CN114231154A - Chromium-free fingerprint-resistant coating for externally crosslinked galvanized steel sheet - Google Patents
Chromium-free fingerprint-resistant coating for externally crosslinked galvanized steel sheet Download PDFInfo
- Publication number
- CN114231154A CN114231154A CN202111565808.0A CN202111565808A CN114231154A CN 114231154 A CN114231154 A CN 114231154A CN 202111565808 A CN202111565808 A CN 202111565808A CN 114231154 A CN114231154 A CN 114231154A
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- China
- Prior art keywords
- water
- galvanized steel
- steel sheet
- resistant coating
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 33
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 33
- 239000011248 coating agent Substances 0.000 title claims abstract description 25
- 238000000576 coating method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 19
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 19
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- -1 polyethylene Polymers 0.000 claims abstract description 10
- 239000004698 Polyethylene Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229920000573 polyethylene Polymers 0.000 claims abstract description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000080 wetting agent Substances 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract 2
- 239000000839 emulsion Substances 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
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- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001541 aziridines Chemical class 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 2
- XKRPWHZLROBLDI-UHFFFAOYSA-N dimethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OC)OC XKRPWHZLROBLDI-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
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- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 7
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- 239000000126 substance Substances 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
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- 239000002253 acid Substances 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005237 degreasing agent Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical class C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical class C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
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- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 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
- 239000007788 liquid Substances 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
Abstract
The invention provides an external cross-linked chromium-free fingerprint-resistant coating for galvanized steel sheets, which comprises 25-50% of a film-forming substance, 1-5% of a silane coupling agent, 1-5% of silica sol, 0.1-0.5% of a wetting agent, 0.1-0.5% of a flatting agent, 0.5-5% of a polyethylene wax dispersoid and the balance of water; the film forming material is formed by uniformly mixing water-based polyurethane resin with a linear structure and water-based acrylic resin with a linear structure, wherein the ratio of the water-based polyurethane resin to the water-based acrylic resin is 1:2-2:1, and then curing and crosslinking through an additional curing agent. According to the invention, the polyurethane resin with a linear structure and the acrylic resin with a linear structure are mixed, the resins are mutually wound, and then the curing and crosslinking are carried out by adding the curing agent, so that the compactness of the film layer is greatly improved, and the performance of the film layer can be adjusted according to different types and dosage of the crosslinking agent.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to an externally crosslinked chromium-free fingerprint-resistant coating for a galvanized steel sheet.
Background
Galvanized steel sheets are widely used in the automotive, building, household electrical appliances, and electromechanical industries, but zinc on the surface of a metal material is easily corroded or white rust occurs in the atmosphere, thereby affecting the appearance of the metal material and causing adverse effects such as low coating performance. In order to improve the corrosion resistance and coating adhesion of galvanized steel sheets, the industry uses a treatment liquid containing chromic acid, dichromic acid, or salts thereof to treat the metal surface, which is commonly referred to as chromium treatment.
However, with the recent increase in domestic environmental awareness, chromium treatment has been gradually eliminated because 6-valent chromium in the treatment solution is harmful to the human body. In addition, the sewage containing 6-valent chromium must be specially treated according to relevant regulations to be discharged, and the problem of increasing the chromium treatment cost is also caused; the chromium-treated metal material cannot be recycled as chromium-containing waste, and is one of the major drawbacks of the chromium treatment technology.
In order to improve the corrosion resistance of metal materials, Japanese patent laid-open No. 53-121034 discloses a method of forming a coating film by applying an aqueous solution containing a water-dispersible silane, an alkyd resin, and a compound trialkoxysilane to the surface of a metal and drying the coating film. Further, a metal surface treatment method for imparting corrosion resistance to a metal material by using a pyrone derivative which is a hydroxyl compound composed of a water-soluble resin, and a metal surface treatment method for imparting corrosion resistance to a metal material by using an aqueous solution or a water-dispersible polymer of a hydroxyl compound are disclosed in Japanese patent laid-open Nos. 57-44751 and 1-177380, respectively. Japanese patent application laid-open No. 11-106945 discloses a metal surface treating agent comprising a metal ion having a valence of 2 or more, an acid, a silane coupling agent and a water-soluble polymer. However, any of the above metal surface treatment methods cannot replace the high corrosion resistance of the chromium film.
In addition, the galvanized steel sheet in some applications requires fingerprint resistance (for example, electronic devices such as tablet computers or household appliances such as refrigerators), that is, fingerprints are not easy to remain on the surface of the galvanized steel sheet, and the galvanized steel sheet needs to be formed after being coated with stamping oil, and then the stamping oil is washed away by using a degreasing agent or a solvent type cleaning agent. Strongly basic solvents are mostly used as degreasing agents. In the degreasing agent cleaning process, the problems that the surface of the galvanized steel sheet is easy to discolor and peel off and the like are caused, so that the fingerprint-resistant steel sheet is required to have certain acid-base resistance and solvent resistance, and therefore, the requirements on corrosion resistance, alkali resistance, solvent resistance and water resistance are high.
Disclosure of Invention
Aiming at the technical problems of the existing galvanized steel sheet, the invention provides the chromium-free fingerprint-resistant coating for the externally crosslinked galvanized steel sheet, which ensures that the coating has better fingerprint resistance and improves other performances such as salt spray resistance, acid and alkali resistance, solvent resistance, water resistance and the like.
The chromium-free fingerprint-resistant coating for the externally crosslinked galvanized steel sheet comprises the following components in percentage by mass:
the film forming substance is formed by uniformly mixing water-based polyurethane resin with a linear structure and water-based acrylic resin with a linear structure and then curing and crosslinking the mixture through an additional curing agent, wherein the ratio of the water-based polyurethane resin to the water-based acrylic resin is 1:2-2:1, and the curing agent is selected from one of polyisocyanates, aziridines, polycarbodiimides, epoxysilanes, N-methylol compounds and polyamine curing agents, and accounts for 1-3% by mass.
Further, the preparation raw materials of the waterborne polyurethane resin with the linear structure comprise 5-20% of diisocyanate, 30-40% of polyether polyol, a proper amount of catalyst, 2-7% of hydrophilic chain extender, 0.5-3% of ethylenediamine, 1-4% of neutralizer, 40-80% of deionized water and 5-10% of organic solvent;
diisocyanate and polyether polyol are mixed and stirred at a proper temperature, then a proper amount of catalyst is added for continuous stirring reaction, then hydrophilic chain extender is added for reaction, ethylene diamine dissolved in an organic solvent is added after the temperature is reduced, triethylamine dissolved in deionized water is added, and the reaction product is obtained by filtration.
Further, the preparation method of the aqueous polyurethane resin with the linear structure specifically comprises the following steps:
step A1, heating diisocyanate and polyether polyol to 80-90 ℃, stirring for 2-3 hours, adding a catalyst of dibutyl tin dilaurate, and continuing stirring for 1-2 hours;
step A2, cooling the reaction solution obtained in the step A1 to 60-65 ℃, adding a hydrophilic chain extender which is fully dispersed in a small amount of organic solvent N-methyl pyrrolidone, and heating to 80-90 ℃ again to react for 2-3 hours to obtain a waterborne polyurethane prepolymer;
step A3, cooling the temperature of the aqueous polyurethane prepolymer to 35-40 ℃, dissolving ethylenediamine in the residual organic solvent N-methyl pyrrolidone, adding the mixture into the aqueous polyurethane prepolymer, and stirring and shearing at a high speed for 0.5-2 hours;
and step A4, dissolving triethylamine in deionized water, adding the solution into the reaction solution obtained by stirring and shearing in the step A3 under high-speed stirring, reacting for 5-15 minutes, and filtering to obtain the triethylamine-containing catalyst.
Further, the diisocyanate is one or a mixture of more of isophorone diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate, cyclohexane diisocyanate and diphenylmethane diisocyanate; the hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid, 1, 4-butanediol, ethylene glycol and diethylene glycol.
Further, the preparation raw materials of the water-based acrylic resin with the linear structure comprise 25-30% of butyl acrylate, 8-15% of styrene, 0.2-1% of acrylic acid, 0.2-1% of hydroxyethyl acrylate, 0.5-1.5% of a nonionic emulsifier, 0.01-0.05% of ammonium persulfate and the balance of water, and the preparation method specifically comprises the following steps:
step B1, mixing ammonium persulfate and water accounting for 5% of the total amount to prepare an initiator;
step B2, mixing butyl acrylate, styrene, acrylic acid, hydroxyethyl acrylate and a nonionic emulsifier in sequence, and stirring until the mixture is uniformly dispersed to prepare a pre-emulsion;
step B3, adding 5-10% of pre-emulsion and 5-10% of initiator into a four-neck flask provided with a thermometer, a stirrer, a condenser and a constant pressure funnel, heating to 70-85 ℃, and reacting for 20-40min to prepare seed emulsion;
step B4, when the seed emulsion turns blue, 80% of pre-emulsion and 80% of initiator are dripped, and the dripping is finished within 3-4.5 h; controlling the temperature to be kept at 75-90 ℃ in the dripping process, and preserving the heat for 0.5-1.5h after dripping;
step B5, dropwise adding the residual pre-emulsion and the initiator, controlling the temperature to be kept at 75-90 ℃ in the dropwise adding process, and preserving the heat for 0.5-1h after the dropwise adding is finished;
and step B6, cooling to 50-60 ℃, neutralizing with ammonia water to pH 7-8, filtering and discharging to obtain milky emulsion slightly blue.
Further, the silane coupling agent contains at least one active hydrogen amino group or epoxy group as a reactive functional group per molecule.
Further, the silane coupling agent is one or more of N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and aminopropyltriethoxysilane, 3-propyltrimethoxysilane, 3-propylmethyldimethoxysilane, 2- (3, 4 epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane.
Further, the silica sol is a silica dispersion with the particle size of 10-100 nm; the wetting agent and the flatting agent are organic silicon auxiliaries; the polyethylene wax dispersoid is oxidized polyethylene wax or non-oxidized polyethylene wax with the particle diameter of 0.1-5 mu m.
The polyurethane resin with a linear structure and the acrylic resin with a linear structure are mixed, the resins are wound with each other, and then the resins are cured and crosslinked by adding the curing agent, so that the compactness of the film layer is greatly improved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Example 1
The chromium-free fingerprint-resistant coating for the externally crosslinked galvanized steel sheet comprises 15% of aqueous polyurethane resin, 25% of aqueous acrylic resin, 1% of silane coupling agent, 1% of silica sol, 0.1% of wetting agent, 0.1% of flatting agent, 0.5% of polyethylene wax dispersoid and the balance of water. The compositions of the film forming substances at this ratio are shown in table 1 below.
TABLE 1
Example 2
The chromium-free fingerprint-resistant coating for the externally crosslinked galvanized steel sheet comprises 25% of aqueous polyurethane resin, 15% of aqueous acrylic resin, 3% of silane coupling agent, 3% of silica sol, 0.3% of wetting agent, 0.3% of flatting agent, 2.5% of polyethylene wax dispersoid and the balance of water. The compositions of the film-forming substances at this ratio are shown in Table 2 below.
TABLE 2
Example 3
The chromium-free fingerprint-resistant coating for the externally crosslinked galvanized steel sheet comprises 30% of aqueous polyurethane resin, 20% of aqueous acrylic resin, 5% of silane coupling agent, 5% of silica sol, 0.5% of wetting agent, 0.5% of flatting agent, 5% of polyethylene wax dispersoid and the balance of water. At this component ratio, the structural compositions of the aqueous polyurethane resin and the aqueous acrylic resin are shown in table 3 below.
TABLE 3
Example 4
A chromium-free fingerprint-resistant coating for an externally crosslinked galvanized steel sheet comprises 24% of aqueous polyurethane resin, 24% of aqueous acrylic resin, 4% of silane coupling agent, 3% of silica sol, 0.2% of wetting agent, 0.3% of leveling agent, 4% of polyethylene wax dispersoid and the balance of water. At this component ratio, the structural compositions of the aqueous polyurethane resin and the aqueous acrylic resin are shown in table 4 below.
TABLE 4
Performance testing of examples 1-4
12 groups of galvanized steel sheets (3 groups in each example) with the same size and shape were selected, the galvanized steel sheets were respectively scraped with the paint in the above example and dried to obtain 12 groups of surface-treated galvanized steel sheets, and the evaluation was performed by the following method.
1. Acid and alkali resistance
A1 mol/L sulfuric acid solution or a 1% sodium hydroxide solution (10. mu.L) was dropped onto the surfaces of 12 groups of surface-treated galvanized steel sheets, and after leaving for 1 minute, the surface appearance was visually observed by rinsing with water. The evaluation criteria are as follows:
stage I: the surface of the skin film has no trace;
and II, stage: the surface of the involucra has marks which can be observed by naked eyes;
grade III: the surface of the film had a clear white mark and the film began to dissolve.
2. Solvent resistance
After immersing the steel sheets in ethanol, a mixed solution of 80% ethanol and 20% water, and acetone, respectively, with gauze, the surfaces of 12 groups of surface-treated galvanized steel sheets were rubbed back and forth with force 50 times, and then the change in surface appearance was visually observed and evaluated. The evaluation criteria are as follows:
stage I: the wiped portion was completely free of traces;
and II, stage: the wiping part has marks which can be observed by naked eyes;
grade III: the wiped portion had a clear white mark and the film began to dissolve.
3. Corrosion resistance
The white rust resistance was visually measured by a salt spray test (JISZ2371), and the time until the white rust area reached 5% was evaluated.
4. Water resistance
A proper amount of 100 ℃ boiling water was dropped onto the surfaces of 12 groups of surface-treated galvanized steel sheets, and after standing for 24 hours, the surface appearance was visually observed by washing with water. The evaluation criteria are as follows:
stage I: the surface of the skin film has no trace;
and II, stage: the surface of the involucra has marks which can be observed by naked eyes;
grade III: the surface of the film had a clear white mark and the film began to dissolve.
The results of the performance tests for examples 1-4 are summarized in Table 5 below.
| Group of | Acid and alkali resistance | Solvent resistance | Corrosion resistance | Water resistance |
| Examples 1 to 1 | Class I | Class I | 120h | Class I |
| Comparative examples 1 to 2 | Stage II | Class I | 96h | Stage II |
| Comparative examples 1 to 3 | Class III | Stage II | 72h | Class III |
| Example 2-1 | Class I | Class I | 120h | Class I |
| Comparative examples 2 to 2 | Class I | Class I | 96h | Class I |
| Comparative examples 2 to 3 | Stage II | Stage II | 72h | Class III |
| Example 3-1 | Class I | Class I | 120h | Class I |
| Comparative examples 3 to 2 | Stage II | Stage II | 72h | Stage II |
| Comparative examples 3 to 3 | Stage II | Stage II | 96h | Stage II |
| Example 4-1 | Class I | Class I | 120h | Class I |
| Comparative examples 4 to 2 | Stage II | Stage II | 96h | Stage II |
| Comparative examples 4 to 3 | Stage II | Stage | 72h | Stage II |
TABLE 5
As can be seen from the performance test results in Table 5, the chromium-free fingerprint-resistant coating for the galvanized steel sheet provided by the invention has the advantages that the polyurethane resin with a linear structure is mixed with the acrylic resin with a linear structure, the resins are mutually wound, and the curing and crosslinking are carried out through the addition of the curing agent, so that the compactness of the film layer is greatly improved, the performance of the film layer can be adjusted according to different types and dosage of the crosslinking agent, and the performance indexes of the fingerprint-resistant film layer, such as salt spray resistance, acid and alkali resistance, solvent resistance, water resistance and the like, are improved. On the contrary, if one of the urethane resin and the acrylic resin is a network structure, the two resins cannot be uniformly mixed as if both resins are linear structures due to steric hindrance, and thus the desired technical effect cannot be achieved.
Finally, it should also be noted that the above list is only one specific embodiment of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (9)
1. The chromium-free fingerprint-resistant coating for the externally crosslinked galvanized steel sheet is characterized by comprising the following components in percentage by mass:
the film forming material is formed by uniformly mixing water-based polyurethane resin with a linear structure and water-based acrylic resin with a linear structure and then curing and crosslinking through a curing agent, wherein the ratio of the water-based polyurethane resin to the water-based acrylic resin is 1:2-2: 1; the curing agent is selected from one of polyisocyanates, aziridines, polycarbodiimide, epoxy silane, N-methylol compounds and polyamine curing agents, and the mass ratio of the curing agent is 1-3%.
2. The chrome-free fingerprint-resistant coating for the externally crosslinked galvanized steel sheet as claimed in claim 1, wherein the raw materials for preparing the aqueous polyurethane resin with the linear structure comprise 5-20% of diisocyanate, 30-40% of polyether polyol, a proper amount of catalyst, 2-7% of hydrophilic chain extender, 0.5-3% of ethylenediamine, 1-4% of neutralizer, 40-80% of deionized water and 5-10% of organic solvent.
3. The chrome-free fingerprint resistant coating for an externally crosslinked galvanized steel sheet according to claim 2, characterized in that,
the preparation method of the waterborne polyurethane resin with the linear structure specifically comprises the following steps:
step A1, heating diisocyanate and polyether polyol to 80-90 ℃, stirring for 2-3 hours, adding a catalyst of dibutyl tin dilaurate, and continuing stirring for 1-2 hours;
step A2, cooling the reaction solution obtained in the step A1 to 60-65 ℃, adding a hydrophilic chain extender which is fully dispersed in a small amount of organic solvent N-methyl pyrrolidone, and heating to 80-90 ℃ again to react for 2-3 hours to obtain a waterborne polyurethane prepolymer;
step A3, cooling the temperature of the aqueous polyurethane prepolymer to 35-40 ℃, dissolving ethylenediamine in the residual organic solvent N-methyl pyrrolidone, adding the mixture into the aqueous polyurethane prepolymer, and stirring and shearing at a high speed for 0.5-2 hours;
and step A4, dissolving a neutralizing agent triethylamine in deionized water, adding the solution into the reaction solution stirred and sheared in the step A3 under high-speed stirring, reacting for 5-15 minutes, and filtering to obtain the product.
4. The chrome-free fingerprint resistant coating for the externally crosslinked galvanized steel sheet according to claim 3, wherein the diisocyanate is one or a mixture of isophorone diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate, cyclohexane diisocyanate and diphenylmethane diisocyanate; the hydrophilic chain extender is one or a mixture of more of dimethylolpropionic acid, dimethylolbutyric acid, 1, 4-butanediol, glycol and diethylene glycol.
5. The chrome-free fingerprint-resistant coating for the externally crosslinked galvanized steel sheet according to claim 1, wherein the acrylic resin with a linear structure is prepared from 25-30% of butyl acrylate, 8-15% of styrene, 0.2-1% of acrylic acid, 0.2-1% of hydroxyethyl acrylate, 0.5-1.5% of a non-ionic emulsifier, 0.01-0.05% of ammonium persulfate, and the balance of water.
6. The chrome-free fingerprint resistant coating for an externally crosslinked galvanized steel sheet according to claim 5, characterized in that,
the preparation method of the acrylic resin with the linear structure specifically comprises the following steps:
step B1, mixing ammonium persulfate and water accounting for 5% of the total amount to prepare an initiator;
step B2, mixing butyl acrylate, styrene, acrylic acid, hydroxyethyl acrylate and a nonionic emulsifier in sequence, and stirring and dispersing uniformly to prepare a pre-emulsion;
step B3, adding 5-10% of pre-emulsion and 5-10% of initiator into a four-neck flask provided with a thermometer, a stirrer, a condenser and a constant pressure funnel, heating to 70-85 ℃, and reacting for 20-40min to prepare seed emulsion;
step B4, when the seed emulsion turns blue, 80% of pre-emulsion and 80% of initiator are dripped, and the dripping is finished within 3-4.5 h; controlling the temperature to be kept at 75-90 ℃ in the dripping process, and preserving the heat for 0.5-1.5h after dripping;
step B5, dropwise adding the residual pre-emulsion and the initiator, controlling the temperature to be kept at 75-90 ℃ in the dropwise adding process, and preserving the heat for 0.5-1h after the dropwise adding is finished;
and step B6, cooling to 50-60 ℃, neutralizing with ammonia water to pH 7-8, filtering and discharging to obtain milky emulsion slightly blue.
7. The chrome-free fingerprint resistant coating for an externally crosslinked galvanized steel sheet according to claim 1, wherein the silane coupling agent contains at least one active hydrogen amino or epoxy group per molecule as a reactive functional group.
8. The chrome-free fingerprint resistant coating for an externally crosslinked galvanized steel sheet according to claim 7, wherein the silane coupling agent is one or more of N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and aminopropyltriethoxysilane, 3-propyltrimethoxysilane, 3-propylmethyldimethoxysilane, 2- (3, 4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane.
9. The chromium-free fingerprint-resistant coating for the externally crosslinked galvanized steel sheet according to claim 1, wherein the silica sol is a silica dispersion having a particle size of 10 to 100 nm; the wetting agent and the flatting agent are organic silicon auxiliaries; the polyethylene wax dispersoid is oxidized polyethylene wax or non-oxidized polyethylene wax with the particle diameter of 0.1-5 mu m.
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