2) | JP5477835B2 (zh) |
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