CN110997833A - 水性涂料组合物 - Google Patents
水性涂料组合物 Download PDFInfo
- Publication number
- CN110997833A CN110997833A CN201780093544.9A CN201780093544A CN110997833A CN 110997833 A CN110997833 A CN 110997833A CN 201780093544 A CN201780093544 A CN 201780093544A CN 110997833 A CN110997833 A CN 110997833A
- Authority
- CN
- China
- Prior art keywords
- coating composition
- polymer
- aqueous coating
- weight
- zinc
- 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.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 75
- 239000000178 monomer Substances 0.000 claims abstract description 79
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000004756 silanes Chemical class 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 15
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 41
- 239000000758 substrate Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 claims description 2
- JDJDVQQBQGSXNG-UHFFFAOYSA-O [NH4+].[Zn].[O-][N+]([O-])=O Chemical compound [NH4+].[Zn].[O-][N+]([O-])=O JDJDVQQBQGSXNG-UHFFFAOYSA-O 0.000 claims description 2
- JWDHKQDZLSVBDO-UHFFFAOYSA-N azane;carbonic acid;zinc Chemical group N.[Zn].OC(O)=O JWDHKQDZLSVBDO-UHFFFAOYSA-N 0.000 claims description 2
- PVKFMRXEWAAGSZ-UHFFFAOYSA-L azanium;zinc;triacetate Chemical compound [NH4+].[Zn+2].CC([O-])=O.CC([O-])=O.CC([O-])=O PVKFMRXEWAAGSZ-UHFFFAOYSA-L 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 claims 1
- 239000011230 binding agent Substances 0.000 description 47
- 239000003973 paint Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 229910001868 water Inorganic materials 0.000 description 22
- -1 hydroxyalkyl acrylate Chemical compound 0.000 description 20
- 238000009472 formulation Methods 0.000 description 19
- 239000000839 emulsion Substances 0.000 description 18
- 235000002639 sodium chloride Nutrition 0.000 description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 12
- 229910000077 silane Inorganic materials 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002562 thickening agent Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000013530 defoamer Substances 0.000 description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000006254 rheological additive Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical class [H]C([*])=C([H])[H] 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000003118 aryl group Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 235000010350 erythorbic acid Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 2
- 229940026239 isoascorbic acid Drugs 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Chemical class 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BPGIOCZAQDIBPI-UHFFFAOYSA-N 2-ethoxyethanamine Chemical compound CCOCCN BPGIOCZAQDIBPI-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 1
- IBZKBSXREAQDTO-UHFFFAOYSA-N 2-methoxy-n-(2-methoxyethyl)ethanamine Chemical compound COCCNCCOC IBZKBSXREAQDTO-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- YOOSAIJKYCBPFW-UHFFFAOYSA-N 3-[4-(3-aminopropoxy)butoxy]propan-1-amine Chemical compound NCCCOCCCCOCCCN YOOSAIJKYCBPFW-UHFFFAOYSA-N 0.000 description 1
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Abstract
提供一种水性涂料组合物,其包含:(a)水性聚合物分散液,其中以聚合物的重量计,所述聚合物包含2重量%到8重量%的α,β‑烯系不饱和羧酸单体的结构单元,和0.05重量%到1.8重量%的烯系不饱和硅烷官能单体的结构单元;(b)锌氨络合物盐的水溶液;和(c)以所述水性涂料组合物的总重量计,60重量%到90重量%的填料;其中所述锌离子与所述聚合物的重量比在0.7%到6%的范围内。所述水性涂料组合物具有长适用期并且与基材粘合良好。还提供一种用于制备所述涂料组合物的方法。
Description
技术领域
本发明涉及水性涂料组合物和其制备方法。
背景技术
可使用聚合物胶乳的水性分散液作为粘结剂配制水基涂料组合物(也称为水性涂料组合物)。在将粘结剂与其它成分混合时,期望所得涂料组合物具有足够长的适用期,以在施用期间易于处置。在将涂料组合物施用到基材上之后,水性载体蒸发,并且各个胶乳颗粒聚结以形成整体的涂料膜。一些应用需要相对厚的涂料膜。举例来说,富含填料的涂料,尤其具有大填料粒子(例如约90-600μm)通常厚度大于2mm。这些厚涂料膜在室温下通常需要数小时或甚至数天蒸发水并且增强膜强度。在高温(70℃-120℃)下固化水基涂料组合物为加速固化用工业设备大批量进行的预制涂料的常规方法。然而,在高温固化之后,常规水性涂料组合物倾向于形成具有气泡的厚涂料膜,并且由此与基材粘合差。
CN102120902(B)涉及用于油墨的水性丙烯酸快干剂,按体积计,包含:12-20份的12%-18%氧化锌溶液、1-3份浓氨水、12-18份去离子水,和65-70份水性丙烯酸乳液;其中丙烯酸乳液的Tg为-30℃到-50℃。这类水性剂适合于施用在塑料基材上以形成厚度通常小于500μm的薄膜,并且然后在相对低的温度(例如40℃-50℃)下干燥。
因此,需要开发具有长适用期并且在高温固化之后提供厚的由其制备的涂层,甚至厚度为2mm或更大,与基材粘合良好的水性涂料组合物。
发明内容
本发明通过将特定粘结剂与锌氨络合物溶液和填料以特定比率组合提供新型水性涂料组合物。水性涂料组合物在室温(20℃-25℃)下具有足够长的适用期用于处置,例如至少3小时。本发明的水性涂料组合物可在70℃或更高的温度(即,高温)下固化以形成厚度为2mm或更大,优选地3mm或更大涂层。同时,涂层还与基材粘合良好,如由从基材拉开强度为0.2MPa或更高指示。根据在下文实例部分中描述的测试方法测量适用期和拉开强度特性。制备涂料的方法可通过在高温下固化水性涂料组合物以便改善制造效率来进行。
在第一方面,本发明为水性涂料组合物,其包含,
(a)包含聚合物的水性聚合物分散液,其中以聚合物的重量计,聚合物包含
2重量%到8重量%的α,β-烯系不饱和羧酸单体的结构单元,和
0.05重量%到1.8重量%的烯系不饱和硅烷官能单体的结构单元;
(b)包含锌离子的锌氨络合物盐的水溶液;和
(c)以水性涂料组合物的总重量计,60重量%到90重量%的填料;
其中锌离子与聚合物的重量比在0.7%到6%的范围内。
在第二方面,本发明为用于制备第一方面的水性涂料组合物的方法。方法包含掺合:
(a)包含聚合物的水性聚合物分散液,其中以聚合物的重量计,聚合物包含
2重量%到8重量%的α,β-烯系不饱和羧酸单体的结构单元,和
0.05重量%到1.8重量%的烯系不饱和硅烷官能单体的结构单元;
(b)包含锌离子的锌氨络合物盐的水溶液;和
(c)以水性涂料组合物的总重量计,60重量%到90重量%的填料;
其中锌离子与聚合物的重量比在0.7%到6%的范围内。
在第三方面,本发明为制备涂层的方法。方法包含,
提供第一方面的水性涂料组合物,
将水性涂料组合物施用到基材,和
在70℃或更高下干燥施用的水性涂料组合物以形成厚度为2mm或更大的涂层。
具体实施方式
在本发明中的“丙烯酸类”包括(甲基)丙烯酸、丙烯酸(甲基)烷基酯、(甲基)丙烯酰胺、(甲基)丙烯腈和其改性形式,如丙烯酸(甲基)羟基烷基酯。在整篇文件中,词语片段“(甲基)丙烯酰基”是指“甲基丙烯酰基”和“丙烯酰基”两者。举例来说,(甲基)丙烯酸是指甲基丙烯酸和丙烯酸两者,并且(甲基)丙烯酸甲酯是指甲基丙烯酸甲酯和丙烯酸甲酯两者。
水性分散液或水性组合物意指粒子分散在水性介质中。本文中通过“水性介质”意指水和以介质的重量计,0到30重量%的(一种或多种)水可混溶化合物,例如醇、二元醇、二醇醚、二醇酯等。
本发明中的“玻璃转化温度”或“Tg”可通过各种技术测量,包括例如差示扫描量热法(“DSC”)或通过使用Fox方程式计算。本文所报告的Tg的具体值是使用Fox方程式计算的那些值(T.G.Fox,《美国物理学会公报(Bull.Am.Physics Soc.)》,第1卷,第3期,第123页(1956)。举例来说,用于计算单体M1和M2的共聚物的Tg,
其中Tg(calc.)为共聚物的所计算的玻璃化转变温度,w(M1)为在共聚物中的单体M1的重量分数,w(M2)为在共聚物中的单体M2的重量分数,Tg(M1)为单体M1的均聚物的玻璃化转变温度并且Tg(M2)为单体M2的均聚物的玻璃化转变温度,所有温度以K为单位。均聚物的玻璃转化温度可见于例如由J.Brandrup和E.H.Immergut编辑的“《聚合物手册(PolymerHandbook)》”,国际科学出版社(Interscience Publishers)。
如本文所使用,术语指定单体的结构单元(也被称为聚合单元)是指在聚合之后单体的残余物,即,呈聚合形式的单体或聚合单体。举例来说,甲基丙烯酸甲酯的结构单元如所示出:
其中虚线表示结构单元与聚合物主链的连接点。
本发明的水性涂料组合物包含水性聚合物分散液。适用于本发明的聚合物,通常为乳液聚合物,可包含烯系不饱和硅烷官能单体的结构单元。烯系不饱和硅烷单体可通式(I)由表示:
其中R1表示选自任何被取代或未被取代的烯系不饱和烃基的官能团;R2独立地选自甲基、乙基、丙基、异丙基、丁基和叔丁基;并且n为1到3的整数。合适的烯系不饱和硅烷官能单体的实例包括烷基乙烯基二烷氧基硅烷;(甲基)丙烯酰氧基烷基三烷氧基硅烷,包括(甲基)丙烯酰氧基乙基三甲氧基硅烷和(甲基)丙烯酰氧基丙基三甲氧基硅烷,如γ-甲基丙烯酰氧基丙基三甲氧基硅烷和甲基丙烯酰氧基丙基三乙氧基硅烷;乙烯基三烷氧基硅烷,如乙烯基三乙氧基硅烷和乙烯基三甲氧基硅烷;其衍生物;或其组合。可商购的烯系不饱和硅烷官能单体包括SILQUEST A-174、A-171、A-151、A-2171和A-172E,以及Coatosil-1706、Coatosil-1757和Y-11878硅烷,均可购自迈图高新材料(Momentive PerformanceMaterials),或其混合物。以聚合物的重量计,聚合物可包含0.05重量%或更多、0.1重量%或更多、0.15重量%或更多、0.2重量%或更多,或甚至0.25重量%或更多,并且同时1.8重量%或更少、1.5重量%或更少、1.2重量%或更少,或甚至1.0重量%或更少的烯系不饱和硅烷官能单体的结构单元。
适用于本发明的聚合物还可包含一种或多种α,β-烯系不饱和羧酸单体的结构单元。合适的α,β-烯系不饱和羧酸单体的实例包括一元酸,如(甲基)丙烯酸、巴豆酸和酰氧基丙酸;和二元酸单体,如顺丁烯二酸、反丁烯二酸和衣康酸;或其混合物。优选的α,β烯系不饱和羧酸单体包括丙烯酸、甲基丙烯酸,或其混合物。以聚合物的重量计,适用于本发明的聚合物可包含2.0重量%或更多、2.1重量%或更多、2.2重量%或更多,或甚至2.3重量%或更多,并且同时8重量%或更少、7重量%或更少、6重量%或更少、5.8重量%或更少、5.5重量%或更少、5重量%或更少、4.5重量%或更少、4重量%或更少,或甚至3.5或更少%的α,β-烯系不饱和羧酸单体的结构单元。
适用于本发明的聚合物可进一步包含一种或多种不包括烯系不饱和硅烷官能单体的附加烯系不饱和官能单体。这类附加烯系不饱和官能单体带有至少一个选自磺酸盐、磺酸或酰胺的官能团。合适的附加烯系不饱和官能单体的实例包括丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-异丙基丙烯酰胺、N-丁基丙烯酰胺、N-叔丁基丙烯酰胺、N-2-乙基己基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、双丙酮丙烯酰胺、对苯乙烯磺酸钠(SSS)、乙烯基磺酸钠(SVS)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、其盐,如2-丙烯酰胺基-2-甲基丙烷磺酸钠,或其混合物。以聚合物的重量计,适用于本发明的聚合物可包含0到5重量%、0.5重量%到4.5重量%或更多、1重量%到4重量%,或2重量%到3.5重量%的附加烯系不饱和官能单体的结构单元。
适用于本发明的聚合物还可包含一种或多种不包括烯系不饱和硅烷官能单体或附加烯系不饱和官能单体的烯系不饱和非离子单体的结构单元。本文中术语“非离子单体”是指在pH=1-14之间不具有离子电荷的单体。烯系不饱和非离子单体的合适的实例包括例如(甲基)丙烯酸的烷基酯,包括(甲基)丙烯酸的C1-C18并且优选地C1-C12烷基酯,如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、丙烯酸月桂酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异癸脂、甲基丙烯酸月桂酯、羟基官能(甲基)丙烯酸烷基酯,如(甲基)丙烯酸羟乙酯和(甲基)丙烯酸羟丙酯;(甲基)丙烯腈;苯乙烯和被取代的苯乙烯;丁二烯;乙烯、丙烯、α-烯烃,如1-癸烯;和乙烯基单体,如乙酸乙烯酯、乙烯基丁酸酯、氯乙烯、偏二氯乙烯、叔碳酸乙烯酯和其它乙烯基酯;或其组合。优选的烯系不饱和非离子单体为丙烯酸丁酯、甲基丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸2-乙基己酯、丙烯酸癸酯、丙烯酸月桂酯、甲基丙烯酸异癸脂、甲基丙烯酸月桂酯、苯乙烯,和其混合物。以聚合物的重量计,适用于本发明的聚合物可包含85重量%或更多、87重量%或更多、88重量%或更多、89重量%或更多,或甚至90重量%或更多,并且同时98重量%或更少、97.5重量%或更少、97重量%或更少、96.5重量%或更少,或甚至95重量%或更少的烯系不饱和非离子单体的结构单元。
适用于本发明的聚合物可从包含以下的单体的混合物获得:烯系不饱和硅烷官能单体、α,β-烯系不饱和羧酸单体、烯系不饱和非离子单体,和任选的附加烯系不饱和官能单体。
在一些优选实施例中,以聚合物的重量计,聚合物包含
0.1重量%到1重量%的烯系不饱和硅烷官能单体的结构单元;
2重量%到4重量%的α,β-烯系不饱和羧酸单体的结构单元;
90重量%到95重量%的烯系不饱和非离子单体的结构单元,如(甲基)丙烯酸的烷基酯;和
0到5重量%的附加烯系不饱和官能单体。
上文所描述的单体的结构单元的总重量浓度可等于100%。可选择上文所描述的单体的类型和水平以提供具有适合于不同应用的玻璃化转变温度(Tg)的获得的聚合物。聚合物的Tg可为-20℃或更高、-15℃或更高、-10℃或更高、-5℃或更高,或甚至0或更高,并且同时60℃或更低、50℃或更低、40℃或更低,或甚至30℃或更低。
适用于本发明的聚合物通常作为平均粒度为10到500纳米(nm)、50到400nm,或80到300nm的聚合物粒子的水性分散液存在。本文中的粒度可通过Brookhaven BI-90+粒度分析仪来测量。
适用于本发明的聚合物可通过上文所描述的单体的自由基聚合,优选地乳液聚合制备。用于制备聚合物的单体的总重量浓度等于100%。以聚合物的重量计,在聚合物中每种单体的结构单元的量与以单体的总重量计这类单体的剂量基本上相同。单体可以纯或于水中的乳液形式添加;或在制备聚合物的反应时间段内以一次或多次添加或连续、线性或非线性地添加。适合于聚合方法的温度可低于100℃、在30℃到95℃的范围内,或在50℃到90℃的范围内。可使用使用上文所描述的单体的多阶段自由基聚合,其依次形成至少两个阶段,并且通常导致形成包含至少两种聚合物组合物的多阶段聚合物。
在制备聚合物的聚合方法中,可使用自由基引发剂。聚合方法可为热引发的或氧化还原引发的乳液聚合。合适的自由基引发剂的实例包括过氧化氢、叔丁基过氧化氢、异丙苯过氧化氢、过硫酸铵和/或碱金属过硫酸盐、过硼酸钠、过磷酸和其盐;高锰酸钾和过二硫酸的铵盐或碱金属盐。以单体的总重量计,自由基引发剂的用量通常可为0.01重量%到3.0重量%。可在聚合方法中使用包含上文所描述的引发剂外加合适的还原剂的氧化还原体系。适合的还原剂的实例包括甲醛次硫酸钠、抗坏血酸、异抗坏血酸、含硫的酸的碱金属盐和铵盐(如亚硫酸钠、亚硫酸氢盐、硫代硫酸盐、次硫酸盐、硫化物、硫氢化物或连二亚硫酸盐)、甲脒亚磺酸、羟甲基磺酸、丙酮亚硫酸氢盐、乙醇酸、乙醛酸水合物、乳酸、甘油酸、苹果酸、酒石酸和前述酸的盐。铁、铜、锰、银、铂、钒、镍、铬、钯或钴的金属盐可用于催化氧化还原反应。可任选地使用金属的螯合剂。
在制备聚合物的聚合方法中,可使用一种或多种表面活性剂。表面活性剂可在单体聚合之前或单体聚合期间或其组合添加。一部分表面活性剂也可在聚合之后添加。这些表面活性剂可包括阴离子和/或非离子乳化剂。表面活性剂可为反应性表面活性剂,例如可聚合表面活性剂。合适的表面活性剂的实例包括烷基、芳基或烷芳基硫酸酯、磺酸酯或磷酸酯的碱金属盐或铵盐;烷基磺酸;磺基丁二酸盐;脂肪酸;和乙氧基化醇或苯酚。在一些优选的实施例中,使用烷基、芳基或烷芳基硫酸酯的碱金属盐或铵盐表面活性剂。以用于制备聚合物的总单体的重量计,使用的表面活性剂通常为0.1重量%到10重量%,优选地0.2重量%到3重量%。
在完成单体的聚合过程之后,获得的水性聚合物分散液可由一种或多种碱中和到pH值例如至少7、7到10或8到9。合适的碱的实例包括氨水;碱金属或碱土金属化合物,如氢氧化钠、氢氧化钾、氢氧化钙、氧化锌、氧化镁、碳酸钠;伯胺、仲胺和叔胺,如三乙胺、乙胺、丙胺、单异丙胺、单丁胺、己胺、乙醇胺、二乙胺、二甲胺、二正丙胺、三丁胺、三乙醇胺、二甲氧基乙胺、2-乙氧基乙胺、3-乙氧基丙胺、二甲基乙醇胺、二异丙醇胺、吗啉、乙二胺、2-二乙氨基乙胺、2,3-二氨基丙烷、1,2-丙二胺、新戊二胺、二甲基氨基丙胺、己二胺、4,9-二氧杂十二烷-1,12-二胺、聚乙烯亚胺或聚乙烯胺;氢氧化铝;或其混合物。
除了水性聚合物分散液外,本发明的水性涂料组合物进一步包含一种或多种锌氨络合物盐的水溶液。锌氨络合物盐为水溶性的。锌氨络合物盐可选自碳酸氢锌铵、硝酸锌铵、乙酸锌铵,或其混合物。碳酸锌氨为优选的。锌氨络合物盐可通过将一种或多种锌盐和/或氧化锌、氨,和任选的水溶性碳酸盐(如碳酸氢铵)混合来制备。以足够的量添加氨水以提供pH高于9,优选地高于9.5的锌氨络合物盐的水溶液,并且在过量当量的氨存在下以形成锌氨络合物。锌盐可为碳酸锌、乙酸锌、氯化锌、硝酸锌,或其混合物。锌氨络合物盐的水溶液包含锌离子和铵离子。锌氨络合物盐的水溶液可以确保锌离子与聚合物的重量比量为0.7%或更大、0.8%或更大、0.9%或更大、1.0%或更大、1.2%或更大,或甚至1.5%或更大,并且同时6%或更小、5.5%或更小、5%或更小、4.5%或更小、4%或更小、3.5%或更小,或甚至3%或更小的量存在。
本发明的水性涂料组合物进一步包含一种或多种填料。填料的筛分粒度可在90到600μm或120到500μm的范围内。筛分粒度可根据GB/T 5330-2003方法测量。合适的填料的实例包括沙子、CaCO3、SiO2、碳酸钙、粘土、硫酸钙、铝硅酸盐、硅酸盐、沸石、云母、硅藻土、实心或中空玻璃、瓷珠、霞石正长岩、长石、硅藻土、煅烧硅藻土、滑石(水合硅酸镁)、二氧化硅、氧化铝、高岭土、叶蜡石、珍珠岩、重晶石、硅灰石、不透明聚合物,如可购自陶氏化学公司(The Dow Chemical Company)的ROPAQUETM Ultra E(ROPAQUE为陶氏化学公司的商标),或其混合物。以水性涂料组合物的总重量计,水性涂料组合物可包含60重量%到90重量%、65重量%到85重量%、70重量%到80重量%的填料。
本发明的水性涂料组合物可以进一步包含一种或多种消泡剂。本文中“消泡剂”是指减少泡沫并且阻止泡沫形成的化学添加剂。消泡剂可为基于硅酮的消泡剂、基于矿物油的消泡剂、基于环氧乙烷/环氧丙烷的消泡剂、聚丙烯酸烷基酯,或其混合物。合适的可商购的消泡剂包括例如均购自迪高(TEGO)的TEGO Airex 902W和TEGO Foamex 1488聚醚硅氧烷共聚物乳液、可购自毕克(BYK)的BYK-024硅酮消泡剂,或其混合物。以水性涂料组合物的总干重计,消泡剂的存在量大体上可为0到0.5重量%、0.01重量%到0.2重量%,或0.03重量%到0.1重量%。
本发明的水性涂料组合物可进一步包含一种或多种增稠剂。增稠剂可包括聚乙烯醇(PVA)、酸衍生物、酸共聚物、氨基甲酸酯缔合增稠剂(UAT)、聚醚脲聚氨基甲酸酯(PEUPU)、聚醚聚氨基甲酸酯(PEPU),或其混合物。合适的增稠剂的实例包括碱溶胀性乳液(ASE),如钠或铵中和的丙烯酸聚合物;疏水改性的碱溶胀性乳液(HASE),如疏水改性的丙烯酸共聚物;缔合增稠剂,如疏水改性的乙氧基化氨基甲酸酯(HEUR);和纤维素增稠剂,如甲基纤维素醚、羟甲基纤维素(HMC)、羟乙基纤维素(HEC)、疏水性改质的羟乙基纤维素(HMHEC)、羧甲基纤维素钠(SCMC)、羧甲基2-羟乙基纤维素钠、2-羟丙基甲基纤维素、2-羟乙基甲基纤维素、2-羟丁基甲基纤维素、2-羟乙基乙基纤维素和2-羟丙基纤维素。优选地,增稠剂为疏水改性的羟乙基纤维素(HMHEC)。以水性涂料组合物的总干重计,增稠剂存在量可大体上为0到2重量%、0.1重量%到1重量%,或0.3重量%到0.8重量%。
本发明的水性涂料组合物可进一步包含一种或多种润湿剂。本文中“润湿剂”是指降低涂料组合物的表面张力,引起涂料组合物更容易扩散通过或渗透基材表面的化学添加剂。润湿剂可为阴离子、两性离子或非离子的聚羧酸酯。以水性涂料组合物的总干重计,湿润剂存在量可为0到0.5重量%、0.1重量%到0.3重量%。
本发明的水性涂料组合物可进一步包含一或多种聚结剂。本文中“聚结剂”是指在环境条件下使聚合物粒子融合成连续膜的缓慢蒸发溶剂。合适的聚结剂的实例包括2-正丁氧基乙醇、二丙二醇正丁醚、丙二醇正丁醚、二丙二醇甲醚、丙二醇甲醚、丙二醇正丙醚、二乙二醇单丁醚、乙二醇单丁醚、乙二醇单己醚、三乙二醇单丁醚、二丙二醇正丙醚、正丁醚或其混合物。以水性涂料组合物的总干重计,聚结剂存在量可为0到5重量%、0.5重量%到3重量%,或1重量%到2重量%。
除上文所描述的组分以外,本发明的涂料组合物可进一步包含以下添加剂中的任一种或组合:缓冲剂、中和剂、保湿剂、防霉剂、杀生物剂、防结皮剂、着色剂、流动剂、抗氧化剂、塑化剂、调平剂、触变剂粘合促进剂和研磨媒剂。当存在时,以水性涂料组合物的总重量计,这些添加剂可以0到1重量%、0.1重量%到0.6重量%,或0.3重量%到0.5重量%的组合量存在。
本发明的水性涂料组合物可通过掺合水性聚合物分散液、锌氨络合物盐的和填料制备。在一些实施例中,水性涂料组合物通过优选地在搅拌下掺合水性聚合物分散液、锌氨络合物盐的水溶液和其它任选的组分,如流变改性剂和消泡剂以形成预混合物,接着将填料添加到预混合物中以得到均匀水性涂料组合物来制备。水性聚合物分散液和锌铵络合物盐的水溶液通常以双组分包装供应,并且在施用时混合。
本发明的水性涂料组合物可在将水性涂料组合物施用到基材之前形成。在将水性涂料组合物中的组分混合后,水性涂料组合物具有足够长的适用期,以使得工人能够现场处置,例如,水性涂料组合物在25℃下稳定3小时或更长、5小时或更长,10小时或更长、15小时或更长,24小时或更长,3天或更长,或甚至1周或更长。水性涂料组合物还适合于在高温下,例如在70℃或更高下干燥,同时仍然提供与基材粘合良好的由其制备的厚度为2mm或更大的涂层,如由从基材,优选地水泥基材的拉开强度为0.2MPa或更高、0.25MPa或更高、0.3MPa或更高、0.35MPa或更高、0.40MPa或更高,或甚至0.45MPa或更高指示。涂层还可具有良好的抗水性。根据在下文实例部分中描述的测试方法测量适用期、拉开强度和抗水性。
本发明还提供制备涂层的方法,其包含,
提供水性涂料组合物,
将水性涂料组合物施用到基材,和
在70℃或更高下干燥施用的涂料组合物,以形成厚度为2mm或更大或3mm或更大,优选地2到5mm的涂层。
在室温下,涂层与基材的拉开强度可为0.2MPa或更高或0.25MPa或更高,如根据在下文实例部分中描述的测试方法测量。水性涂料组合物可施用并且粘附到各种基材,包括(例如)木材、金属、塑料、泡沫、石头、弹性体基材、织物、混凝土和水泥类基材,如纤维素纤维水泥片材。涂层可为预制的精饰系统的一部分。水性涂料组合物可在高温,例如70℃或更高、80℃或更高、90℃或更高、100℃或更高、110℃或更高,或甚至120℃或更高下干燥,或允许干燥以形成膜(即涂层)。水性涂料组合物可通过包括刷涂、辊涂和喷涂的现有方式施用到基材。水性涂料组合物适合于各种应用,如外部隔热和精饰系统(EIFS)、屋顶胶、预制的隔热和精饰系统(PRIFS)、建筑涂料、土建涂料或液体施用的声音阻尼涂料(LASD)。涂料组合物特别适合于制备预制的精饰系统,例如PRIFS。水性涂料组合物可单独使用或与其它涂料组合使用以形成多层涂层。举例来说,多层涂层可包含本发明的涂料组合物作为中间涂层。
实例
现在将在以下实例中描述本发明的一些实施例,除非另外说明,否则其中所有份数和百分比均以重量计。
POLYSTEP P-12A(“P-12A”)表面活性剂,可购自斯泰潘(Stepan),为聚乙二醇单十三烷基醚磷酸酯。
丙烯酸2-乙基己酯(“EHA”)、甲基丙烯酸甲酯(“MMA”)、甲基丙烯酸(“MAA”)和过硫酸铵(“APS”)均可购自中化试剂集团(中国)(Sinoreagent Group(China))。
SILQUEST A-174(“A-174”)硅烷,可购自迈图高新材料,为γ-甲基丙烯酰氧基丙基三甲氧基硅烷。
SILQUEST A-187(“A-187”)硅烷,可购自迈图高新材料,为γ-缩水甘油氧基丙基三甲氧基硅烷。
氨水、碳酸氢铵叔丁基氢过氧化物(“t-BHP”)和异抗坏血酸(“IAA”)均可购自上海化学试剂有限公司(Shanghai Chemical Reagent Co.,Ltd)。
NATROSOL 250HBR(“250HBR”)流变改性剂可购自亚什兰(Ashland)。
FOAMASTER NXZ,可购自巴斯夫(BASF),用作消泡剂。
TEXANOL酯醇,可购自伊士曼化学(Eastman Chemical),用作聚结剂。
AMP-95,可购自Angus化学公司(Angus Chemical Company)用作中和剂。
ACRYSOL TT-935,可购自陶氏化学公司,用作流变改性剂。
丙二醇可购自陶氏化学公司。
沙子的筛分粒度为90到600μm。
在实例中使用以下标准分析设备和方法。
拉开强度
将漆配制物以3mm的湿膜厚度施用在基材(纤维素纤维水泥片材,高压处理)上。然后将涂布的基材在80℃下的烘箱中干燥1小时直到所得漆膜完全固化,如由如通过水分计测量的漆膜的水含量小于5%指示。根据ISO 4624在室温下使用拉伸机(HaftprufsystemHP1000,粘结强度测试系统)评估获得的干燥漆膜的拉开强度。拉开强度为0.2MPa或更高的漆膜指示漆膜与基材粘合良好。否则,如果拉开强度小于0.2MPa,那么漆膜与基材粘合差。
锌离子的测量
称量0.5克(g)的样品(精确到0.0001g)并且将其添加到消化容器中。加入5ml浓硝酸。然后将容器在热板上缓慢加热,直到所有残留物溶解。将所得溶液用去离子(DI)水稀释到50mL。取出1mL溶液,并且用DI水进一步稀释到100mL,并且然后用电感耦合等离子体(ICP)光谱仪测量。
制备浓度为0、1、2、5、10ppm的Zn标准溶液。
仪器条件:光谱仪-Perkin Elmer Optima 5300DV;RF功率-1.3kW;等离子体视图-轴向;和测试Zn离子的波长-206.2nm。测试前将仪器升温4小时。
抗水性测试
将漆配制物以3mm的湿膜厚度施用在基材(纤维素纤维水泥片材,高压处理)上。然后将涂布的基材在80℃下的烘箱中干燥1小时直到所得漆膜完全固化,如由如通过水分计测量的漆膜的水含量小于5%指示。在室温下将获得的干漆膜浸入蒸馏水中一半。将浸入水中的漆膜的表面连续监测至多7天并且以肉眼观察。如果在7天之后漆膜的表面示出没有白化、起泡、开裂或从基材剥离,那么指示漆膜具有良好的抗水性。在浸入部分和非浸入部分之间轻微的表面颜色变化为可接受的。
适用期
基于在室温下储存某一时间段之前和之后这类漆配制物与基材拉开强度的改变评估漆配制物的适用期。
根据如在上文拉开强度测试中所描述,漆配制物在混合所有组分时首先形成为漆膜,并且测量漆膜的拉开强度并且记录为拉开强度(初始)。
然后,将同一漆配制物在室温下存储某一时间(t),并且测量由其制备的漆膜的拉开强度并且记录为拉开强度(t)。最长时间段,当拉开强度的变化(即,拉开强度(初始)-拉开强度(t)小于拉开强度(初始)的20%时,记录为适用期。
制备水性锌氨络合物溶液
将120g的碳酸氢铵(NH4HCO3)添加在具有610g水和190g氨(NH3H2O浓度:25%-28%)的烧杯中。将80g氧化锌(ZnO)添加到上述所得溶液中。将所得混合物在连续搅动下混合约20分钟直到氧化锌溶解,由此形成锌氨络合物溶液。
如下制备水性聚合物分散液(即,粘结剂),
合成粘结剂1
单体乳液通过将538g的DI水、17g的POLYSTEP P-12A(25%活性)、770g的EHA、615g的MMA、36g的MAA,和4.25g的A-174硅烷混合制备。
将一加仑搅拌反应器装入870g的DI水、71g的作为釜用皂的P-12A(25%活性)和2.42g的氨水。在将反应内容物加热到95℃之后,添加88g的单体乳液,接着20g的DI水冲洗。其后立刻添加4.14g的碳酸氢铵于20g的DI水中和4.262g的APS于20g的DI水中的溶液。在90分钟内将剩余单体乳液添加到反应器同时维持88℃的温度。反应完成之后,在一小时期间将23g的7%t-BHP和25g的3%IAA进料到反应器。添加14g的28%氨水溶液作为中和剂。然后将所得聚合物胶乳冷却到室温。
合成粘结剂2
根据与上述制备粘结剂1相同的程序制备粘结剂2,例外为用于制备粘结剂2的单体乳液通过将538g的DI水、17g的P-12A(25%活性)、764.7g的EHA、628g的MMA、25.9g的MAA,和4.25g的A-174硅烷混合来制备。
合成粘结剂3
根据与上述制备粘结剂1相同的程序制备粘结剂3,例外为用于制备粘结剂3的单体乳液通过将538g的DI水、17g的P-12A(25%活性)、790g的EHA、542g的MMA、86.4g的MAA,和4.25g的A-174硅烷混合来制备。
合成粘结剂4
根据与上述制备粘结剂1相同的程序制备粘结剂4,例外为单体乳液直接装入到反应器中的和P-12A表面活性剂的剂量不同。用于制备粘结剂4的单体乳液通过将538g的DI水、17g的P-12A(25%活性)、768.8g的EHA、621g的MMA、28.8g的MAA,和4.25g的A-174硅烷混合来制备。将5.67g的P-12A(25%活性)直接装入到反应器中作为釜用皂。
合成粘结剂5
根据与上述制备粘结剂1相同的程序制备粘结剂5,例外为用于制备粘结剂5的单体乳液通过将538g的DI水、17g的P-12A(25%活性)、754.6g的EHA、603.8g的MMA、36g的MAA,和28.36g的A-174硅烷混合来制备。
合成粘结剂6
根据与上述制备粘结剂1相同的程序制备粘结剂6,例外为用于制备粘结剂6的单体乳液通过将538g的DI水、17g的P-12A(25%活性)、766g的EHA、621g的MMA,和36g的MAA混合来制备。
合成粘结剂7
通过首先如上文所描述制备粘合剂6,然后将4.25的A-187硅烷添加到反应器中以得到粘结剂7,从而获得粘结剂7。
合成粘结剂8
根据与制备上述粘结剂1相同的程序制备粘结剂8,例外为用于制备粘结剂8的单体乳液通过将538g的DI水、17g的P-12A(25%活性)、772g的EHA、597g的MMA,和50.4g的MAA,和4.25g的A-174硅烷混合来制备。
合成粘结剂9
根据与制备上述粘结剂1相同的程序制备粘结剂9,例外为用于制备粘结剂9的单体乳液通过将538g的DI水、17g的P-12A(25%活性)、779g的EHA、568.5g的MMA,和72g的MAA,和4.25g的A-174硅烷混合来制备。
上述获得的粘结剂的特性在表1中给出。
表1.粘结剂的特性
*以单体的总重量计的重量百分比
实例(Ex)1-9
基于在表2中给出的配方,上述获得的粘结剂用于制备Ex 1-9的漆配制物(即,涂料组合物)。水、粘结剂和每种漆配制物的其它成分使用常规实验室混合器混合。最后将沙子添加到所得混合物中。根据上文所描述的测试方法评估获得的漆配制物,并且结果在表2中给出。
比较(Comp)实例A-G
基于在表3中描述的配方,制备包含上述获得的粘结剂的Comp Ex A-G的漆配制物。水、粘结剂和每种漆配制物的其它成分使用常规实验室混合器混合。最后将沙子添加到所得混合物中。根据上文所描述的测试方法评估获得的漆配制物,并且结果在表3中给出。
如在表2中所示,本发明的漆配制物均具有长适用期,例如大于3小时或甚至大于16小时。Ex 1-9的漆配制物在80℃下干燥1小时后还提供由其制备的漆膜的拉开强度为0.45MPa或更高。此外,Ex 1-9的漆膜均展现良好的抗水性,如由没有在表面上的白化、起泡或开裂,或在浸入水中7天之后从基材剥离指示。
相比之下,如在表3中所示,不包含A-174硅烷的结构单元的粘结剂提供具有非常短的适用期(小于0.3小时)的漆配制物(Comp Ex E和F)。由2%A-174硅烷获得的粘结剂提供具有差抗水性的由其制备的漆膜(Comp Ex G)。包含1.8%的MAA的结构单元的粘结剂还提供适用期小于0.3小时的漆配制物(Comp Ex C)。锌离子与粘结剂固体的重量比为0.33%、0.66%或6.7%的漆配制物(Comp Ex A、B和D)均提供具有不可接受的低拉开强度(<0.2MPa)和差的抗水性的漆膜。
表2涂料组合物
表3.比较涂料组合物
Claims (10)
1.一种水性涂料组合物,其包含,
(a)包含聚合物的水性聚合物分散液,其中以所述聚合物的重量计,所述聚合物包含
2重量%到8重量%的α,β-烯系不饱和羧酸单体的结构单元,和
0.05重量%到1.8重量%的烯系不饱和硅烷官能单体的结构单元;
(b)包含锌离子的锌氨络合物盐的水溶液;和
(c)以所述水性涂料组合物的总重量计,60重量%到90重量%的填料;
其中所述锌离子与所述聚合物的重量比在0.7%到6%的范围内。
2.根据权利要求1所述的水性涂料组合物,其中所述烯系不饱和硅烷官能单体选自(甲基)丙烯酰氧基乙基三甲氧基硅烷、(甲基)丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、其衍生物,或其组合。
3.根据权利要求1所述的水性涂料组合物,其中以所述聚合物的重量计,所述聚合物包含0.1重量%到1重量%的所述烯系不饱和硅烷官能单体的结构单元。
4.根据权利要求1所述的水性涂料组合物,其中所述锌离子与所述聚合物的重量比在1.5%到3%的范围内。
5.根据权利要求1所述的水性涂料组合物,其中所述锌氨络合物盐选自碳酸氢锌铵、硝酸锌铵、乙酸锌铵,或其混合物。
6.根据权利要求1所述的水性涂料组合物,其中以所述聚合物的重量计,所述聚合物包含2重量%到4重量%的α,β-烯系不饱和羧酸单体的结构单元。
7.根据权利要求1所述的水性涂料组合物,其中所述填料的筛分粒度为90到600μm。
8.一种用于制备根据权利要求1到7中任一项所述的水性涂料组合物的方法,其包含掺合:
(a)包含聚合物的水性聚合物分散液,其中以所述聚合物的重量计,所述聚合物包含
2重量%到8重量%的α,β-烯系不饱和羧酸单体的结构单元,和
0.05重量%到1.8重量%的烯系不饱和硅烷官能单体的结构单元;
(b)包含锌离子的锌氨络合物盐的水溶液;和
(c)以所述水性涂料组合物的总重量计,60重量%到90重量%的填料;
其中所述锌离子与所述聚合物的重量比在0.7%到6%的范围内。
9.根据权利要求8所述的方法,其中所述锌氨络合物盐的水溶液通过将氨、锌盐或氧化锌,和任选的水溶性碳酸盐混合来获得。
10.一种制备涂层的方法,其包含:
提供根据权利要求1到7中任一项所述的水性涂料组合物,
将所述水性涂料组合物施用到基材,和
在70℃或更高下干燥施用的水性涂料组合物以形成厚度为2mm或更大的所述涂层。
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- 2017-07-27 BR BR112020001458-3A patent/BR112020001458A2/pt not_active Application Discontinuation
- 2017-07-27 EP EP17918904.8A patent/EP3658637B1/en active Active
- 2017-07-27 WO PCT/CN2017/094613 patent/WO2019019077A1/en unknown
- 2017-07-27 US US16/634,204 patent/US11542405B2/en active Active
- 2017-07-27 JP JP2020503706A patent/JP6903219B2/ja active Active
- 2017-07-27 CN CN201780093544.9A patent/CN110997833B/zh active Active
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Publication number | Priority date | Publication date | Assignee | Title |
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CN113174155A (zh) * | 2021-05-08 | 2021-07-27 | 扬州工业职业技术学院 | 一种水性涂料用抗菌型润湿分散剂及其制备方法 |
CN113174155B (zh) * | 2021-05-08 | 2021-12-10 | 扬州工业职业技术学院 | 一种水性涂料用抗菌型润湿分散剂及其制备方法 |
CN113461359A (zh) * | 2021-06-29 | 2021-10-01 | 江苏先帅科技有限公司 | 一种管片预制件用复合聚羧酸减水剂及其制备方法 |
CN113461359B (zh) * | 2021-06-29 | 2022-05-10 | 江苏先帅科技有限公司 | 一种管片预制件用复合聚羧酸减水剂及其制备方法 |
Also Published As
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CN110997833B (zh) | 2022-01-18 |
EP3658637A1 (en) | 2020-06-03 |
US20210102087A1 (en) | 2021-04-08 |
WO2019019077A1 (en) | 2019-01-31 |
KR102376460B1 (ko) | 2022-03-18 |
JP6903219B2 (ja) | 2021-07-14 |
EP3658637B1 (en) | 2023-10-25 |
EP3658637A4 (en) | 2021-04-14 |
BR112020001458A2 (pt) | 2020-07-28 |
US11542405B2 (en) | 2023-01-03 |
KR20200032123A (ko) | 2020-03-25 |
JP2020528099A (ja) | 2020-09-17 |
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