WO2021168062A1 - Stain-blocking polymers, primers, kits, and methods - Google Patents
Stain-blocking polymers, primers, kits, and methods Download PDFInfo
- Publication number
- WO2021168062A1 WO2021168062A1 PCT/US2021/018494 US2021018494W WO2021168062A1 WO 2021168062 A1 WO2021168062 A1 WO 2021168062A1 US 2021018494 W US2021018494 W US 2021018494W WO 2021168062 A1 WO2021168062 A1 WO 2021168062A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomers
- acrylate
- meth
- primer
- stain
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 223
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 329
- 239000004816 latex Substances 0.000 claims abstract description 184
- 229920000126 latex Polymers 0.000 claims abstract description 175
- 239000000839 emulsion Substances 0.000 claims abstract description 105
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 102
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 70
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- -1 ethylhexyl Chemical group 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 125000005396 acrylic acid ester group Chemical group 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 21
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000002562 thickening agent Substances 0.000 claims abstract description 9
- 230000003115 biocidal effect Effects 0.000 claims abstract description 8
- 239000003139 biocide Substances 0.000 claims abstract description 8
- 239000003086 colorant Substances 0.000 claims abstract description 8
- 239000008365 aqueous carrier Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 84
- 239000003550 marker Substances 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 52
- 238000000576 coating method Methods 0.000 claims description 45
- 238000012360 testing method Methods 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 33
- 229920001519 homopolymer Polymers 0.000 claims description 14
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 14
- 230000000903 blocking effect Effects 0.000 claims description 12
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- 239000002245 particle Substances 0.000 description 26
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 150000001721 carbon Chemical group 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000012855 volatile organic compound Substances 0.000 description 17
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 238000010186 staining Methods 0.000 description 14
- 238000009472 formulation Methods 0.000 description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 12
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 12
- 239000000908 ammonium hydroxide Substances 0.000 description 12
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 235000010350 erythorbic acid Nutrition 0.000 description 12
- 239000004318 erythorbic acid Substances 0.000 description 12
- 229940026239 isoascorbic acid Drugs 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000008199 coating composition Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000001023 inorganic pigment Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 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 5
- 241000218645 Cedrus Species 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000006254 rheological additive Substances 0.000 description 5
- 239000001648 tannin Substances 0.000 description 5
- 229920001864 tannin Polymers 0.000 description 5
- 235000018553 tannin Nutrition 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000012527 feed solution Substances 0.000 description 4
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002959 polymer blend Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 240000005020 Acaciella glauca Species 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001250616 Intsia palembanica Species 0.000 description 2
- 241000158728 Meliaceae Species 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 241001106462 Ulmus Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000003499 redwood Nutrition 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- NFGXHKASABOEEW-UHFFFAOYSA-N 1-methylethyl 11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate Chemical compound COC(C)(C)CCCC(C)CC=CC(C)=CC(=O)OC(C)C NFGXHKASABOEEW-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-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
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- MGFFVSDRCRVHLC-UHFFFAOYSA-N butyl 3-sulfanylpropanoate Chemical compound CCCCOC(=O)CCS MGFFVSDRCRVHLC-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- PBJZAYSKNIIHMZ-UHFFFAOYSA-N ethyl carbamate;oxirane Chemical class C1CO1.CCOC(N)=O PBJZAYSKNIIHMZ-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- 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
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
-
- 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
- C09D7/43—Thickening agents
Definitions
- Aqueous coating compositions have found limited success in providing coatings with desirable properties for multiple substrates. Typically, transitioning from solvent-borne compositions to aqueous coating compositions, while providing environmental advantages, have resulted in sacrificing properties. The balance of coating performance attributes required for a coating composition to be suitable for use on a variety of substrates is not easily achieved with aqueous coating compositions.
- aqueous coating compositions have found limited success in providing coatings with desirable properties for forming primers, especially those with stain-blocking ability.
- Stain-blocking primers i.e., coating compositions
- substrates including uncoated surfaces or previously coated substrates.
- These coatings promote adhesion and also serve as a barrier coating to underlying polar or non-polar staining agents.
- Substrates frequently contain soluble or mobile staining agents.
- the staining agents often leach from the substrate into and/or through the coating, causing surface discoloration of the coating.
- tannins contained in woods such as redwood, cedar, elm, merbau, and mahogany can leach from the substrate into the coating, causing tannin staining, which appears as discoloration on the surface of the coating.
- the visual appearance of localized stains or discoloration also can be manifested from extractives of previously coated substrates due to substrate exposure to water or humidity spots.
- salts contained in cementitious substrates often cause efflorescence, which is a staining caused by the migration of the salt from the substrate to the paint coating, where it appears as white deposits.
- Staining of the substrate, and of coatings previously applied to the substrate can also be caused by sources external to the substrate. For example, cigarette smoke causes nicotine staining, which discolors light colored coatings; inks from pens cause marker stains on the substrate. Each of these types of staining is highly undesirable in coatings.
- the present disclosure provides stain-blocking polymers, as well as primers, kits, and methods that include such stain-blocking polymers, wherein the stain-blocking polymer is an emulsion latex polymer.
- a stain-blocking primer includes: at least 10 wt-%, based on the total nonvolatile weight of the primer, of an emulsion latex polymer including interpolymerized monomers including: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
- RO-C(0)-CH CH 2
- R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (in certain embodiments, and R has 20 or fewer carbon atoms); optionally, one or more (meth)acrylate monomers (i.e., acrylate or methacrylate monomers) selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; an aqueous carrier; and optionally, one or more additives selected from a surfactant, thickener, coalescent, biocide, mildewcide, colorant (e.g., inorganic pigment), and combinations thereof.
- a surfactant thickener, coalescent, biocide, mildewcide, colorant (e.g
- a stain-blocking polymer in another embodiment, includes: an emulsion latex polymer comprising interpolymerized monomers including: at least 1 wt-% of one or more acrylic acid ester monomers of Formula (I):
- R is a branched alkyl having a tertiary carbon atom (in certain embodiments, R has 20 or fewer carbon atoms); at least 10 wt-% of one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; and at least 1 wt-% styrene; wherein the weight percentages are based on the total weight of the interpolymerized monomers; wherein a hardened coating formed from the stain-blocking polymer has one or more of the following properties: a stain-blocking performance, based on the Stainblocking Test described in the Examples Section (based on ASTM D7514-14), characterized by a DE value of: at most 20, preferably at most 18, for a black water-washable marker (e.g., Marks a Lot Black); and
- a stained substrate having a stain-blocking polymer coated thereon wherein the stain-blocking polymer is an emulsion latex polymer including interpolymerized monomers including: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
- RO-C(0)-CH CH 2
- R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (in certain embodiments, R has 20 or fewer carbon atoms); optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
- kits for making a stain-blocking primer that includes: an emulsion latex polymer including interpolymerized monomers including: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
- RO-C(0)-CH CH 2
- R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (in certain embodiments, R has 20 or fewer carbon atoms); optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; and instructions for forming a stain-blocking primer, wherein a coating formed from the primer has a stain-blocking performance, based on the Stain-blocking Test described in the Examples Section (based on ASTM D7514-14), characterized by a DE value of: at most 20, preferably at most 18, for a water-washable black marker (e.g., Marks a Lot Black); or at most 16 for a water
- At least one of these colored marker values is met. In certain preferred embodiments, two of these three colored marker (black, blue, or green) values are met. In certain more preferred embodiments, all three colored marker (black, blue, or green) values are met.
- a method in another embodiment, includes: causing a stain-blocking polymer to be applied to a stained substrate, wherein the stain-blocking polymer is an emulsion latex polymer including interpolymerized monomers including: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
- R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (in certain embodiments, R has 20 or fewer carbon atoms); optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
- polymer and polymeric material include, but are not limited to, organic homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, etc., and blends and modifications thereof.
- polymer shall include all possible geometrical configurations of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and atactic symmetries.
- stain as used herein includes any mark, blemish, discoloration, or any deposit, whether or not visible or readily apparent to the naked eye.
- stain thus includes marks caused by inks, crayons, lipstick, grease pencils, smoke residue, tannins, water extracts, and the like. These stains may be found on residential or commercial walls as graffiti, markings from pens or color markers, on or native to wooden substrates, on wood-composite substrates, on concrete substrates, on paper substrates (such as wail board coverings), and on other substrates that are normally painted with one or more liquid coatings.
- stain-blocking means binding, blocking or masking a stain where it cannot be seen, or is substantially less visible, once one or more liquid coatings are applied and dried, or in those cases where the stain is not visible or only slightly visible, that the stain cannot migrate through the one or more subsequently applied and dried liquid coatings. This is in contrast to a polymer or primer that is “stain-proof’ or ‘'stain-resistant” or “stain- repelling.”
- the phrase “consisting essentially of’ indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present depending upon whether or not they materially affect the activity or action of the listed elements.
- room temperature refers to a temperature of 20 °C to 25 °C.
- the present disclosure provides stain-blocking polymers, as well as primers, kits, and methods that include such stain-blocking polymers, wherein the stain-blocking polymer is an emulsion latex polymer.
- a stain-blocking primer is provided.
- a primer is a coating composition that forms a continuous coating (e.g., by rolling, brushing, spraying) on a substrate such as wood (e.g., redwood, cedar, elm, merbau, and mahogany), metal (e.g., steel), etc., which adheres well and is sandable when dry.
- a primer is used between a substrate, whether previously coated or not, and a topcoat such as a paint.
- the primer is used to hide or block a staining agent in or on a substrate (i.e., a stained substrate) from showing through the topcoat. That is, the primer of the present disclosure acts as a barrier coating to a variety of underlying stairsing agents (whether polar or non-polar, hydrophilic or hydrophobic), such as tannins, inks, crayons, lipstick, grease pencils, smoke residue, water extracts, and the like, which can leached out of the underlying substrate. 'This is in contrast to surface staining and snail trails that result from a component (e.g., surfactant) leaching out of the topcoat.
- stairsing agents whether polar or non-polar, hydrophilic or hydrophobic
- the present disclosure also provides a stained substrate (i.e., a substrate such as wood containing a staining agent, such as tannins, inks, etc.) having a stain-blocking polymer, which may be included in a stain-blocking primer, coated thereon.
- a stained substrate i.e., a substrate such as wood containing a staining agent, such as tannins, inks, etc.
- the substrate may include a metal, wood, wood composite, concrete, paper (such as wail board coverings), and other such substrates that are normally painted with one or more liquid coatings.
- the substrate can be a primed surface and even a previously painted surface.
- the primers of the present disclosure are aqueous coating compositions, preferably have a viscosity of 60-120 units measured by Krebs Viscometer at room temperature (suitable for spray, roll, or brush).
- a hardened coating i.e., dry film formed from a latex polymer described herein (or aqueous composition in the form of a primer including a latex polymer described herein) on a substrate surface (e.g., a wood or metal surface), has one or more of the following properties: a stain-blocking performance, based on the Stainblocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a water-washable black marker (e.g., Marks a Lot Black); and/or at most 16 for a water-washable blue marker (e.g., Window Marker Blue); and/or at most 15, preferably at most 12, for a water-washable green marker (e.g., Window Marker Green) (or in certain embodiments, such as for single-stage latex polymers, the DE value is: at most 14 for black water-washable marker; at most 7 for a blue water-washable marker; and/or at most 8 for a green water-washable marker);
- At least one of these colored marker values is met by a hardened coating. In certain preferred embodiments, two of these three colored marker (black, blue, or green) values are met. In certain more preferred embodiments, all three colored marker (black, blue, or green) values are met.
- a hardened coating of the present disclosure includes all of these characteristics - stain-blocking performance, adhesion performance, and pendulum hardness.
- the primer formulation is a flat primer formulation that includes the emulsion latex polymer of the present disclosure, a pigment grind, a coalescent, a biocide (1,2- benzisothiazolin-3-one), sodium nitrite, rheology modifiers (i.e., thickeners such as hydrophobically modified polyether and hydrophobically modified ethylene oxide urethane) used in amounts to achieve coalescence below 50 °F and a KU viscosity range of 100 ⁇ 3.
- rheology modifiers i.e., thickeners such as hydrophobically modified polyether and hydrophobically modified ethylene oxide urethane
- the emulsion latex polymer (i.e., emulsion polymerized latex polymer) includes interpolymerized monomers including: at least 1 wt-%, or at least 2 wt-% (in certain embodiments, at least 1 wt-% to less than 20 wt-%), based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
- RO-C(0)-CH CH 2
- R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
- the acrylic acid ester monomers of Formula (I) have a homopolymer glass transition temperature (Tg) of less than 1 10 °C, or less than 50 € In certain embodiments, the acrylic acid ester monomers of Formula (I) have a homopolymer Tg of at least 20 °C, or at least 30 °C.
- a mixture of the acrylic acid ester monomers of Formula (I) are used to form the emulsion latex polymer.
- R of Formula (I) is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (e.g., a cyclohexane group with a t-butyl substituent).
- R of Formula (I) has no more than 20 carbon atoms (i.e., 20 or fewer carbon atoms), no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms.
- R of Formula (I) is a branched alkyl group having a tertiary carbon atom. In certain embodiments, R of Formula (I) is a branched alkyl group of 4 to 10 carbon atoms having a tertiary carbon atom.
- the one or more monomers of Formula (I) are selected from isobornyl acrylate, cyclohexyl acrylate, t-butyl acrylate, and a mixture thereof. In certain embodiments, the one or more monomers of Formula (I) comprise t-butyl acrylate.
- the emulsion latex polymer includes at least 1 wt-%, at least 2 wt-%, at least 5 wt-%, of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers. In certain embodiments, the emulsion latex polymer includes less than 20 wt-%, up to 15 wt-% (including 15 wt-%), or up to 10 wt-%, of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
- the interpolymerized monomers of the emulsion latex polymer include one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof.
- the emulsion latex polymer includes at least 10 wt-%, at least 20 wt-%, at least 30 wt-%, at least 40 wt-%, at least 50 wt-%, at least 60 wt-%, at least 70 wt-%, at least 75 wt-%, at least 80 wt-%, at least 83 wt-%, at least 84 wt-%, least 85 wt-%, or at least 90 wt-%, of these one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers.
- these one or more (meth)acrylate monomers e.g., two or more (meth)acrylate monomers
- the emulsion latex polymer includes up to 99 wt-%, up to 98 wt-%, or up to 95 wt-%, of these one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers.
- the interpolymerized monomers of the emulsion latex polymer include n-butyl methacrylate (n-BMA), it is present in an amount of no more than 12 wt-%, based on the total weight of the interpolymerized monomers. While not being bound by theory, it is believed that n-BMA negates the benefits of the monomer of Formula (I).
- the interpolymerized monomers of the emulsion latex polymer include one or more wet adhesion monomers.
- wet adhesion monomers include N- (2-methacryloyloxyethyl) ethylene urea (available as a 50 % aqueous solution under the tradename SIPOMER WAM E W 50, as a 50 % methyl methacrylate solution under the tradename SIPOMER WAM E MMA50, or as a 25 % methyl methacrylate solution under the tradename SIPOMER WAM E MMA25, all from Solvay), l-(2-((3-(allyloxy)-2- hydroxyproypl)amino)ethyl)imidazolidine-2-one (available as a 90 wt-% aqueous solution under the tradename SIPOMER WAM from Solvay), N-(2-methacryloyloxyethyl) ethylene urea (available as a 50 % aqueous solution under the
- the emulsion latex polymer includes at least 0.2 wt-% of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers. In certain embodiments, the emulsion latex polymer includes up to 2.0 wt-%, or up to 1.0 wt-%, of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
- the interpolymerized monomers of the emulsion latex polymer include styrene.
- the emulsion latex polymer includes at least 1 wt-%, at least 5 wt-%, at least 10 wt-%, or at least 15 wt-%, styrene, based on the total weight of the interpolymerized monomers.
- the emulsion latex polymer includes up to 75 wt-%, or up to 50 wt-% styrene, based on the total weight of the interpolymerized monomers.
- a stain-blocking polymer is an emulsion latex polymer that includes interpolymerized monomers including: at least 1 wt-%, or at least 2 wt-%, of one or more acrylic acid ester monomers of Formula (I):
- R is a branched alkyl having a tertiary carbon atom (in certain embodiments, R has 20 or fewer carbon atoms); at least 10 wt-% of one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; and at least 1 wt-%, at least 5 wt-%, at least 10 wt-%, or at least 15 wt-%, styrene; wherein the weight percentages are based on the total weight of the interpolymerized monomers.
- the latex polymer is a single stage latex polymer. In certain embodiments, the latex polymer is a multistage latex polymer, such as a gradient Tg latex polymer or a core-shell(s) latex polymer. In certain embodiments, the emulsion latex polymer is a two- or more-stage emulsion latex polymer (e.g., resulting from a power feed process).
- multistage when used with respect to a latex polymer means the polymer was made using discrete charges of two or more monomers, made using a varying (e.g., continuously varying) charge of two or more monomers, or made using a combination of both discrete charges and varying charges of two or more monomers.
- a multistage polymer is distinct from a single stage polymer made using one type of monomer blend with distinct polymer seed particles.
- a multistage polymer consists of polymer stages with different Tg’s, where the higher Tg stages are considered the hard stages and the lower Tg stages are considered the soft stages.
- a multistage latex will not exhibit a single Tg inflection point as measured by differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- a DSC curve for a multistage latex made using discrete charges of two or more monomers may exhibit two or more Tg inflection points.
- a DSC curve for a multistage latex made using a continuously varied charge of two or more monomers may exhibit no Tg inflection points.
- a DSC curve for a single stage latex made using a single monomer charge or a non-varying charge of two monomers may exhibit only a single Tg inflection point.
- a lower Tg inflection point may sometimes be detected on closer inspection, or the synthetic scheme used to make the latex may be examined to determine whether or not a multistage latex would be expected to be produced.
- latex polymers are typically made using seed particles as a nucleating agent for polymerization.
- seed particles may be in the form of inorganic particulate seed (e.g., clay or glass particles), preformed particulate polymer seed (latex or non-latex polymer seed), or particulate seed polymer formed in situ.
- Polymer seed can be an emulsion polymerized polymer seed, but does not encompass polymeric surfactant.
- seed particles are used in an amount of no more than 10 wt-%, or no more than 5 wt-%, based on latex polymer solids in the final latex.
- inorganic particulate seed, preformed particulate polymer seed, or particulate seed polymer formed in situ such seed particles will not be deemed to provide a stage of a multistage polymer or to provide a basis for designating a single stage polymer made using such seed polymer as a multistage polymer.
- the one or more monomers of Formula (I) is present in a hard stage of the emulsion latex polymer.
- Latex polymers described herein may or may not have a glass transition temperature that is measurable.
- glass transition temperature or “Tg” refers to the temperature at which an amorphous, solid material undergoes a reversible transition to a molten, rubber-like state.
- the Tg may be measured using DSC, or calculated using the Fox equation. Application of the Fox equation to estimate the Tg of polymers is well known to one skilled in the art.
- the latex polymer has a measured Tg, as measured by DSC. Such Tg may be measured at the beginning, mid-point, or end of polymerization. In certain embodiments, however, the latex polymer may have no clearly measurable Tg. Thus, a latex polymer may be referred to as a “gradient Tg polymer,” it may not have a clearly measurable Tg using DSC.
- the latex polymer is a multistage polymer having at least one measured Tg and at least one Fox Tg (which are not alternative representations of the same glass transition).
- Fox Tg and “calculated Tg” and “calculated Fox Tg” are used interchangeably.
- the Tg of a particular stage, or combination of stages can be estimated (i.e., calculated) using the Fox equation.
- the theoretical Tg may be calculated using the Fox equation as follows:
- Tga and Tgb are the respective glass transition temperatures in Kelvin of homopolymers made from monomers “a” and “b”;
- Wa and Wb are the respective weight fractions of polymers “a” and “b”.
- the value of Tg of the monomers used to estimate the polymer Tg are based on literature values. Typically, there is some variation of the Tg values of the homopolymers of monomers listed in such literature. The difference arises from the test method used to measure the Tg. The differences also arise from influence of comonomers polymerized together.
- the values used for the homopolymer Tg of certain monomers, particularly monomers used in the examples are listed herein (e.g., in the Materials Table in the Examples Section).
- the method of determining the Tg of a homopolymer can be determined using the DSC procedure described in the Examples Section, particularly if the literature values are significantly different (e.g., the literature values vary by at least 15 °C). If the literature values vary by less than 15 °C, then use the lower literature value.
- the multistage polymer is a gradient latex polymer (i.e., gradient Tg latex polymer).
- a gradient Tg latex polymer will have a DSC (differential scanning calorimetry) curve that exhibits no Tg inflection points, and could be said to have an essentially infinite number of Tg stages.
- DSC differential scanning calorimetry
- the resulting multistage latex polymer will have a gradient Tg from high to low. In other embodiments, it may be favorable to feed a high Tg hard stage monomer composition into a low Tg soft stage monomer composition.
- a multistage latex described herein will contain at least 10 wt-%, at least 20 wt-%, or at least 25 wt-%, of high Tg or hard stage monomers. In some embodiments, a multistage latex described herein will include up to 50 wt-%, up to 40 wt-%, or up to 35 wt-%, of high Tg or hard stage monomers. In some embodiments, a multistage latex described herein will include at least 50 wt-%, at least 60 wt-%, or at least 65 wt-%, of low Tg or soft stage monomers. In some embodiments, a multistage latex described herein will include up to 90 wt-%, up to 80 wt-%, or up to 75 wt-%, of low Tg or soft stage monomers.
- a multistage latex described herein preferably includes at least two polymer portions, e.g., a first stage and a second stage, with different Tg values, where the difference in Tg (ATg) is at least 35 °C, at least 50 °C, or at least 60 °C, or at least about 65 °C. In certain aspects, the ATg is less than 200 °C, less than 150 °C, or less than 100 °C.
- a gradient Tg polymer may also be used in conjunction with multiple Tg polymers.
- a Tg differential may be determined by using the Fox equation to calculate the theoretical Tg for a copolymer made from the monomer feed at the start of polymerization and comparing the result to the calculated theoretical Tg for a copolymer made from the second feed.
- Such gradient Tg can result from the second monomer feed being combined into the first monomer feed to form a gradient architecture, or ultimately result from two monomer feeds being combined at differential rates (e.g., the rate of one monomer feed increases while the rate of a second monomer feed decreases).
- Tg there may be a discrete measurable Tg of an otherwise gradient Tg latex polymer, such discreet Tg is typically corresponding to the polymer resulting from polymerization of the first monomer feed, or to a mixture of the first monomer feed and a small amount of the second monomer feed.
- the emulsion latex polymer of the present disclosure has at least one Fox Equation (theoretical calculated) Tg of 10 °C to 45 °C (in certain embodiments, 25 °C to 45 °C, or 10 °C to 35 °C, and in certain embodiments, the Fox Equation Tg is 35 °C). In certain embodiments, the emulsion latex polymer of the present disclosure has at least one Fox Equation (theoretical calculated) Tg of 45 °C to -10 °C (in certain embodiments, -45 °C to -22 °C, and in certain embodiments, the Fox Equation Tg is -32 °C, or -22 °C).
- the emulsion latex polymer of the present disclosure has an acid number of up to 30 (per kg OH). In certain embodiments, the emulsion latex polymer of the present disclosure has an acid number of at least 5 (per kg OH).
- the emulsion latex polymer of the present disclosure includes latex particles having a volume average particle size of at least 50 nm, or at least 60 nm, or at least 70 nm. In certain embodiments, the emulsion latex polymer of the present disclosure includes latex particles having a volume average particle size of up to 150 nm, or up to 130 nm.
- Latex polymers may be made from the described monomers using a variety of techniques known to one skilled in the art. Typically, such polymers are made from an aqueous emulsion that includes one or more monomers as described herein, preferably using a multistage feed process. In certain embodiments, after the latex polymer is formed in water, more water may be added to obtain a desired solids level.
- Such multistage feed processes for producing emulsion copolymers are well-known. They enable one to constantly vary the composition of monomers being polymerized to produce copolymers having a variety (e.g., gradient) of desired properties. For example, in certain embodiments a gradient is achieved by changing the feed rate of a second monomer mixture into a first monomer mixture.
- the one or more monomers of Formula (I) are added in the first stage of a multistage process.
- the latex polymer is formed from components that also include one or more radical transfer agents (i.e., chain transfer agents), although such agent is not required.
- the radical transfer agents are selected from dodecanethiol, mercaptopropionic acid, isooctyl thioglycolate, butyl mercapto propionate, and combinations thereof.
- the one or more radical transfer agents are present in an amount of at least 0.1 wt-%, based on the total weight of monomers, although typically, no radical transfer agent is needed. If used, in certain embodiments, the one or more radical transfer agents are present in an amount of up to 0.5 wt-%, based on the total weight of monomers.
- the stain-blocking primer includes at least 10 wt-%, or at least 15 wt-% of a stain-blocking polymer, which is an emulsion latex polymer, based on the total nonvolatile weight of the primer. In certain embodiments, the stain-blocking primer includes up to 50 wt-%, or up to 30 wt-% of a stain-blocking polymer, which is an emulsion latex polymer, based on the total nonvolatile weight of the primer.
- the primers of the present disclosure also include an aqueous carrier (e.g., water and one or more optional organic solvents), and optionally, one or more additives selected from a surfactant, thickener, biocide, mildewcide, colorant (e.g., inorganic pigment), and combinations thereof.
- aqueous carrier e.g., water and one or more optional organic solvents
- additives selected from a surfactant, thickener, biocide, mildewcide, colorant (e.g., inorganic pigment), and combinations thereof.
- the stain-blocking primer includes water in an amount of at least 50 wt-%, based on the total weight of the primer. In certain embodiments, the stain blocking primer includes water in an amount of up to 90 wt-%, based on the total weight of the primer.
- the primers of the present disclosure include a substantial amount of water and may further include one or more optional organic solvents. Such primers are referred to herein as aqueous coating compositions.
- water constitutes greater than 20 wt-%, or greater than 35 wt-%, or greater than 50 wt-%, of the total weight of the aqueous carrier. In some embodiments, water constitutes 100 wt-% or less, less than 95 wt- %, or less than 90 wt-%, of the total weight of the aqueous carrier.
- Suitable optional organic solvents include ketones, glycol ethers, esters, alcohols, aromatics, and combinations thereof.
- solvents include carbitol, butyl carbitol, butylcellosolve, propylene glycol monomethyl ether, dibasic ester, ethyl carbitol, diisobutyl ketone, dipropylene glycol n-butyl ether (DPNB), and 2, 2, 4-trimethyl- 1, 3 -pentanediol monoisobutyrate (available under the tradename TEXANOL), and mixtures thereof.
- DPNB dipropylene glycol n-butyl ether
- TEXANOL 2, 2, 4-trimethyl- 1, 3 -pentanediol monoisobutyrate
- the primer includes one or more additives selected from a surfactant (e.g., fluorinated surfactants, ethylenically unsaturated surfactants), thickener (e.g., to allow the polymer to coat out on a substrate surface), coalescent (e.g., a glycol ether such as EASTMAN EP, EASTMAN DM, EASTMAN DE, EASTMAN DP, EASTMAN DB and EASTMAN PM from Eastman Chemical Co., an ester alcohol such as TEXANOL ester alcohol from Eastman Chemical Co., or a low VOC coalescent compound such as is described in U.S. Patent No.
- a surfactant e.g., fluorinated surfactants, ethylenically unsaturated surfactants
- thickener e.g., to allow the polymer to coat out on a substrate surface
- coalescent e.g., a glycol ether such as EASTMAN EP, EASTMAN DM, EASTMAN DE
- the primer includes one or more additives for wet hide capability (e.g., titanium dioxide particles, opaque polymeric spheres, and kaolin clay platelets). Such additives may be added during polymerization or after polymerization.
- additives for wet hide capability e.g., titanium dioxide particles, opaque polymeric spheres, and kaolin clay platelets. Such additives may be added during polymerization or after polymerization.
- one or more additives may be present in an amount of at least 0.1 wt-%, at least 0.5 wt-%, or at least 1 wt-%, based on the total weight of polymer solids. In certain embodiments, one or more additives may be present in an amount of up to 5 wt-%, up to 4 wt-%, up to 3 wt-%, up to 2 wt-%, or up to 1 wt-%, based on the total weight of polymer solids.
- primers of the present disclosure are low VOC primers.
- a multistage latex suitable for low VOC primers may be formed.
- the phrase “low VOC” when used with respect to a primer means that the primer contains less than 10 weight percent (wt-%) volatile organic compounds, more preferably less than 7 wt-% volatile organic compounds, and most preferably less than 4 wt-% volatile organic compounds, based upon the total primer weight.
- VOC volatile organic compound
- EPA Environmental Protection Agency
- VOC content volatile organic compound content
- ASTM method D2369-90 refers to the weight of VOC per volume of the coating solids, and is reported, for example, as grams VOC per liter (g/L).
- the primer is a clear (i.e., unpigmented) primer.
- the present disclosure also provides a kit for making a stain-blocking primer.
- the kit includes an emulsion latex polymer described herein and instructions for forming a stainblocking primer as described herein.
- the emulsion latex polymer and the instructions are typically physically packaged together; however, the two do not need to be physically delivered together in a physical package to be a kit.
- the present disclosure also provides a method (e.g., a method of blocking stains).
- the method includes causing a stain-blocking polymer as described herein, which may be in a primer) to be applied to a stained substrate (i.e., a substrate that has a stain or a staining agent therein or thereon).
- a stain-blocking polymer as described herein, which may be in a primer
- causing means applying the polymer (e.g., in an aqueous primer formulation) to the stained substrate, instructing it to be applied to the stained substrate, supplying it to a user to apply it to a stained substrate, or supplying it to a manufacturer to make a primer for use on a stained substrate.
- the method also includes causing a primer that includes a stain-blocking polymer to be applied to a stained substrate, and drying or allowing the primer to harden to form a hardened stain-blocking coating and block the stain (i.e., form a barrier for the staining agent to show ' through a topcoat).
- the step of applying the aqueous coating composition may be any of a wide variety of coating techniques known to one skilled in the art.
- the step of allowing a primer (i.e., aqueous composition) to harden and form a hardened coating may include exposing the primer to a wide variety of conditions known to one skilled in the art.
- such conditions include exposing the aqueous composition to a temperature of at least 10°C, and in certain embodiments up to 100°C, for a period of time of at least 60 minutes and up to 168 hours.
- such conditions may include hardening (e.g., drying or curing) the primer at a temperature of at least 10°C for at least 168 hours.
- such conditions may include using a temperature of no more than (i.e., up to) 100°C for no more than (i.e., up to) 60 minutes.
- Such hardening may occur in one or more steps.
- a coated (e.g., primed) stained substrate including a substrate surface having a hardened coating disposed thereon is provided by the present disclosure. Such coated stained substrate may be prepared by this method.
- a stain-blocking primer includes: at least 10 wt-%, based on the total nonvolatile weight of the primer, of an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-%, based on total weight of monomers, of one or more acrylic acid ester monomers of Formula (I):
- R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; an aqueous carrier; and optionally, one or more additives selected from a surfactant, thickener, coalescent, biocide, mildewcide, colorant (e.g., inorganic pigment), and combinations thereof.
- a surfactant thickener, coalescent, biocide, mildewcide, colorant (e.g., inorganic pigment), and combinations thereof.
- a primer of embodiment 1 wherein R of Formula (I) has no more than 20 carbon atoms, no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms.
- R of Formula (I) is a branched alkyl group having a tertiary carbon atom.
- a primer of any of the previous embodiments is provided wherein R of Formula (I) is a branched alkyl group of 4 to 10 carbon atoms having a tertiary carbon atom.
- a primer of any of the previous embodiments wherein the monomer of Formula (I) has a homopolymer Tg of less than 110 °C, or less than 50 °C. In certain embodiments (embodiment 6), a primer of any of the previous embodiments is provided wherein the monomer of Formula (I) has a homopolymer Tg of at least 20 °C, or at least 30 °C,
- a primer of any of the previous embodiments is provided wherein the emulsion latex polymer comprises a mixture of monomers of Formula (I).
- a primer of any of the previous embodiments wherein the one or more monomers of Formula (I) are selected from isobomyl acrylate, cyclohexyl acrylate, t-butyl acrylate, and a mixture thereof.
- a primer of embodiment 8 is provided wherein the one or more monomers of Formula (I) comprise t-butyl acrylate.
- a primer of any of the previous embodiments wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of 10 °C to 45 °C (in certain embodiments, 25 °C to 45 °C, or 10 °C to 35 °C).
- a primer of embodiment 10 is provided wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of -45 °C to -10 °C (in certain embodiments, -45 °C to -22 °C, -32 °C, or -22 °C).
- a primer of any of the previous embodiments wherein the latex polymer has an acid number of up to 30 (per kg OH). In certain embodiments (embodiment 13), a primer of any of the previous embodiments is provided wherein the latex polymer has an acid number of at least 5 (per kg OH).
- a primer of any of the previous embodiments wherein the latex polymer comprises latex particles having a volume average particle size of at least 50 nm, or at least 60 nm, or at least 70 nm.
- a primer of any of the previous embodiments is provided wherein the latex polymer comprises latex particles having a volume average particle size of up to 150 nm, or up to 130 nm.
- a primer of any of the previous embodiments comprising at least 15 wt-% of the emulsion latex polymer, based on the total nonvolatile weight of the primer.
- a primer of any of the previous embodiments is provided comprising up to 50 wt-% of the emulsion latex polymer, based on the total nonvolatile weight of the primer.
- a primer of embodiment 17 is provided comprising up to 30 wt-% of the emulsion latex polymer, based on the total nonvolatile weight of the primer.
- a primer of any of the previous embodiments is provided wherein the polymer is a two- or more- stage emulsion latex polymer (e.g., resulting from a power feed process).
- a primer of embodiment 19 is provided wherein the monomer of Formula (I) is present in a hard stage of the emulsion latex polymer.
- a primer of any of the previous embodiments wherein the interpolymerized monomers comprise at least 2 wt-%, or at least 5 wt- %, of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
- a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise less than 20 wt-% (or up to 15 wt-%, or up to 10 wt-%) of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
- a primer of any of the previous embodiments wherein the interpolymerized monomers comprise one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate (n-BA and n-BMA), ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof.
- the interpolymerized monomers comprise one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate (n-BA and n-BMA), ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof.
- a primer of any of the previous embodiments wherein the interpolymerized monomers comprise at least 10 wt-% (or at least 20 wt-%, at least 30 wt-%, at least 40 wt-%, at least 50 wt- %, at least 60 wt-%, at least 70 wt-%, at least 75 wt-%, at least 80 wt-%, at least 83 wt-%, at least 84 wt-%, at least 85 wt-%, or at least 90 wt-%) of one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers.
- the interpolymerized monomers comprise at least 10 wt-% (or at least 20 wt-%, at least 30 wt-%, at least 40 wt-%, at least 50 wt- %, at least 60 wt-%
- a primer of any of the previous embodiments wherein the interpolymerized monomers comprise up to 99 wt-% (or up to 98 wt-%, or up to 95 wt-%) of one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers.
- the interpolymerized monomers of the emulsion latex polymer include n-butyl methacrylate (n-BMA), it is present in an amount of no more than 12 wt-%, based on the total weight of the interpolymerized monomers.
- a primer of any of the previous embodiments wherein the interpolymerized monomers comprise styrene.
- a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise at least 1 wt-% (or at least 5 wt-%, at least 10 wt-%, or at least 15 wt-%) styrene, based on the total weight of the interpolymerized monomers.
- a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise up to 75 wt-% (or up to 50 wt-%) styrene, based on the total weight of the interpolymerized monomers.
- a primer of any of the previous embodiments wherein the interpolymerized monomers comprise one or more wet adhesion monomers (e.g., those selected from N-(2-methacryloyloxyethyl) ethylene urea, l-(2-((3- (allyloxy)-2-hydroxyproypl)amino)ethyl)imidazolidine-2-one, and combinations thereof).
- a primer of embodiment 29 is provided wherein the interpolymerized monomers comprise at least 0.2 wt-% of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
- a primer of embodiment 29 or 30 wherein the interpolymerized monomers comprise up to 2.0 wt-% (or up to 1.0 wt-%) of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
- a primer of any of the previous embodiments is provided which is a clear (i.e., unpigmented) primer.
- a primer of any of the previous embodiments is provided further comprising one or more additives selected from a surfactant, thickener, coalescent, biocide, mildewcide, colorant (e.g., inorganic pigment), and mixtures thereof.
- a primer of embodiment 33 is provided comprising an inorganic pigment (e.g., CaCCb, TiCk).
- a primer of embodiment 33 or 34 is provided comprising a thickener (e.g., to allow the polymer to coat out on a substrate surface).
- a primer of any of the previous embodiments is provided comprising one or more additives for wet hide capability (e.g., titanium dioxide particles, opaque polymeric spheres, and kaolin clay platelets).
- a primer of any of the previous embodiments having a viscosity of 60-120 units measured by Krebs Viscometer at room temperature (suitable for spray, roll, or brush).
- a primer of any of the previous embodiments wherein a hardened coating formed from the primer has a stain-blocking performance, based on the Stain-blocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a black water-washable marker; at most 16 for a blue water- washable marker; and/or at most 15, preferably at most 12 for a green water-washable marker.
- the DE value is: at most 14 for black water-washable marker; at most 7 for a blue water-washable marker; and/or at most 8 for a green water- washable marker.
- a primer of any of the previous embodiments wherein a hardened coating formed from the primer has an adhesion performance of at least 2 based on the ASTM 3359 Cross-cut Adhesion Test.
- a primer of any of the previous embodiments is provided wherein a hardened coating formed from the primer has a pendulum hardness of at least 4 based on the Konig Pendulum Hardness Test.
- a primer of any of the previous embodiments is provided which is a low VOC primer (i.e., contains less than 10 wt-% volatile organic compounds, based on the total weight of the primer).
- a primer of embodiment 41 which includes less than 7 wt-%, or less than 4 wt-%, volatile organic compounds, based on the total weight of the primer).
- a stain-blocking polymer includes: an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-% of one or more acrylic acid ester monomers of Formula (I):
- RO-C(0)-CH CH2
- R is a branched alkyl having a tertiary carbon atom; at least 10 wt-% of one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; and at least 1 wt-% styrene; wherein the weight percentages are based on the total weight of the interpolymerized monomers; wherein a hardened coating formed from the stain-blocking polymer has one or more of the following properties: a stain-blocking performance, based on the Stain-blocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a black water- washable marker; at most 16 for a blue water-washable marker (or in certain embodiments, such as in single-stage latex polymers, the DE value is: at most 14 for black water-washable
- a stain-blocking polymer of embodiment 43 wherein R of Formula (I) has no more than 20 carbon atoms, no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms.
- a stain blocking polymer of embodiment 43 or 44 is provided wherein R of Formula (I) is a branched alkyl group having a tertiary carbon atom.
- a stain blocking polymer of embodiments 43 through 45 wherein R of Formula (I) is a branched alkyl group of 4 to 10 carbon atoms having a tertiary carbon atom.
- a stain-blocking polymer of embodiments 43 through 46 is provided wherein the monomer of Formula (I) has a homopolymer Tg of less than 110 °C, or less than 50 °C.
- a stain-blocking polymer of embodiments 43 through 47 wherein the monomer of Formula (I) has a homopolymer Tg of at least 20 °C, or at least 30 °C.
- a stain-blocking polymer of embodiments 43 through 48 wherein the emulsion latex polymer comprises a mixture of monomers of Formula (I).
- a stain-blocking polymer of embodiments 43 through 49 wherein the one or more monomers of Formula (I) are selected from isobornyl acrylate, cyclohexyl acrylate, t-butyl acrylate, and a mixture thereof.
- a stain-blocking polymer of embodiment 50 is provided wherein the one or more monomers of Formula (I) comprise t-butyl acrylate.
- a stain-blocking polymer of embodiments 43 through 51 wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of 10 °C to 45 °C (in certain embodiments, 25 °C to 45 °C, or 10 °C to 35 °C).
- a stain-blocking polymer of embodiment 52 wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of -45 °C to -10 °C (in certain embodiments, -45 °C to -22 °C, -32 °C, or -22 °C).
- a stain-blocking polymer of embodiments 43 through 53 wherein the latex polymer has an acid number of up to 30 (per kg OH).
- a stain-blocking polymer of embodiments 43 through 54 is provided wherein the latex polymer has an acid number of at least 5 (per kg OH).
- a stain-blocking polymer of embodiments 43 through 55 wherein the latex polymer comprises latex particles having a volume average particle size of at least 50 nm, or at least 60 nm, or at least 70 nm.
- a stain-blocking polymer of embodiments 43 through 56 is provided wherein the latex polymer comprises latex particles having a volume average particle size of up to 150 nm, or up to 130 nm.
- a stain-blocking polymer of embodiments 43 through 57 wherein the polymer is a two- or more- stage emulsion latex polymer (e.g., resulting from a power feed process).
- a stain blocking polymer of embodiment 58 is provided wherein the monomer of Formula (I) is present in a hard stage of the emulsion latex polymer.
- a stain-blocking polymer of embodiments 43 through 59 wherein the interpolymerized monomers comprise at least 2 wt-%, or at least 5 wt-%, of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
- a stain-blocking polymer of embodiments 43 through 60 is provided wherein the interpolymerized monomers comprise less than 20 wt-% (or up to 15 wt-%, or up to 10 wt-%) of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
- a stain-blocking polymer of embodiments 43 through 61 wherein the interpolymerized monomers comprise at least 75 wt-% (or least 80 wt-%, at least 83 wt-%, at least 84 wt-%, at least 85 wt-%, or at least 90 wt-%) of one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers.
- the interpolymerized monomers comprise at least 75 wt-% (or least 80 wt-%, at least 83 wt-%, at least 84 wt-%, at least 85 wt-%, or at least 90 wt-%) of one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers.
- a stain-blocking polymer of embodiments 43 through 62 wherein the interpolymerized monomers comprise up to 99 wt-% (or up to 98 wt-%, or up to 95 wt-%) of one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers.
- the interpolymerized monomers of the emulsion latex polymer include n-butyl methacrylate (n-BMA), it is present in an amount of no more than 12 wt-%, based on the total weight of the interpolymerized monomers.
- a stain-blocking polymer of embodiments 43 through 63 wherein the interpolymerized monomers comprise at least 5 wt-% (or at least 10 wt-%, or at least 15 wt-%) styrene, based on the total weight of the interpolymerized monomers.
- a stain-blocking polymer of embodiments 43 through 64 is provided wherein the interpolymerized monomers comprise up to 75 wt-% (or up to 50 wt-%) styrene, based on the total weight of the interpolymerized monomers.
- a stain-blocking polymer of embodiments 43 through 65 wherein the interpolymerized monomers comprise one or more wet adhesion monomers (e.g., those selected from N-(2-methacryloyloxy ethyl) ethylene urea, l-(2- ((3-(allyloxy)-2-hydroxyproypl)amino)ethyl)imidazolidine-2-one, and combinations thereof).
- wet adhesion monomers e.g., those selected from N-(2-methacryloyloxy ethyl) ethylene urea, l-(2- ((3-(allyloxy)-2-hydroxyproypl)amino)ethyl)imidazolidine-2-one, and combinations thereof.
- a stain-blocking polymer of embodiments 43 through 66 wherein the interpolymerized monomers comprise at least 0.2 wt-% of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
- a stain-blocking polymer of embodiment 66 or 67 is provided wherein the interpolymerized monomers comprise up to 2.0 wt-% (or up to 1.0 wt-%) of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
- a stained substrate having a stainblocking primer of any of embodiments 1 through 42 coated thereon or a stain-blocking polymer of any of embodiments 43 through 68 coated thereon.
- a stained substrate having a stainblocking polymer coated thereon, wherein the stain-blocking polymer is an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
- R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
- a stained substrate of embodiment 70 wherein R of Formula (I) has no more than 20 carbon atoms, no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms.
- R of Formula (I) has no more than 20 carbon atoms, no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms.
- R of Formula (I) has no more than 20 carbon atoms, no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms.
- R of Formula (I) is a branched alkyl group having a tertiary carbon atom.
- a stained substrate of embodiments 70 through 73 wherein the monomer of Formula (I) has a bomopoiymer Tg of less than 110 °C, or less than 50 °C.
- a stained substrate of embodiments 70 through 74 is provided wherein the monomer of Formula (I) has a homopolymer Tg of at least 20 °C, or at least 30 °C.
- a stained substrate of embodiments 70 through 75 wherein the emulsion latex polymer comprises a mixture of monomers of Formula (I).
- a stained substrate of embodiments 70 through 76 is provided wherein the one or more monomers of Formula (I) are selected from isobornyl acrylate, cyclohexyl acrylate, t-butyl acrylate, and a mixture thereof.
- a stained substrate of embodiment 77 is provided wherein the one or more monomers of Formula (I) comprise t-butyl acrylate.
- a stained substrate of embodiments 70 through 78 wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of Tg of 10 °C to 45 °C (in certain embodiments, 25 °C to 45 °C, or 10 °C to 35 °C).
- a stained substrate of embodiment 79 is provided wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of 45 °C to -10 °C (in certain embodiments, -45 °C to -22 °C, -32 °C, or -22 °C).
- a stained substrate of embodiments 70 through 80 is provided wherein the latex polymer has an acid number of up to 30 (per kg OH). In certain embodiments (embodiment 82), a stained substrate of embodiments 70 through 81 is provided wherein the latex polymer has an acid number of at least 5 (per kg OH).
- a stained substrate of embodiments 70 through 82 wherein the latex polymer comprises latex particles having a volume average particle size of at least 50 nm, or at least 60 nm, or at least 70 nm.
- a stained substrate of embodiments 70 through 83 wherein the latex polymer comprises latex particles having a volume average particle size of up to 150 nm, or up to 130 nm.
- a stained substrate of embodiments 70 through 84 wherein the polymer is a two- or more- stage emulsion latex polymer (e.g., resulting from a power feed process).
- a stained substrate of embodiment 85 is provided wherein the monomer of Formula (I) is present in a hard stage of the emulsion latex polymer.
- a stained substrate of embodiments 70 through 85 wherein the interpolymerized monomers comprise at least 2 wt-% (or at least 5 wt-%) of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
- a stained substrate of embodiments 70 through 86 is provided wherein the interpolymerized monomers comprise less than 20 wt-% (or up to 15 wt-%, or up to 10 wt-%) of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
- a stained substrate of embodiments 70 through 87 wherein the interpolymerized monomers comprise one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof.
- a stained substrate of embodiments 70 through 88 wherein the interpolymerized monomers comprise at least 10 wt-% (or at least 20 wt-%, at least 30 wt-%, at least 40 wt-%, at least 50 wt-%, at least 60 wt-%, at least 70 wt-%, at least 75 wt-%, at least 80 wt-%, at least 83 wt-%, at least 84 wt-%, at least 85 wt-%, or at least 90 wt-%) of one or more (meth)acrylate monomers, based on the total weight of the interpolymerized monomers.
- a stained substrate of embodiments 70 through 89 wherein the interpolymerized monomers comprise up to up to 99 wt-% (or up to 98 wt-%, or up to 95 wt-%) of one or more (meth)acrylate monomers, based on the total weight of the interpolymerized monomers.
- a stained substrate of embodiments 70 through 90 wherein the interpolymerized monomers comprise styrene.
- a stained substrate of embodiments 70 through 91 is provided wherein the interpolymerized monomers comprise at least 1 wt-% (or at least 5 wt-%, at least 10 wt-%, or at least 15 wt-%) styrene, based on the total weight of the interpolymerized monomers.
- a stained substrate of embodiments 70 through 92 wherein the interpolymerized monomers comprise up to 75 wt-% (or up to 50 wt-%) styrene, based on the total weight of the interpolymerized monomers.
- a stained substrate of embodiments 70 through 93 wherein the interpolymerized monomers comprise one or more wet adhesion monomers (e.g., those selected from N-(2-methacryloyloxy ethyl) ethylene urea, l-(2- ((3-(allyloxy)-2-hydroxyproypl)amino)ethyl)imidazolidine-2-one, and combinations thereof).
- wet adhesion monomers e.g., those selected from N-(2-methacryloyloxy ethyl) ethylene urea, l-(2- ((3-(allyloxy)-2-hydroxyproypl)amino)ethyl)imidazolidine-2-one, and combinations thereof.
- a stained substrate of embodiments 70 through 94 wherein the interpolymerized monomers comprise at least 0.2 wt-% of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
- the interpolymerized monomers comprise up to 2.0 wt-% (or up to 1.0 wt-%) of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
- a stained substrate of embodiments 70 through 96 wherein a hardened coating formed from the stain-blocking polymer has a stain blocking performance, based on the Stain-blocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a black water- washable marker; at most 16 for a blue water-washable marker; and/or at most 15, preferably at most 12, for a green water-washable marker (or in certain embodiments, such as in single-stage latex polymers, the DE value is: at most 14 for black water-washable marker; at most 7 for a blue water-washable marker; and/or at most 8 for a green water-washable marker).
- a stained substrate of embodiments 70 through 97 wherein a hardened coating formed from the stain-blocking polymer has an adhesion performance of at least 2 based on the ASTM 3359 Cross-cut Adhesion Test.
- a stained substrate of embodiments 70 through 98 is provided wherein a hardened coating formed from the stain blocking polymer has a pendulum hardness of at least 4 based on the Konig Pendulum Hardness Test.
- kits for making a stain-blocking primer includes: an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
- RO-C(0)-CH CH 2
- R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; and instructions for forming a stain-blocking primer.
- a kit for making a stain-blocking primer of embodiment 100 wherein a hardened coating formed from the primer has a stain blocking performance, based on the Stainblocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a black water-washable marker; at most 16 for a blue water- washable marker; and/or at most 15, preferably at most 12, for a green water-washable marker (or in certain embodiments, such as in single-stage latex polymers, the DE value is: at most 14 for black water-washable marker; at most 7 for a blue water-washable marker; and/or at most 8 for a green water-washable marker).
- a kit for making a stain-blocking primer of embodiment 100 or 101 wherein the emulsion latex polymer and the instructions are physically packaged together (but the two don’t need to be physically delivered together in a physical package to be a kit).
- a method includes: causing a stain-blocking polymer (e.g., of embodiments 43 through 68) to be applied to a stained substrate.
- a stain-blocking polymer e.g., of embodiments 43 through 68
- a method includes: causing a stain-blocking polymer to be applied to a stained substrate wherein the stain-blocking polymer is an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt- %, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
- R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
- ppm parts per million
- phr parts per hundred rubber
- mL milliliter
- L liter
- m meter
- mm millimeter
- cm centimeter
- kg kilogram
- g gram
- min minute
- s second
- hrs hour
- °C degrees Celsius
- °F degrees Fahrenheit
- MPa megapascals
- N-m Newton-meter
- Mn number average molecular weight
- cP centipoise.
- the Glass Transition Temperature (Tg) of the disclosed polymer composition is predicted from the Fox Equation, a generalized form of which is shown below: where WA, WB, WC, . . WN respectively represent the weight fraction of each monomer type A, B, C,.. N in the copolymer composition, and TgA, TgB, Tgc,.. TgN represent the corresponding Tg’s (expressed in Kelvin) of the homopolymers prepared from the respective monomer type A, B, C,.. N.
- the Fox equation is also known to adequately predict the effective overall Tg of a miscible polymer mixture.
- the overall Tg of the polymer blend can be determined by applying the Tg and weight fraction of each polymer stage in the Fox equation.
- the actual Tg of a polymer or polymer blend can determined experimentally by techniques such as differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). All actual Tg disclosed in the current disclosure are evaluated using a DSC25 differential scanning calorimeter equipped with a RSC90 cooler, both purchased from TA Instruments. Calibration was performed on an indium standard and all experiments use a standardized heat-cool -heat cycle at a 20 °C/min ramp rate.
- DSC differential scanning calorimetry
- DMA dynamic mechanical analysis
- monomer emulsion 1 was prepared by sequentially adding deionized water (113 g), DISPONIL FES 32 (16.5 g), SIPOMER PAM-4000 (5 g), VISIOMER MEEU 25M (6.8 g), methacrylic acid (4.3 g), 28 % ammonium hydroxide (2.3 g), dodecyl mercaptan (0.3 g), and a mixture of monomers (TABLE 1) under constant mixing with a three-blade impeller.
- monomer emulsion 2 was prepared by sequentially adding deionized water (201 g), DISPONIL FES 32 (33 g), SIPOMER PAM-4000 (9.8 g), VISIOMER MEEU 25M (13.6 g), methacrylic acid (8 g), 28 % ammonium hydroxide (4.6 g), dodecyl mercaptan (0.7 g), 2-ethylhexyl acrylate (2-EHA) (313 g), and styrene (261 g) under constant mixing with a three-blade agitator.
- an oxidizer solution containing 70 % aqueous tert-butyl hydroperoxide (4.3 g) in deionized water (90 g) and a reducer solution containing erythorbic acid (2.6 g) in deionized water (90 g) were fed separately and simultaneously into the reactor over 5.5 hr.
- monomer emulsion 2 was fed into the reactor over 2.5 hr.
- aqueous tert-butyl hydroperoxide 0.7 g
- erythorbic acid 0.5 g
- the reactor solution was cooled to below 40 °C and neutralized with 28 % ammonium hydroxide (7.4 g).
- the resulting emulsion was diluted with deionized water (50 g) and filtered through a 100 mhi filter.
- a 30 ⁇ 5 nm, 30 wt-% seed latex (182 g) and deionized water (459 g) were added.
- the reactor was fitted with a four-blade impeller, a condenser, and an internal temperature probe.
- the reactor assembly was heated to an internal temperature of 58-60 °C with constant agitation maintained throughout the synthetic process.
- monomer emulsion 1 was prepared by sequentially adding deionized water (113 g), DISPONIL FES 32 (16.5 g), SIPOMER PAM-4000 (5 g), VISIOMER MEEU 25M (6.8 g), methacrylic acid (4.3 g), 28 % ammonium hydroxide (2.3 g), dodecyl mercaptan (0.3 g), 2-ethylhexyl acrylate (17 g), and tert-butyl acrylate (291 g) under constant mixing with a three-blade impeller.
- monomer emulsion 2 was prepared by sequentially adding deionized water (201 g), DISPONIL FES 32 (33 g), SIPOMER PAM-4000 (9.8 g), VISIOMER MEEU 25M (13.6 g), methacrylic acid (8 g), 28 % ammonium hydroxide (4.6 g), dodecyl mercaptan (0.7 g), and a mixture of monomers (Table 2) under constant mixing with a three-blade agitator.
- an oxidizer solution containing 70 % aqueous tert- butyl hydroperoxide (4.3 g) in deionized water (90 g) and a reducer solution containing erythorbic acid (2.6 g) in deionized water (90 g) were fed separately and simultaneously into the reactor over 5.5 hr.
- monomer emulsion 2 was fed into the reactor over 2.5 hr.
- aqueous tert-butyl hydroperoxide 0.7 g
- erythorbic acid 0.5 g
- the reactor solution was cooled to below 40 °C and neutralized with 28 % ammonium hydroxide (7.4 g).
- the resulting emulsion was diluted with deionized water (50 g) and filtered through a 100 micrometers (pm) filter.
- LATEX PREPARATION PROCEDURE C POWERFEED LATEX
- a 30 ⁇ 5 nanometer (nm) 30 wt-% seed latex (182 g) and deionized water (459 g) were added.
- the reactor was fitted with a four-blade impeller, a condenser, and an internal temperature probe.
- the reactor assembly was heated to an internal temperature of 58-60 °C with constant agitation maintained throughout the synthetic process.
- monomer emulsion 1 was prepared by sequentially adding deionized water (113 g), DISPONIL FES 32 (16.5 g), SIPOMER PAM-4000 (5 g), VISIOMER MEEU 25M (6.8 g), methacrylic acid (4.3 g), 28 % ammonium hydroxide (2.3 g), dodecyl mercaptan (0.3 g), 2- ethylhexyl acrylate (53.3 g), styrene (154.4 g), and tert-butyl acrylate (100 g) under constant mixing with a three-blade impeller.
- Monomer Emulsion 2 was prepared by sequentially adding deionized water (201 g), DISPONIL FES 32 (33 g), SIPOMER PAM-4000 (9.8 g), VISIOMER MEEU 25M (13.6 g), methacrylic acid (8 g), 28 % ammonium hydroxide (4.6 g), dodecyl mercaptan (0.7 g), 2-ethylhexyl acrylate (313 g), and styrene (261 g) under constant mixing with a three-blade agitator.
- aqueous tert-butyl hydroperoxide 0.7 g
- erythorbic acid 0.5 g
- 7 % aqueous DISSOLVINE E-FE-13 0.2 g
- an oxidizer solution containing 70 % aqueous tert-butyl hydroperoxide (4.3 g) in deionized water (90 g) and a reducer solution containing erythorbic acid (2.6 g) in deionized water (90 g) were fed separately and simultaneously into the reactor over 5.5 hr.
- 70 % aqueous tert-butyl hydroperoxide (0.7 g) and erythorbic acid (0.5 g) were respectively added to the remaining oxidizer and reducer feed solutions.
- the reactor solution was cooled to below 40 °C and neutralized with 28 % ammonium hydroxide (7.4 g).
- the resulting emulsion was diluted with deionized water (50 g) and filtered through a 100 pm filter.
- LATEX PREPARATION PROCEDURE D SINGLE-STAGE LATEX
- a 30 ⁇ 5 nm, 30 wt-% seed latex (182 grams (g)) and deionized water (450 g) were added.
- the reactor was fitted with a four-blade impeller, a condenser, and an internal temperature probe.
- the reactor assembly was heated to an internal temperature of 58-60 °C with constant agitation maintained throughout the synthetic process.
- monomer emulsion was prepared by sequentially adding deionized water (340 g), DISPONIL FES 32 (49.5 g), SIPOMER PAM-4000 (14.8 g), VISIOMER MEEU 25M (20.4 g), methacrylic acid (12.2 g), 28 % ammonium hydroxide (7.5 g), and a mixture of monomers (TABLE 3) under constant mixing with a three-blade impeller.
- aqueous tert-butyl hydroperoxide Prior to addition of monomer emulsion to reactor, 70 % aqueous tert-butyl hydroperoxide (0.7 g), erythorbic acid (0.5 g), and 7 % aqueous DISSOLVINE E-FE-13 (0.2 g) were added to the reactor. Monomer emulsion was fed into the reactor over 3 hours (hr). Upon initiation of monomer emulsion feed, an oxidizer solution containing 70 % aqueous tert-butyl hydroperoxide (4.3 g) in deionized water (90 g) and a reducer solution containing erythorbic acid (2.6 g) in deionized water (90 g) were fed separately and simultaneously into the reactor over 4.5 hr.
- aqueous tert-butyl hydroperoxide 70 % aqueous tert-butyl hydroperoxide (0.7 g) and erythorbic acid (0.5 g) were respectively added to the remaining oxidizer and reducer feed solutions.
- the reactor solution was cooled to below 40 °C and neutralized with 28 % ammonium hydroxide (5.4 g).
- the resulting emulsion was diluted with deionized water (50 g) and filtered through a 100 pm filter.
- Examples 1-6 were 2-stage latexes prepared according to the Latex Preparation Procedure A for a two-stage latex, using the Example 1-6 components as indicated in TABLE 1 above. Examples 1-6 included 1 wt-%, 2 wt-%, 5 wt-%, 10 wt-%, 20 wt-%, and 30 wt-% of tBA, respectively, based on total weight of monomers.
- Examples 7-9 were 2-stage latexes prepared according to the Latex Preparation Procedure B for a two-stage latex, using the Example 7-9 components as indicated in TABLE 2 above.
- Example 7 included 30 wt-% of tBA in monomer emulsion 1 and 10 wt-% of tBA in monomer emulsion 2, based on total weight of monomers.
- Example 8 included 30 wt-% of tBA in monomer emulsion 1 and 20 wt-% of tBA in monomer emulsion 2, based on total weight of monomers.
- Example 9 included 30 wt-% of tBA in monomer emulsion 1 and 32 wt-% of tBA in monomer emulsion 2, based on total weight of monomers.
- Example 10 was a powerfeed latex prepared according to the Latex Preparation Procedure C for a powerfeed latex, using the Example 10 components (same as Example 4 components) as indicated in TABLE 1 above.
- Example 10 included 10 wt-% of tBA based on total weight of monomers.
- Example 11-14 were 2-stage latexes prepared according to the Latex Preparation Procedure A for a two-stage latex, using the Example 11-14 components as indicated in TABLE 1 above.
- Example 11 included 10 wt-% of iso-bomyl acrylate based on total weight of monomers.
- Example 12 included 10 wt-% of cyclohexyl acrylate based on total weight of monomers.
- Example 13 included 10 wt-% of iso-butyl acrylate based on total weight of monomers.
- Example 14 included 10 wt-% of t-butyl methacrylate based on total weight of monomers.
- COMPARATIVE EXAMPLE 15 included 10 wt-% of iso-bomyl acrylate based on total weight of monomers.
- Example 12 included 10 wt-% of cyclohexyl acrylate based on total weight of monomers.
- Example 13 included 10 wt-% of iso-butyl
- Example 15 was a 2-stage latex prepared according to the Latex Preparation Procedure A for a two-stage latex, using the Example 15 components as indicated in TABLE 1 above.
- Example 16 included 5 wt-% of tert-butyl acrylate based on total weight of monomers.
- Example 17 included 10 wt-% of tert-butyl acrylate based on total weight of monomers.
- Example 1 Primer labelled “Example 1 Primer,” “Example 2 Primer,” etc. made with the respective Example latex above) and used for further testing.
- a flat primer formula was prepared by adding a pigment grind to a stirring Example latex, followed by the addition of let down ingredients.
- the pigment grind was prepared by sequentially adding, in the order listed and under constant mixing with a Cowles blade to maintain a vortex, 100 g of water, 5 g of ATTAGEL 50, 11 g of TAMOL 165A, 1 g of
- Example latex Let down ingredients were added, sequentially in the order listed, to the pigmented Example latex: EPS 9147 coalescent (see TABLE 4 for amounts), 1.5 g of NUOSEPT 498, 1.2 g of 4 % aqueous sodium nitrite, 112 g of water, 6 g of AQUAFLOW NHS-310, and ACRYSOL RM-8W (see TABLE 4 for amounts) to afford a flat primer formulation with a KU viscosity of 100 ⁇ 3.
- coalescent and rheology modifiers were adjusted for each Example latex to achieve coalescence below 50 °F and a KE1 viscosity range of 100 ⁇ 3.
- the levels used are listed in TABLE 4.
- a flat primer formula was prepared by adding a pigment grind to a stirring Example latex, followed by the addition of let down ingredients.
- the pigment grind was prepared by sequentially adding, in the order listed and under constant mixing with a Cowles blade to maintain a vortex, 100 g of water, 5 g of ATTAGEL 50, 11 g of TAMOL 165 A, 1 g of STRODEX NB-20, 3 g of AMP-95, 3.5 g of DREWPLUS L-475, 150 g of Ti-Pure R-706, 150 g of CAMEL-WHITE, and 2 g of water.
- the grind was added to 498 g of stirring Example latex in a quart-size can and the mixture was agitated for 20 minutes.
- Example latex Let down ingredients were added, sequentially in the order listed, to the pigmented Example latex: Texanol coalescent (see TABLE 6 for amounts), 1.5 g of NUOSEPT 498, 1.2 g of 4 % aqueous sodium nitrite, 112 g of water, 6 g of AQUAFLOW NHS-310, and ACRYSOL RM-8W (see TABLE 4 for amounts) to afford a flat primer formulation with a KU viscosity of 95 ⁇ 3.
- a flat paint formulation was prepared for use in the Stainblocking Test.
- a pigment grind was added to a stirring EPS 2741 latex, followed by the addition of let down ingredients.
- the pigment grind was prepared by sequentially adding, in the order listed and under constant mixing with a Cowles blade to maintain a vortex, 75 g of water, 6 g of TAMOL 165A, 2 g of SURFYNOL 104 A, 2 g of DREWPLUS L-475, 3 g of ATTAGEL 50, 3 g of NUOSEPT 498, 327 g of KRONOS 4311, 115 g of MINEX 4, and 60 g of DIAFIL 525.
- the grind was added to 537 g of EPS 2741 latex stirring in a quart-size can and the mixture was agitated for 20 minutes. Let down ingredients were added, sequentially in the order listed, to the pigmented EPS 2741 latex : 1 g of ammonium hydroxide, 11 g of EPS 9147 coalescent, 1 g of DREWPLUS L-475,
- Example primer formulations (Example Primer 1 - Example Primer 15) were applied over the stained areas using a 3 mil (0.0762 mm) square applicator (4 inch (101.6 mm) width, AP-B5356, Paul N. Gardner Company). The primer coat was allowed to dry for 6 hr at room temperature.
- a top coat of Flat Paint Formulation was applied over the dried primer coat using a 6 mil (0.1524 mm) square applicator (3 inch (0.0762 mm) width, AP-B5353, Paul N. Gardner Company). The top coat was allowed to dry for at least 1 day before colorimetric measurements were taken. The unstained sample was treated in the same way.
- each paint film was perpendicularly cross-cut using a 6-line, 2-millimiter (2 -mm) template with an OLFA Slimline Knife (available from OLFA Corp. in Rosemont, IL) with a fresh sharp blade.
- OLFA Slimline Knife available from OLFA Corp. in Rosemont, IL
- a 3-inch (76.2 mm) piece of ELCOMETER 99 adhesive test tape (available from Elcometer in Warren, MI) was applied to the cross-cut region and peeled off at 180° angle, and the resulting film removal was rated as specified in ASTM 3359 Method B.
- the adhesion results are shown in TABLE 6 below. The range of the adhesion test score is from 0 to 5, with higher numbers indicating higher adhesion.
- Each primer containing an Example Latex was applied as a 10 mil (0.254 mm) wet film on a 4 inch x 6 inch x 0.25 inch (101.6 mm x 152.4 mm x 6.35 mm) smooth glass plate and allowed to air dry for 24 hr at ambient temperature.
- the one-day hardness was recorded on a BYK Konig pendulum hardness tester using a 3° angle.
- a second hardness value was measured after air drying at ambient temperature for 7 days.
- the Konig hardness data, shown in TABLE 6, are averages of three repeat measurements. A higher Konig hardness value indicates higher hardness.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Stain-blocking polymers, as well as primers, kits, and methods that include such polymers, wherein the stain-blocking polymer is an emulsion latex polymer including interpolymerized monomers including: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I): RO-C(O)-CH=CH2 wherein: R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; and wherein the stain-blocking primer includes at least 10 wt-%, based on the total nonvolatile weight of the primer, of the emulsion latex polymer; an aqueous carrier; and optionally, one or more additives selected from a surfactant, thickener, coalescent, biocide, mildewcide, colorant, and combinations thereof.
Description
STAIN-BLOCKING POLYMERS, PRIMERS, KITS, AND METHODS
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application claims the benefit of U.S. Provisional Patent Application Serial No., 62/979,931, filed on February 21, 2020, which is incorporated herein by reference.
BACKGROUND
Aqueous coating compositions have found limited success in providing coatings with desirable properties for multiple substrates. Typically, transitioning from solvent-borne compositions to aqueous coating compositions, while providing environmental advantages, have resulted in sacrificing properties. The balance of coating performance attributes required for a coating composition to be suitable for use on a variety of substrates is not easily achieved with aqueous coating compositions.
Accordingly, aqueous coating compositions have found limited success in providing coatings with desirable properties for forming primers, especially those with stain-blocking ability.
Stain-blocking primers (i.e., coating compositions) are applied to the surfaces of substrates, including uncoated surfaces or previously coated substrates. These coatings promote adhesion and also serve as a barrier coating to underlying polar or non-polar staining agents. Substrates frequently contain soluble or mobile staining agents. Given the nature of water-based coatings, the staining agents often leach from the substrate into and/or through the coating, causing surface discoloration of the coating. For example, tannins contained in woods such as redwood, cedar, elm, merbau, and mahogany can leach from the substrate into the coating, causing tannin staining, which appears as discoloration on the surface of the coating. The visual appearance of localized stains or discoloration also can be manifested from extractives of previously coated substrates due to substrate exposure to water or humidity spots. In addition, salts contained in cementitious substrates often cause efflorescence, which is a staining caused by the migration of the salt from the substrate to the paint coating, where it appears as white deposits. Staining of the substrate, and of coatings previously applied to the substrate, can also
be caused by sources external to the substrate. For example, cigarette smoke causes nicotine staining, which discolors light colored coatings; inks from pens cause marker stains on the substrate. Each of these types of staining is highly undesirable in coatings.
What is needed in the art are aqueous coating compositions that function as primers having improved stain-blocking performance.
SUMMARY OF THE DISCLOSURE
The present disclosure provides stain-blocking polymers, as well as primers, kits, and methods that include such stain-blocking polymers, wherein the stain-blocking polymer is an emulsion latex polymer.
In one embodiment, a stain-blocking primer is provided that includes: at least 10 wt-%, based on the total nonvolatile weight of the primer, of an emulsion latex polymer including interpolymerized monomers including: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (in certain embodiments, and R has 20 or fewer carbon atoms); optionally, one or more (meth)acrylate monomers (i.e., acrylate or methacrylate monomers) selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; an aqueous carrier; and optionally, one or more additives selected from a surfactant, thickener, coalescent, biocide, mildewcide, colorant (e.g., inorganic pigment), and combinations thereof.
In another embodiment, a stain-blocking polymer is provided that includes: an emulsion latex polymer comprising interpolymerized monomers including: at least 1 wt-% of one or more acrylic acid ester monomers of Formula (I):
RO-C(O)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom (in certain embodiments, R has 20 or fewer carbon atoms); at least 10 wt-% of one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; and at least 1 wt-% styrene; wherein the weight percentages are based on the total weight of the interpolymerized monomers; wherein a hardened coating formed from the stain-blocking polymer has one or more of the following properties:
a stain-blocking performance, based on the Stainblocking Test described in the Examples Section (based on ASTM D7514-14), characterized by a DE value of: at most 20, preferably at most 18, for a black water-washable marker (e.g., Marks a Lot Black); and/or at most 16 for a blue water- washable marker (e.g., Window Marker Blue); and/or at most 15, preferably at most 12, for a green water- washable marker (e.g., Window Marker Green); an adhesion performance of at least 2 based on the ASTM 3359 Cross-cut Adhesion Test described in the Examples Section; and a pendulum hardness of at least 4 based on the Konig Pendulum Hardness Test described in the Examples Section.
In another embodiment, a stained substrate having a stain-blocking polymer coated thereon is provided, wherein the stain-blocking polymer is an emulsion latex polymer including interpolymerized monomers including: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (in certain embodiments, R has 20 or fewer carbon atoms); optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
In another embodiment, is a kit for making a stain-blocking primer that includes: an emulsion latex polymer including interpolymerized monomers including: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (in certain embodiments, R has 20 or fewer carbon atoms); optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; and instructions for forming a stain-blocking primer, wherein a coating formed from the primer has a stain-blocking performance, based on the Stain-blocking Test described in the Examples Section (based on ASTM D7514-14), characterized by a DE value of: at most 20, preferably at most 18, for a water-washable black marker (e.g., Marks a Lot Black); or at most 16 for a water-washable blue marker (e.g., Window
Marker Blue); or at most 15, preferably at most 12, for a water-washable green marker (e.g., Window Marker Green). In certain embodiments, at least one of these colored marker values (black, blue, or green) is met. In certain preferred embodiments, two of these three colored marker (black, blue, or green) values are met. In certain more preferred embodiments, all three colored marker (black, blue, or green) values are met.
In another embodiment, a method is formed that includes: causing a stain-blocking polymer to be applied to a stained substrate, wherein the stain-blocking polymer is an emulsion latex polymer including interpolymerized monomers including: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(O)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (in certain embodiments, R has 20 or fewer carbon atoms); optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
The terms “polymer” and “polymeric material” include, but are not limited to, organic homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, etc., and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible geometrical configurations of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and atactic symmetries.
The term “stain” as used herein includes any mark, blemish, discoloration, or any deposit, whether or not visible or readily apparent to the naked eye. The term “stain” thus includes marks caused by inks, crayons, lipstick, grease pencils, smoke residue, tannins, water extracts, and the like. These stains may be found on residential or commercial walls as graffiti, markings from pens or color markers, on or native to wooden substrates, on wood-composite substrates, on concrete substrates, on paper substrates (such as wail board coverings), and on other substrates that are normally painted with one or more liquid coatings.
The term “stain-blocking” as used herein means binding, blocking or masking a stain where it cannot be seen, or is substantially less visible, once one or more liquid coatings are applied and dried, or in those cases where the stain is not visible or only slightly visible, that the stain cannot migrate through the one or more subsequently applied and dried liquid coatings.
This is in contrast to a polymer or primer that is “stain-proof’ or ‘'stain-resistant” or “stain- repelling.”
Herein, the term “comprises” and variations thereof do not have a limiting meaning where these terms appear in the description and claims. Such terms will be understood to imply the inclusion of a stated step or element or group of steps or elements but not the exclusion of any other step or element or group of steps or elements. By “consisting of’ is meant including, and limited to, whatever follows the phrase “consisting of.” Thus, the phrase “consisting of’ indicates that the listed elements are required or mandatory, and that no other elements may be present. By “consisting essentially of’ is meant including any elements listed after the phrase, and limited to other elements that do not interfere with or contribute to the activity or action specified in the disclosure for the listed elements. Thus, the phrase “consisting essentially of’ indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present depending upon whether or not they materially affect the activity or action of the listed elements. Any of the elements or combinations of elements that are recited in this specification in open-ended language (e.g., comprise and derivatives thereof), are considered to additionally be recited in closed-ended language (e.g., consist and derivatives thereof) and in partially closed-ended language (e.g., consist essentially, and derivatives thereof).
The words “preferred” and “preferably” refer to embodiments of the disclosure that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other claims are not useful, and is not intended to exclude other embodiments from the scope of the disclosure.
In this application, terms such as “a,” “an,” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terms “a,” “an,” and “the” are used interchangeably with the term “at least one.” The phrases “at least one of’ and “comprises at least one of’ followed by a list refers to any one of the items in the list and any combination of two or more items in the list.
As used herein, the term “or” is generally employed in its usual sense including “and/or” unless the content clearly dictates otherwise.
The term “and/or” means one or all of the listed elements or a combination of any two or more of the listed elements.
Also herein, all numbers are assumed to be modified by the term “about” and in certain
embodiments, preferably, by the term “exactly.” As used herein in connection with a measured quantity, the term “about” refers to that variation in the measured quantity as would be expected by the skilled artisan making the measurement and exercising a level of care commensurate with the objective of the measurement and the precision of the measuring equipment used. Herein, “up to” a number (e.g., up to 50) includes the number (e.g., 50).
Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range as well as the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.) and any sub-ranges (e.g., 1 to 5 includes 1 to 4, 1 to 3, 2 to 4, etc.).
As used herein, the term “room temperature” refers to a temperature of 20 °C to 25 °C.
The term “in the range” or “within a range” (and similar statements) includes the endpoints of the stated range.
Reference throughout this specification to “one embodiment,” “an embodiment,”
“certain embodiments,” or “some embodiments,” etc., means that a particular feature, configuration, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of such phrases in various places throughout this specification are not necessarily referring to the same embodiment of the disclosure. Furthermore, the particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.
The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples may be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list. Thus, the scope of the present disclosure should not be limited to the specific illustrative structures described herein, but rather extends at least to the structures described by the language of the claims, and the equivalents of those structures. Any of the elements that are positively recited in this specification as alternatives may be explicitly included in the claims or excluded from the claims, in any combination as desired. Although various theories and possible mechanisms may have been discussed herein, in no event should such discussions serve to limit the claimable subject matter.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
The present disclosure provides stain-blocking polymers, as well as primers, kits, and methods that include such stain-blocking polymers, wherein the stain-blocking polymer is an emulsion latex polymer.
In one embodiment, a stain-blocking primer is provided. As used herein, a primer is a coating composition that forms a continuous coating (e.g., by rolling, brushing, spraying) on a substrate such as wood (e.g., redwood, cedar, elm, merbau, and mahogany), metal (e.g., steel), etc., which adheres well and is sandable when dry. Typically, a primer is used between a substrate, whether previously coated or not, and a topcoat such as a paint.
Herein, the primer is used to hide or block a staining agent in or on a substrate (i.e., a stained substrate) from showing through the topcoat. That is, the primer of the present disclosure acts as a barrier coating to a variety of underlying stairsing agents (whether polar or non-polar, hydrophilic or hydrophobic), such as tannins, inks, crayons, lipstick, grease pencils, smoke residue, water extracts, and the like, which can leached out of the underlying substrate. 'This is in contrast to surface staining and snail trails that result from a component (e.g., surfactant) leaching out of the topcoat.
Thus, the present disclosure also provides a stained substrate (i.e., a substrate such as wood containing a staining agent, such as tannins, inks, etc.) having a stain-blocking polymer, which may be included in a stain-blocking primer, coated thereon. The substrate may include a metal, wood, wood composite, concrete, paper (such as wail board coverings), and other such substrates that are normally painted with one or more liquid coatings. In some embodiments, the substrate can be a primed surface and even a previously painted surface.
The primers of the present disclosure are aqueous coating compositions, preferably have a viscosity of 60-120 units measured by Krebs Viscometer at room temperature (suitable for spray, roll, or brush).
A hardened coating (i.e., dry film) formed from a latex polymer described herein (or aqueous composition in the form of a primer including a latex polymer described herein) on a substrate surface (e.g., a wood or metal surface), has one or more of the following properties: a stain-blocking performance, based on the Stainblocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a water-washable black marker (e.g., Marks a Lot Black); and/or at most 16 for a water-washable blue marker (e.g., Window Marker Blue); and/or at most 15, preferably at most 12, for a water-washable green marker (e.g., Window Marker Green) (or in certain embodiments, such as for single-stage latex polymers, the DE
value is: at most 14 for black water-washable marker; at most 7 for a blue water-washable marker; and/or at most 8 for a green water-washable marker); an adhesion performance of at least 2 based on the ASTM 3359 Cross-cut Adhesion Test described in the Examples Section (using a coating thickness of 3 mils (0.0762 mm) wet film on cedar wood or dull matte steel; and a pendulum hardness (which demonstrates sandability) of at least 4 based on the Konig Pendulum Hardness Test described in the Examples Section (using a coating thickness of 10 mil (0.254 mm) wet film on a smooth glass plate and allowed to air dry for 24 hours (in certain embodiments, for 7 days) at ambient temperature using a BYK Konig pendulum hardness tester at a 3° angle).
In certain embodiments, at least one of these colored marker values (black, blue, or green) is met by a hardened coating. In certain preferred embodiments, two of these three colored marker (black, blue, or green) values are met. In certain more preferred embodiments, all three colored marker (black, blue, or green) values are met.
Preferably, a hardened coating of the present disclosure includes all of these characteristics - stain-blocking performance, adhesion performance, and pendulum hardness.
For these tests, the primer formulation is a flat primer formulation that includes the emulsion latex polymer of the present disclosure, a pigment grind, a coalescent, a biocide (1,2- benzisothiazolin-3-one), sodium nitrite, rheology modifiers (i.e., thickeners such as hydrophobically modified polyether and hydrophobically modified ethylene oxide urethane) used in amounts to achieve coalescence below 50 °F and a KU viscosity range of 100 ± 3.
The emulsion latex polymer (i.e., emulsion polymerized latex polymer) includes interpolymerized monomers including: at least 1 wt-%, or at least 2 wt-% (in certain embodiments, at least 1 wt-% to less than 20 wt-%), based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
In certain embodiments, the acrylic acid ester monomers of Formula (I) have a homopolymer glass transition temperature (Tg) of less than 1 10 °C, or less than 50 € In
certain embodiments, the acrylic acid ester monomers of Formula (I) have a homopolymer Tg of at least 20 °C, or at least 30 °C.
In certain embodiments, a mixture of the acrylic acid ester monomers of Formula (I) are used to form the emulsion latex polymer.
In certain embodiments, R of Formula (I) is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof (e.g., a cyclohexane group with a t-butyl substituent).
In certain embodiments, R of Formula (I) has no more than 20 carbon atoms (i.e., 20 or fewer carbon atoms), no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms.
In certain embodiments, R of Formula (I) is a branched alkyl group having a tertiary carbon atom. In certain embodiments, R of Formula (I) is a branched alkyl group of 4 to 10 carbon atoms having a tertiary carbon atom.
In certain embodiments, the one or more monomers of Formula (I) are selected from isobornyl acrylate, cyclohexyl acrylate, t-butyl acrylate, and a mixture thereof. In certain embodiments, the one or more monomers of Formula (I) comprise t-butyl acrylate.
In certain embodiments, the emulsion latex polymer includes at least 1 wt-%, at least 2 wt-%, at least 5 wt-%, of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers. In certain embodiments, the emulsion latex polymer includes less than 20 wt-%, up to 15 wt-% (including 15 wt-%), or up to 10 wt-%, of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
In certain embodiments, the interpolymerized monomers of the emulsion latex polymer include one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof. In certain embodiments, the emulsion latex polymer includes at least 10 wt-%, at least 20 wt-%, at least 30 wt-%, at least 40 wt-%, at least 50 wt-%, at least 60 wt-%, at least 70 wt-%, at least 75 wt-%, at least 80 wt-%, at least 83 wt-%, at least 84 wt-%, least 85 wt-%, or at least 90 wt-%, of these one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers. In certain embodiments, the emulsion latex polymer includes up to 99 wt-%, up to 98 wt-%, or up to 95 wt-%, of these one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers.
In certain embodiments, if the interpolymerized monomers of the emulsion latex polymer include n-butyl methacrylate (n-BMA), it is present in an amount of no more than 12 wt-%, based on the total weight of the interpolymerized monomers. While not being bound by theory, it is believed that n-BMA negates the benefits of the monomer of Formula (I).
In certain embodiments, the interpolymerized monomers of the emulsion latex polymer include one or more wet adhesion monomers. Examples of wet adhesion monomers include N- (2-methacryloyloxyethyl) ethylene urea (available as a 50 % aqueous solution under the tradename SIPOMER WAM E W 50, as a 50 % methyl methacrylate solution under the tradename SIPOMER WAM E MMA50, or as a 25 % methyl methacrylate solution under the tradename SIPOMER WAM E MMA25, all from Solvay), l-(2-((3-(allyloxy)-2- hydroxyproypl)amino)ethyl)imidazolidine-2-one (available as a 90 wt-% aqueous solution under the tradename SIPOMER WAM from Solvay), N-(2-methacryloyloxyethyl) ethylene urea (available as a 50 % aqueous solution under the tradename VISIOMER MEEU 50 W from Evonik Industries AG), and combinations thereof. In certain embodiments, the emulsion latex polymer includes at least 0.2 wt-% of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers. In certain embodiments, the emulsion latex polymer includes up to 2.0 wt-%, or up to 1.0 wt-%, of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
In certain embodiments, the interpolymerized monomers of the emulsion latex polymer include styrene. In certain embodiments, the emulsion latex polymer includes at least 1 wt-%, at least 5 wt-%, at least 10 wt-%, or at least 15 wt-%, styrene, based on the total weight of the interpolymerized monomers. In certain embodiments, the emulsion latex polymer includes up to 75 wt-%, or up to 50 wt-% styrene, based on the total weight of the interpolymerized monomers.
In certain embodiments, a stain-blocking polymer is an emulsion latex polymer that includes interpolymerized monomers including: at least 1 wt-%, or at least 2 wt-%, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom (in certain embodiments, R has 20 or fewer carbon atoms); at least 10 wt-% of one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; and at least 1 wt-%, at least 5 wt-%, at least 10 wt-%, or at least 15 wt-%,
styrene; wherein the weight percentages are based on the total weight of the interpolymerized monomers.
In certain embodiments, the latex polymer is a single stage latex polymer. In certain embodiments, the latex polymer is a multistage latex polymer, such as a gradient Tg latex polymer or a core-shell(s) latex polymer. In certain embodiments, the emulsion latex polymer is a two- or more-stage emulsion latex polymer (e.g., resulting from a power feed process).
In this context, the term “multistage” when used with respect to a latex polymer means the polymer was made using discrete charges of two or more monomers, made using a varying (e.g., continuously varying) charge of two or more monomers, or made using a combination of both discrete charges and varying charges of two or more monomers. A multistage polymer is distinct from a single stage polymer made using one type of monomer blend with distinct polymer seed particles. Frequently, a multistage polymer consists of polymer stages with different Tg’s, where the higher Tg stages are considered the hard stages and the lower Tg stages are considered the soft stages.
Usually, a multistage latex will not exhibit a single Tg inflection point as measured by differential scanning calorimetry (DSC). For example, a DSC curve for a multistage latex made using discrete charges of two or more monomers may exhibit two or more Tg inflection points. Also, a DSC curve for a multistage latex made using a continuously varied charge of two or more monomers may exhibit no Tg inflection points. By way of further explanation, a DSC curve for a single stage latex made using a single monomer charge or a non-varying charge of two monomers may exhibit only a single Tg inflection point. Occasionally when only one Tg inflection point is observed it may be difficult to determine whether the latex represents a multistage latex. In such cases a lower Tg inflection point may sometimes be detected on closer inspection, or the synthetic scheme used to make the latex may be examined to determine whether or not a multistage latex would be expected to be produced.
In certain embodiments, latex polymers (whether single stage or multistage) are typically made using seed particles as a nucleating agent for polymerization. Such seed particles may be in the form of inorganic particulate seed (e.g., clay or glass particles), preformed particulate polymer seed (latex or non-latex polymer seed), or particulate seed polymer formed in situ. Polymer seed can be an emulsion polymerized polymer seed, but does not encompass polymeric surfactant. In certain embodiments, seed particles are used in an amount of no more than 10 wt-%, or no more than 5 wt-%, based on latex polymer solids in the final latex.
Herein, whether inorganic particulate seed, preformed particulate polymer seed, or particulate seed polymer formed in situ , such seed particles will not be deemed to provide a stage of a multistage polymer or to provide a basis for designating a single stage polymer made using such seed polymer as a multistage polymer.
In certain embodiments, the one or more monomers of Formula (I) is present in a hard stage of the emulsion latex polymer.
Latex polymers described herein may or may not have a glass transition temperature that is measurable. As used herein, the term “glass transition temperature” or “Tg” refers to the temperature at which an amorphous, solid material undergoes a reversible transition to a molten, rubber-like state. The Tg may be measured using DSC, or calculated using the Fox equation. Application of the Fox equation to estimate the Tg of polymers is well known to one skilled in the art.
In certain embodiments, the latex polymer has a measured Tg, as measured by DSC. Such Tg may be measured at the beginning, mid-point, or end of polymerization. In certain embodiments, however, the latex polymer may have no clearly measurable Tg. Thus, a latex polymer may be referred to as a “gradient Tg polymer,” it may not have a clearly measurable Tg using DSC.
In certain embodiments, the latex polymer is a multistage polymer having at least one measured Tg and at least one Fox Tg (which are not alternative representations of the same glass transition). Herein, “Fox Tg” and “calculated Tg” and “calculated Fox Tg” are used interchangeably.
The Tg of a particular stage, or combination of stages, can be estimated (i.e., calculated) using the Fox equation. For example, for a polymer made from two monomers in a particular stage, the theoretical Tg may be calculated using the Fox equation as follows:
1/Tg = Wa/Tga + Wb/Tgb wherein:
Tga and Tgb are the respective glass transition temperatures in Kelvin of homopolymers made from monomers “a” and “b”; and
Wa and Wb are the respective weight fractions of polymers “a” and “b”.
When additional monomer feeds “c” and “d” and so on are employed, additional fractions Wc/Tgc, Wd/Tgd and so on are added to the right-hand side of the above equation. Unless
indicated otherwise, the “calculated” stage or copolymer Tg’s referenced herein are calculated using the Fox equation. Also, the calculation is based on all of the monomers that are reacted together to form a stage, and not upon merely a portion of such monomers.
The value of Tg of the monomers used to estimate the polymer Tg are based on literature values. Typically, there is some variation of the Tg values of the homopolymers of monomers listed in such literature. The difference arises from the test method used to measure the Tg. The differences also arise from influence of comonomers polymerized together. For the purposes of this disclosure, the values used for the homopolymer Tg of certain monomers, particularly monomers used in the examples are listed herein (e.g., in the Materials Table in the Examples Section). Alternatively, the method of determining the Tg of a homopolymer can be determined using the DSC procedure described in the Examples Section, particularly if the literature values are significantly different (e.g., the literature values vary by at least 15 °C). If the literature values vary by less than 15 °C, then use the lower literature value.
In certain embodiments, the multistage polymer is a gradient latex polymer (i.e., gradient Tg latex polymer). Typically, a gradient Tg latex polymer will have a DSC (differential scanning calorimetry) curve that exhibits no Tg inflection points, and could be said to have an essentially infinite number of Tg stages. For example, one may start with a high Tg monomer feed and then at a certain point in the polymerization start to feed a low Tg soft stage monomer composition into the high Tg hard stage monomer feed. The resulting multistage latex polymer will have a gradient Tg from high to low. In other embodiments, it may be favorable to feed a high Tg hard stage monomer composition into a low Tg soft stage monomer composition.
In some embodiments, a multistage latex described herein will contain at least 10 wt-%, at least 20 wt-%, or at least 25 wt-%, of high Tg or hard stage monomers. In some embodiments, a multistage latex described herein will include up to 50 wt-%, up to 40 wt-%, or up to 35 wt-%, of high Tg or hard stage monomers. In some embodiments, a multistage latex described herein will include at least 50 wt-%, at least 60 wt-%, or at least 65 wt-%, of low Tg or soft stage monomers. In some embodiments, a multistage latex described herein will include up to 90 wt-%, up to 80 wt-%, or up to 75 wt-%, of low Tg or soft stage monomers.
In certain aspects, a multistage latex described herein preferably includes at least two polymer portions, e.g., a first stage and a second stage, with different Tg values, where the difference in Tg (ATg) is at least 35 °C, at least 50 °C, or at least 60 °C, or at least about 65 °C. In certain aspects, the ATg is less than 200 °C, less than 150 °C, or less than 100 °C.
A gradient Tg polymer may also be used in conjunction with multiple Tg polymers. For gradient Tg latex polymers, a Tg differential may be determined by using the Fox equation to calculate the theoretical Tg for a copolymer made from the monomer feed at the start of polymerization and comparing the result to the calculated theoretical Tg for a copolymer made from the second feed. Such gradient Tg can result from the second monomer feed being combined into the first monomer feed to form a gradient architecture, or ultimately result from two monomer feeds being combined at differential rates (e.g., the rate of one monomer feed increases while the rate of a second monomer feed decreases).
In certain embodiments, there may be a discrete measurable Tg of an otherwise gradient Tg latex polymer, such discreet Tg is typically corresponding to the polymer resulting from polymerization of the first monomer feed, or to a mixture of the first monomer feed and a small amount of the second monomer feed.
In certain embodiments, the emulsion latex polymer of the present disclosure has at least one Fox Equation (theoretical calculated) Tg of 10 °C to 45 °C (in certain embodiments, 25 °C to 45 °C, or 10 °C to 35 °C, and in certain embodiments, the Fox Equation Tg is 35 °C). In certain embodiments, the emulsion latex polymer of the present disclosure has at least one Fox Equation (theoretical calculated) Tg of 45 °C to -10 °C (in certain embodiments, -45 °C to -22 °C, and in certain embodiments, the Fox Equation Tg is -32 °C, or -22 °C).
In certain embodiments, the emulsion latex polymer of the present disclosure has an acid number of up to 30 (per kg OH). In certain embodiments, the emulsion latex polymer of the present disclosure has an acid number of at least 5 (per kg OH).
In certain embodiments, the emulsion latex polymer of the present disclosure includes latex particles having a volume average particle size of at least 50 nm, or at least 60 nm, or at least 70 nm. In certain embodiments, the emulsion latex polymer of the present disclosure includes latex particles having a volume average particle size of up to 150 nm, or up to 130 nm.
Latex polymers may be made from the described monomers using a variety of techniques known to one skilled in the art. Typically, such polymers are made from an aqueous emulsion that includes one or more monomers as described herein, preferably using a multistage feed process. In certain embodiments, after the latex polymer is formed in water, more water may be added to obtain a desired solids level.
Such multistage feed processes (e.g., powerfeed methods) for producing emulsion copolymers are well-known. They enable one to constantly vary the composition of monomers being polymerized to produce copolymers having a variety (e.g., gradient) of desired properties.
For example, in certain embodiments a gradient is achieved by changing the feed rate of a second monomer mixture into a first monomer mixture.
There is no required order of mixing monomers or required combination of monomers. Furthermore, there is no requirements regarding which monomers may be mixed with which monomers. In certain preferred embodiments, however, the one or more monomers of Formula (I) are added in the first stage of a multistage process.
In certain embodiments, the latex polymer is formed from components that also include one or more radical transfer agents (i.e., chain transfer agents), although such agent is not required. In certain embodiments, the radical transfer agents are selected from dodecanethiol, mercaptopropionic acid, isooctyl thioglycolate, butyl mercapto propionate, and combinations thereof. In certain embodiments, the one or more radical transfer agents are present in an amount of at least 0.1 wt-%, based on the total weight of monomers, although typically, no radical transfer agent is needed. If used, in certain embodiments, the one or more radical transfer agents are present in an amount of up to 0.5 wt-%, based on the total weight of monomers.
In certain embodiments, the stain-blocking primer includes at least 10 wt-%, or at least 15 wt-% of a stain-blocking polymer, which is an emulsion latex polymer, based on the total nonvolatile weight of the primer. In certain embodiments, the stain-blocking primer includes up to 50 wt-%, or up to 30 wt-% of a stain-blocking polymer, which is an emulsion latex polymer, based on the total nonvolatile weight of the primer.
The primers of the present disclosure also include an aqueous carrier (e.g., water and one or more optional organic solvents), and optionally, one or more additives selected from a surfactant, thickener, biocide, mildewcide, colorant (e.g., inorganic pigment), and combinations thereof.
In certain embodiments, the stain-blocking primer includes water in an amount of at least 50 wt-%, based on the total weight of the primer. In certain embodiments, the stain blocking primer includes water in an amount of up to 90 wt-%, based on the total weight of the primer.
In certain embodiments, the primers of the present disclosure include a substantial amount of water and may further include one or more optional organic solvents. Such primers are referred to herein as aqueous coating compositions. In some embodiments, water constitutes greater than 20 wt-%, or greater than 35 wt-%, or greater than 50 wt-%, of the total weight of
the aqueous carrier. In some embodiments, water constitutes 100 wt-% or less, less than 95 wt- %, or less than 90 wt-%, of the total weight of the aqueous carrier.
Suitable optional organic solvents include ketones, glycol ethers, esters, alcohols, aromatics, and combinations thereof. Examples of such solvents include carbitol, butyl carbitol, butylcellosolve, propylene glycol monomethyl ether, dibasic ester, ethyl carbitol, diisobutyl ketone, dipropylene glycol n-butyl ether (DPNB), and 2, 2, 4-trimethyl- 1, 3 -pentanediol monoisobutyrate (available under the tradename TEXANOL), and mixtures thereof.
In certain embodiments, the primer includes one or more additives selected from a surfactant (e.g., fluorinated surfactants, ethylenically unsaturated surfactants), thickener (e.g., to allow the polymer to coat out on a substrate surface), coalescent (e.g., a glycol ether such as EASTMAN EP, EASTMAN DM, EASTMAN DE, EASTMAN DP, EASTMAN DB and EASTMAN PM from Eastman Chemical Co., an ester alcohol such as TEXANOL ester alcohol from Eastman Chemical Co., or a low VOC coalescent compound such as is described in U.S. Patent No. 6,762,230 B2), biocide, mildewcide, colorant (e.g., inorganic pigment such as CaC03, T1O2), and mixtures thereof. In certain embodiments, the primer includes one or more additives for wet hide capability (e.g., titanium dioxide particles, opaque polymeric spheres, and kaolin clay platelets). Such additives may be added during polymerization or after polymerization.
In certain embodiments, one or more additives may be present in an amount of at least 0.1 wt-%, at least 0.5 wt-%, or at least 1 wt-%, based on the total weight of polymer solids. In certain embodiments, one or more additives may be present in an amount of up to 5 wt-%, up to 4 wt-%, up to 3 wt-%, up to 2 wt-%, or up to 1 wt-%, based on the total weight of polymer solids.
In certain embodiments, primers of the present disclosure are low VOC primers. By controlling the type of monomers selected for the feed process, a multistage latex suitable for low VOC, primers may be formed. The phrase “low VOC” when used with respect to a primer means that the primer contains less than 10 weight percent (wt-%) volatile organic compounds, more preferably less than 7 wt-% volatile organic compounds, and most preferably less than 4 wt-% volatile organic compounds, based upon the total primer weight. The term “volatile organic compound” (“VOC”), as defined by the Environmental Protection Agency (EPA) in 40 C.F.R. 51.100(s), refers to any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in 20 atmospheric photochemical reactions. Typically, volatile organic compounds
have a vapor pressure equal to or greater than 0.1 mm Hg. As used herein, “volatile organic compound content” (“VOC content”) is as measured by ASTM method D2369-90, refers to the weight of VOC per volume of the coating solids, and is reported, for example, as grams VOC per liter (g/L).
In certain embodiments, the primer is a clear (i.e., unpigmented) primer.
The present disclosure also provides a kit for making a stain-blocking primer. The kit includes an emulsion latex polymer described herein and instructions for forming a stainblocking primer as described herein. The emulsion latex polymer and the instructions are typically physically packaged together; however, the two do not need to be physically delivered together in a physical package to be a kit.
The present disclosure also provides a method (e.g., a method of blocking stains). The method includes causing a stain-blocking polymer as described herein, which may be in a primer) to be applied to a stained substrate (i.e., a substrate that has a stain or a staining agent therein or thereon). Herein, “causing” means applying the polymer (e.g., in an aqueous primer formulation) to the stained substrate, instructing it to be applied to the stained substrate, supplying it to a user to apply it to a stained substrate, or supplying it to a manufacturer to make a primer for use on a stained substrate.
Typically, the method also includes causing a primer that includes a stain-blocking polymer to be applied to a stained substrate, and drying or allowing the primer to harden to form a hardened stain-blocking coating and block the stain (i.e., form a barrier for the staining agent to show' through a topcoat).
The step of applying the aqueous coating composition may be any of a wide variety of coating techniques known to one skilled in the art.
The step of allowing a primer (i.e., aqueous composition) to harden and form a hardened coating may include exposing the primer to a wide variety of conditions known to one skilled in the art. Typically, such conditions include exposing the aqueous composition to a temperature of at least 10°C, and in certain embodiments up to 100°C, for a period of time of at least 60 minutes and up to 168 hours. For example, such conditions may include hardening (e.g., drying or curing) the primer at a temperature of at least 10°C for at least 168 hours. Alternatively, such conditions may include using a temperature of no more than (i.e., up to) 100°C for no more than (i.e., up to) 60 minutes. Such hardening may occur in one or more steps.
A coated (e.g., primed) stained substrate including a substrate surface having a hardened coating disposed thereon is provided by the present disclosure. Such coated stained substrate may be prepared by this method.
EXEMPLARY EMBODIMENTS
In certain embodiments (embodiment 1), a stain-blocking primer is provided that includes: at least 10 wt-%, based on the total nonvolatile weight of the primer, of an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-%, based on total weight of monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(O)-CH=CH2 wherein: R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; an aqueous carrier; and optionally, one or more additives selected from a surfactant, thickener, coalescent, biocide, mildewcide, colorant (e.g., inorganic pigment), and combinations thereof.
In certain embodiments (embodiment 2), a primer of embodiment 1 is provided wherein R of Formula (I) has no more than 20 carbon atoms, no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms. In certain embodiments (embodiment 3), a primer of embodiment 1 or 2), is provided wherein R of Formula (I) is a branched alkyl group having a tertiary carbon atom.
In certain embodiments (embodiment 4), a primer of any of the previous embodiments is provided wherein R of Formula (I) is a branched alkyl group of 4 to 10 carbon atoms having a tertiary carbon atom.
In certain embodiments (embodiment 5), a primer of any of the previous embodiments is provided wherein the monomer of Formula (I) has a homopolymer Tg of less than 110 °C, or less than 50 °C. In certain embodiments (embodiment 6), a primer of any of the previous embodiments is provided wherein the monomer of Formula (I) has a homopolymer Tg of at least 20 °C, or at least 30 °C,
In certain embodiments (embodiment 7), a primer of any of the previous embodiments is provided wherein the emulsion latex polymer comprises a mixture of monomers of Formula (I).
In certain embodiments (embodiment 8), a primer of any of the previous embodiments is provided wherein the one or more monomers of Formula (I) are selected from isobomyl
acrylate, cyclohexyl acrylate, t-butyl acrylate, and a mixture thereof. In certain embodiments (embodiment 9), a primer of embodiment 8 is provided wherein the one or more monomers of Formula (I) comprise t-butyl acrylate.
In certain embodiments (embodiment 10), a primer of any of the previous embodiments is provided wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of 10 °C to 45 °C (in certain embodiments, 25 °C to 45 °C, or 10 °C to 35 °C). In certain embodiments (embodiment 11), a primer of embodiment 10 is provided wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of -45 °C to -10 °C (in certain embodiments, -45 °C to -22 °C, -32 °C, or -22 °C).
In certain embodiments (embodiment 12), a primer of any of the previous embodiments is provided wherein the latex polymer has an acid number of up to 30 (per kg OH). In certain embodiments (embodiment 13), a primer of any of the previous embodiments is provided wherein the latex polymer has an acid number of at least 5 (per kg OH).
In certain embodiments (embodiment 14), a primer of any of the previous embodiments is provided wherein the latex polymer comprises latex particles having a volume average particle size of at least 50 nm, or at least 60 nm, or at least 70 nm. In certain embodiments (embodiment 15), a primer of any of the previous embodiments is provided wherein the latex polymer comprises latex particles having a volume average particle size of up to 150 nm, or up to 130 nm.
In certain embodiments (embodiment 16), a primer of any of the previous embodiments is provided comprising at least 15 wt-% of the emulsion latex polymer, based on the total nonvolatile weight of the primer. In certain embodiments (embodiment 17), a primer of any of the previous embodiments is provided comprising up to 50 wt-% of the emulsion latex polymer, based on the total nonvolatile weight of the primer. In certain embodiments (embodiment 18), a primer of embodiment 17 is provided comprising up to 30 wt-% of the emulsion latex polymer, based on the total nonvolatile weight of the primer.
In certain embodiments (embodiment 19), a primer of any of the previous embodiments is provided wherein the polymer is a two- or more- stage emulsion latex polymer (e.g., resulting from a power feed process). In certain embodiments (embodiment 20), a primer of embodiment 19 is provided wherein the monomer of Formula (I) is present in a hard stage of the emulsion latex polymer.
In certain embodiments (embodiment 21), a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise at least 2 wt-%, or at least 5 wt-
%, of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 22), a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise less than 20 wt-% (or up to 15 wt-%, or up to 10 wt-%) of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 23), a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate (n-BA and n-BMA), ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof. In certain embodiments (embodiment 24), a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise at least 10 wt-% (or at least 20 wt-%, at least 30 wt-%, at least 40 wt-%, at least 50 wt- %, at least 60 wt-%, at least 70 wt-%, at least 75 wt-%, at least 80 wt-%, at least 83 wt-%, at least 84 wt-%, at least 85 wt-%, or at least 90 wt-%) of one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 25), a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise up to 99 wt-% (or up to 98 wt-%, or up to 95 wt-%) of one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers. In certain embodiments, if the interpolymerized monomers of the emulsion latex polymer include n-butyl methacrylate (n-BMA), it is present in an amount of no more than 12 wt-%, based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 26), a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise styrene. In certain embodiments (embodiment 27), a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise at least 1 wt-% (or at least 5 wt-%, at least 10 wt-%, or at least 15 wt-%) styrene, based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 28), a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise up to 75 wt-% (or up to 50 wt-%) styrene, based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 29), a primer of any of the previous embodiments is provided wherein the interpolymerized monomers comprise one or more wet adhesion monomers (e.g., those selected from N-(2-methacryloyloxyethyl) ethylene urea, l-(2-((3- (allyloxy)-2-hydroxyproypl)amino)ethyl)imidazolidine-2-one, and combinations thereof). In
certain embodiments (embodiment 30), a primer of embodiment 29 is provided wherein the interpolymerized monomers comprise at least 0.2 wt-% of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 31), a primer of embodiment 29 or 30 is provided wherein the interpolymerized monomers comprise up to 2.0 wt-% (or up to 1.0 wt-%) of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 32), a primer of any of the previous embodiments is provided which is a clear (i.e., unpigmented) primer.
In certain embodiments (embodiment 33), a primer of any of the previous embodiments is provided further comprising one or more additives selected from a surfactant, thickener, coalescent, biocide, mildewcide, colorant (e.g., inorganic pigment), and mixtures thereof. In certain embodiments (embodiment 34), a primer of embodiment 33 is provided comprising an inorganic pigment (e.g., CaCCb, TiCk). In certain embodiments (embodiment 35), a primer of embodiment 33 or 34 is provided comprising a thickener (e.g., to allow the polymer to coat out on a substrate surface). In certain embodiments (embodiment 36), a primer of any of the previous embodiments is provided comprising one or more additives for wet hide capability (e.g., titanium dioxide particles, opaque polymeric spheres, and kaolin clay platelets).
In certain embodiments (embodiment 37), a primer of any of the previous embodiments is provided having a viscosity of 60-120 units measured by Krebs Viscometer at room temperature (suitable for spray, roll, or brush).
In certain embodiments (embodiment 38), a primer of any of the previous embodiments is provided wherein a hardened coating formed from the primer has a stain-blocking performance, based on the Stain-blocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a black water-washable marker; at most 16 for a blue water- washable marker; and/or at most 15, preferably at most 12 for a green water-washable marker. In certain embodiments, such as in single-stage latex polymers, the DE value is: at most 14 for black water-washable marker; at most 7 for a blue water-washable marker; and/or at most 8 for a green water- washable marker. In certain embodiments (embodiment 39), a primer of any of the previous embodiments is provided wherein a hardened coating formed from the primer has an adhesion performance of at least 2 based on the ASTM 3359 Cross-cut Adhesion Test. In certain embodiments (embodiment 40), a primer of any of the previous embodiments is provided wherein a hardened coating formed from the primer has a pendulum hardness of at least 4 based on the Konig Pendulum Hardness Test.
In certain embodiments (embodiment 41), a primer of any of the previous embodiments is provided which is a low VOC primer (i.e., contains less than 10 wt-% volatile organic compounds, based on the total weight of the primer).
In certain embodiments (embodiment 42), a primer of embodiment 41 is provided which includes less than 7 wt-%, or less than 4 wt-%, volatile organic compounds, based on the total weight of the primer).
In certain embodiments (embodiment 43), a stain-blocking polymer is provided that includes: an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-% of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom; at least 10 wt-% of one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; and at least 1 wt-% styrene; wherein the weight percentages are based on the total weight of the interpolymerized monomers; wherein a hardened coating formed from the stain-blocking polymer has one or more of the following properties: a stain-blocking performance, based on the Stain-blocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a black water- washable marker; at most 16 for a blue water-washable marker (or in certain embodiments, such as in single-stage latex polymers, the DE value is: at most 14 for black water-washable marker; at most 7 for a blue water- washable marker; and/or at most 8 for a green water- washable marker); at most 15, preferably at most 12, for a green water- washable marker; an adhesion performance of at least 2 based on the ASTM 3359 Cross-cut Adhesion Test; and a pendulum hardness of at least 4 based on the Konig Pendulum Hardness Test.
In certain embodiments (embodiment 44), a stain-blocking polymer of embodiment 43 is provided wherein R of Formula (I) has no more than 20 carbon atoms, no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms. In certain embodiments (embodiment 45), a stain blocking polymer of embodiment 43 or 44 is provided wherein R of Formula (I) is a branched alkyl group having a tertiary carbon atom. In certain embodiments (embodiment 46), a stain blocking polymer of embodiments 43 through 45 is provided wherein R of Formula (I) is a branched alkyl group of 4 to 10 carbon atoms having a tertiary carbon atom. In certain embodiments (embodiment 47), a stain-blocking polymer of embodiments 43 through 46 is provided wherein the monomer of Formula (I) has a homopolymer Tg of less than 110 °C, or
less than 50 °C. In certain embodiments (embodiment 48), a stain-blocking polymer of embodiments 43 through 47 is provided wherein the monomer of Formula (I) has a homopolymer Tg of at least 20 °C, or at least 30 °C.
In certain embodiments (embodiment 49), a stain-blocking polymer of embodiments 43 through 48 is provided wherein the emulsion latex polymer comprises a mixture of monomers of Formula (I).
In certain embodiments (embodiment 50), a stain-blocking polymer of embodiments 43 through 49 is provided wherein the one or more monomers of Formula (I) are selected from isobornyl acrylate, cyclohexyl acrylate, t-butyl acrylate, and a mixture thereof. In certain embodiments (embodiment 51), a stain-blocking polymer of embodiment 50 is provided wherein the one or more monomers of Formula (I) comprise t-butyl acrylate.
In certain embodiments (embodiment 52), a stain-blocking polymer of embodiments 43 through 51 is provided wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of 10 °C to 45 °C (in certain embodiments, 25 °C to 45 °C, or 10 °C to 35 °C).
In certain embodiments (embodiment 53), a stain-blocking polymer of embodiment 52 is provided wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of -45 °C to -10 °C (in certain embodiments, -45 °C to -22 °C, -32 °C, or -22 °C).
In certain embodiments (embodiment 54), a stain-blocking polymer of embodiments 43 through 53 is provided wherein the latex polymer has an acid number of up to 30 (per kg OH). In certain embodiments (embodiment 55), a stain-blocking polymer of embodiments 43 through 54 is provided wherein the latex polymer has an acid number of at least 5 (per kg OH).
In certain embodiments (embodiment 56), a stain-blocking polymer of embodiments 43 through 55 is provided wherein the latex polymer comprises latex particles having a volume average particle size of at least 50 nm, or at least 60 nm, or at least 70 nm. In certain embodiments (embodiment 57), a stain-blocking polymer of embodiments 43 through 56 is provided wherein the latex polymer comprises latex particles having a volume average particle size of up to 150 nm, or up to 130 nm.
In certain embodiments (embodiment 58), a stain-blocking polymer of embodiments 43 through 57 is provided wherein the polymer is a two- or more- stage emulsion latex polymer (e.g., resulting from a power feed process). In certain embodiments (embodiment 59), a stain blocking polymer of embodiment 58 is provided wherein the monomer of Formula (I) is present in a hard stage of the emulsion latex polymer.
In certain embodiments (embodiment 60), a stain-blocking polymer of embodiments 43 through 59 is provided wherein the interpolymerized monomers comprise at least 2 wt-%, or at least 5 wt-%, of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 61), a stain-blocking polymer of embodiments 43 through 60 is provided wherein the interpolymerized monomers comprise less than 20 wt-% (or up to 15 wt-%, or up to 10 wt-%) of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 62), a stain-blocking polymer of embodiments 43 through 61 is provided wherein the interpolymerized monomers comprise at least 75 wt-% (or least 80 wt-%, at least 83 wt-%, at least 84 wt-%, at least 85 wt-%, or at least 90 wt-%) of one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 63), a stain-blocking polymer of embodiments 43 through 62 is provided wherein the interpolymerized monomers comprise up to 99 wt-% (or up to 98 wt-%, or up to 95 wt-%) of one or more (meth)acrylate monomers (e.g., two or more (meth)acrylate monomers), based on the total weight of the interpolymerized monomers. In certain embodiments, if the interpolymerized monomers of the emulsion latex polymer include n-butyl methacrylate (n-BMA), it is present in an amount of no more than 12 wt-%, based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 64), a stain-blocking polymer of embodiments 43 through 63 is provided wherein the interpolymerized monomers comprise at least 5 wt-% (or at least 10 wt-%, or at least 15 wt-%) styrene, based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 65), a stain-blocking polymer of embodiments 43 through 64 is provided wherein the interpolymerized monomers comprise up to 75 wt-% (or up to 50 wt-%) styrene, based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 66), a stain-blocking polymer of embodiments 43 through 65 is provided wherein the interpolymerized monomers comprise one or more wet adhesion monomers (e.g., those selected from N-(2-methacryloyloxy ethyl) ethylene urea, l-(2- ((3-(allyloxy)-2-hydroxyproypl)amino)ethyl)imidazolidine-2-one, and combinations thereof).
In certain embodiments (embodiment 67), a stain-blocking polymer of embodiments 43 through 66 is provided wherein the interpolymerized monomers comprise at least 0.2 wt-% of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers. In
certain embodiments (embodiment 68), a stain-blocking polymer of embodiment 66 or 67 is provided wherein the interpolymerized monomers comprise up to 2.0 wt-% (or up to 1.0 wt-%) of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 69), a stained substrate is provided having a stainblocking primer of any of embodiments 1 through 42 coated thereon or a stain-blocking polymer of any of embodiments 43 through 68 coated thereon.
In certain embodiments (embodiment 70), a stained substrate is provided having a stainblocking polymer coated thereon, wherein the stain-blocking polymer is an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(O)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
In certain embodiments (embodiment 71), a stained substrate of embodiment 70 is provided wherein R of Formula (I) has no more than 20 carbon atoms, no more than 16 carbon atoms, no more than 12 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms. In certain embodiments (embodiment 72), a stained substrate of embodiment 70 or 71 is provided wherein R of Formula (I) is a branched alkyl group having a tertiary carbon atom. In certain embodiments (embodiment 73), a stained substrate of embodiments 70 through 72 is provided wherein R of Formula (I) is a branched alkyl group of 4 to 10 carbon atoms having a tertiary carbon atom.
In certain embodiments (embodiment 74), a stained substrate of embodiments 70 through 73 is provided wherein the monomer of Formula (I) has a bomopoiymer Tg of less than 110 °C, or less than 50 °C. In certain embodiments (embodiment 75), a stained substrate of embodiments 70 through 74 is provided wherein the monomer of Formula (I) has a homopolymer Tg of at least 20 °C, or at least 30 °C.
In certain embodiments (embodiment 76), a stained substrate of embodiments 70 through 75 is provided wherein the emulsion latex polymer comprises a mixture of monomers of Formula (I).
In certain embodiments (embodiment 77), a stained substrate of embodiments 70 through 76 is provided wherein the one or more monomers of Formula (I) are selected from isobornyl acrylate, cyclohexyl acrylate, t-butyl acrylate, and a mixture thereof. In certain embodiments (embodiment 78), a stained substrate of embodiment 77 is provided wherein the one or more monomers of Formula (I) comprise t-butyl acrylate.
In certain embodiments (embodiment 79), a stained substrate of embodiments 70 through 78 is provided wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of Tg of 10 °C to 45 °C (in certain embodiments, 25 °C to 45 °C, or 10 °C to 35 °C). In certain embodiments (embodiment 80), a stained substrate of embodiment 79 is provided wherein the latex polymer has at least one Fox Equation (theoretical calculated) Tg of 45 °C to -10 °C (in certain embodiments, -45 °C to -22 °C, -32 °C, or -22 °C).
In certain embodiments (embodiment 81), a stained substrate of embodiments 70 through 80 is provided wherein the latex polymer has an acid number of up to 30 (per kg OH). In certain embodiments (embodiment 82), a stained substrate of embodiments 70 through 81 is provided wherein the latex polymer has an acid number of at least 5 (per kg OH).
In certain embodiments (embodiment 83), a stained substrate of embodiments 70 through 82 is provided wherein the latex polymer comprises latex particles having a volume average particle size of at least 50 nm, or at least 60 nm, or at least 70 nm. In certain embodiments (embodiment 84), a stained substrate of embodiments 70 through 83 is provided wherein the latex polymer comprises latex particles having a volume average particle size of up to 150 nm, or up to 130 nm.
In certain embodiments (embodiment 85), a stained substrate of embodiments 70 through 84 is provided wherein the polymer is a two- or more- stage emulsion latex polymer (e.g., resulting from a power feed process). In certain embodiments (embodiment 86), a stained substrate of embodiment 85 is provided wherein the monomer of Formula (I) is present in a hard stage of the emulsion latex polymer.
In certain embodiments (embodiment 86), a stained substrate of embodiments 70 through 85 is provided wherein the interpolymerized monomers comprise at least 2 wt-% (or at least 5 wt-%) of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 87), a stained substrate of embodiments 70 through 86 is provided wherein the interpolymerized monomers comprise less than 20 wt-% (or up to 15 wt-%, or up to 10 wt-%) of one or more monomers of Formula (I), based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 88), a stained substrate of embodiments 70 through 87 is provided wherein the interpolymerized monomers comprise one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof. In certain embodiments (embodiment 89), a stained substrate of embodiments 70 through 88 is provided wherein the interpolymerized monomers comprise at least 10 wt-% (or at least 20 wt-%, at least 30 wt-%, at least 40 wt-%, at least 50 wt-%, at least 60 wt-%, at least 70 wt-%, at least 75 wt-%, at least 80 wt-%, at least 83 wt-%, at least 84 wt-%, at least 85 wt-%, or at least 90 wt-%) of one or more (meth)acrylate monomers, based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 90), a stained substrate of embodiments 70 through 89 is provided wherein the interpolymerized monomers comprise up to up to 99 wt-% (or up to 98 wt-%, or up to 95 wt-%) of one or more (meth)acrylate monomers, based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 91), a stained substrate of embodiments 70 through 90 is provided wherein the interpolymerized monomers comprise styrene. In certain embodiments (embodiment 92), a stained substrate of embodiments 70 through 91 is provided wherein the interpolymerized monomers comprise at least 1 wt-% (or at least 5 wt-%, at least 10 wt-%, or at least 15 wt-%) styrene, based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 93), a stained substrate of embodiments 70 through 92 is provided wherein the interpolymerized monomers comprise up to 75 wt-% (or up to 50 wt-%) styrene, based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 94), a stained substrate of embodiments 70 through 93 is provided wherein the interpolymerized monomers comprise one or more wet adhesion monomers (e.g., those selected from N-(2-methacryloyloxy ethyl) ethylene urea, l-(2- ((3-(allyloxy)-2-hydroxyproypl)amino)ethyl)imidazolidine-2-one, and combinations thereof).
In certain embodiments (embodiment 95), a stained substrate of embodiments 70 through 94 is provided wherein the interpolymerized monomers comprise at least 0.2 wt-% of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers. In certain embodiments (embodiment 96), a stained substrate of embodiments 70 through 95 is provided wherein the interpolymerized monomers comprise up to 2.0 wt-% (or up to 1.0 wt-%) of one or more wet adhesion monomers, based on the total weight of the interpolymerized monomers.
In certain embodiments (embodiment 97), a stained substrate of embodiments 70 through 96 is provided wherein a hardened coating formed from the stain-blocking polymer has a stain blocking performance, based on the Stain-blocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a black water- washable marker; at most 16 for a blue water-washable marker; and/or at most 15, preferably at most 12, for a green water-washable marker (or in certain embodiments, such as in single-stage latex polymers, the DE value is: at most 14 for black water-washable marker; at most 7 for a blue water-washable marker; and/or at most 8 for a green water-washable marker). In certain embodiments (embodiment 98), a stained substrate of embodiments 70 through 97 is provided wherein a hardened coating formed from the stain-blocking polymer has an adhesion performance of at least 2 based on the ASTM 3359 Cross-cut Adhesion Test. In certain embodiments (embodiment 99), a stained substrate of embodiments 70 through 98 is provided wherein a hardened coating formed from the stain blocking polymer has a pendulum hardness of at least 4 based on the Konig Pendulum Hardness Test.
In certain embodiments (embodiment 100), a kit for making a stain-blocking primer (e.g., of embodiments 1 through 42) is provided that includes: an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; and instructions for forming a stain-blocking primer.
In certain embodiments (embodiment 101), a kit for making a stain-blocking primer of embodiment 100 is provided wherein a hardened coating formed from the primer has a stain blocking performance, based on the Stainblocking Test, characterized by a DE value of: at most 20, preferably at most 18, for a black water-washable marker; at most 16 for a blue water- washable marker; and/or at most 15, preferably at most 12, for a green water-washable marker (or in certain embodiments, such as in single-stage latex polymers, the DE value is: at most 14 for black water-washable marker; at most 7 for a blue water-washable marker; and/or at most 8 for a green water-washable marker).
In certain embodiments (embodiment 102), a kit for making a stain-blocking primer of embodiment 100 or 101 is provided wherein the emulsion latex polymer and the instructions are physically packaged together (but the two don’t need to be physically delivered together in a physical package to be a kit).
In certain embodiments (embodiment 103), a method is provided that includes: causing a stain-blocking polymer (e.g., of embodiments 43 through 68) to be applied to a stained substrate.
In certain embodiments, (embodiment 104), a method is provided that includes: causing a stain-blocking polymer to be applied to a stained substrate wherein the stain-blocking polymer is an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt- %, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
EXAMPLES
These Examples are merely for illustrative purposes and are not meant to be overly limiting on the scope of the appended claims. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the present disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all reagents used in the examples were obtained, or are available, from general chemical suppliers such as, for example, Sigma-Aldrich Company, Saint Louis, Missouri, or may be synthesized by conventional methods. The following abbreviations may be used in the following examples: ppm = parts per million; phr = parts per hundred
rubber; mL = milliliter; L = liter; m = meter, mm = millimeter, cm = centimeter, kg = kilogram, g = gram, min = minute, s = second, hrs = hour, °C = degrees Celsius, °F = degrees Fahrenheit, MPa = megapascals, and N-m = Newton-meter, Mn = number average molecular weight, cP = centipoise.
THEORETICAL FOX Tg CALCULATION
The Glass Transition Temperature (Tg) of the disclosed polymer composition is predicted from the Fox Equation, a generalized form of which is shown below:
where WA, WB, WC, . . WN respectively represent the weight fraction of each monomer type A, B, C,.. N in the copolymer composition, and TgA, TgB, Tgc,.. TgN represent the corresponding Tg’s (expressed in Kelvin) of the homopolymers prepared from the respective monomer type A, B, C,.. N. For example, a polymer composition consisting of 55.8 wt-% styrene (Tg, styrene = 373.15K), 42.8 wt-% 2-ethylhexyl acrylate (Tg, 2-EHA = 193.15 K), and 1.4 wt-% methacrylic acid (Tg, MAA = 458.15) will have a predicted Fox Tg of r 0.558 0.428 0.014
Tg = [: + ]_1 = 267.25 K, or equivalently, -5.9 °C.
3 -73.15 K + 193.15 K 458.15 KJ The Fox equation is also known to adequately predict the effective overall Tg of a miscible polymer mixture. In the case of a multi-stage polymer blend, the overall Tg of the polymer blend can be determined by applying the Tg and weight fraction of each polymer stage in the Fox equation.
ACTUAL Tg
The actual Tg of a polymer or polymer blend can determined experimentally by techniques such as differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). All actual Tg disclosed in the current disclosure are evaluated using a DSC25 differential scanning calorimeter equipped with a RSC90 cooler, both purchased from TA Instruments. Calibration was performed on an indium standard and all experiments use a standardized heat-cool -heat cycle at a 20 °C/min ramp rate.
LATEX EXAMPLES
Various latex samples were prepared and the properties of the samples were tested using a Stainblocking Test, Adhesion Test, and Konig Pendulum Hardness Test.
All latex examples were synthesized under starved fed condition to reduce chances of block copolymerization. Various branched meth(acrylates) with and without at least one tertiary carbon in their ester side chain are substituted in a common latex formula. Some of resulting latexes surprisingly produce coatings that demonstrate noticeably improved stainblocking compared to that of the comparative example latex. To attempt to account for the dependence of polymer Tg on the composition of the monomers, the theoretical Fox Tg of the example latexes are adjusted to the same value within ± 1 °C.
LATEX PREPARATION PROCEDURE A — TWO-STAGE LATEX To a 3 -liter (3-L) reactor, a 30 ± 5 nm, 30 wt-% seed latex (182 grams (g)) and deionized water (459 g) were added. The reactor was fitted with a four-blade impeller, a condenser, and an internal temperature probe. The reactor assembly was heated to an internal temperature of 58-60 °C with constant agitation maintained throughout the synthetic process. In a separate 0.8 L container, monomer emulsion 1 was prepared by sequentially adding deionized water (113 g), DISPONIL FES 32 (16.5 g), SIPOMER PAM-4000 (5 g), VISIOMER MEEU 25M (6.8 g), methacrylic acid (4.3 g), 28 % ammonium hydroxide (2.3 g), dodecyl mercaptan (0.3 g), and a mixture of monomers (TABLE 1) under constant mixing with a three-blade impeller. In a separate 1.8 L container, monomer emulsion 2 was prepared by sequentially adding deionized water (201 g), DISPONIL FES 32 (33 g), SIPOMER PAM-4000 (9.8 g), VISIOMER MEEU 25M (13.6 g), methacrylic acid (8 g), 28 % ammonium hydroxide (4.6 g), dodecyl mercaptan (0.7 g), 2-ethylhexyl acrylate (2-EHA) (313 g), and styrene (261 g) under constant mixing with a three-blade agitator. Prior to addition of monomer emulsion 1 to reactor, 70 % aqueous tert-butyl hydroperoxide (0.7 g), erythorbic acid (0.5 g), and 7 % aqueous DISSOLVINE E-FE-13 (0.2 g) were added to the reactor. Monomer emulsion 1 was fed into the reactor over 1.5 hours (hr). Upon initiation of monomer emulsion 1 feed, an oxidizer solution containing 70 % aqueous tert-butyl hydroperoxide (4.3 g) in deionized water (90 g) and a reducer solution containing erythorbic acid (2.6 g) in deionized water (90 g) were fed separately and simultaneously into the reactor over 5.5 hr. Upon depletion of monomer emulsion 1, monomer emulsion 2 was fed into the reactor over 2.5 hr. At the end of monomer emulsion 2 feed, 70 % aqueous tert-butyl hydroperoxide (0.7 g) and erythorbic acid (0.5 g) were respectively added to the remaining oxidizer and reducer feed solutions. At the end of oxidizer and reducer feeds, the reactor solution was cooled to below 40 °C and neutralized with 28 %
ammonium hydroxide (7.4 g). The resulting emulsion was diluted with deionized water (50 g) and filtered through a 100 mhi filter.
LATEX PREPARATION PROCEDURE B — TWO-STAGE LATEX
To a 3-L reactor, a 30 ± 5 nm, 30 wt-% seed latex (182 g) and deionized water (459 g) were added. The reactor was fitted with a four-blade impeller, a condenser, and an internal temperature probe. The reactor assembly was heated to an internal temperature of 58-60 °C with constant agitation maintained throughout the synthetic process. In a separate 0.8 L container, monomer emulsion 1 was prepared by sequentially adding deionized water (113 g), DISPONIL FES 32 (16.5 g), SIPOMER PAM-4000 (5 g), VISIOMER MEEU 25M (6.8 g), methacrylic acid (4.3 g), 28 % ammonium hydroxide (2.3 g), dodecyl mercaptan (0.3 g), 2-ethylhexyl acrylate (17 g), and tert-butyl acrylate (291 g) under constant mixing with a three-blade impeller. In a separate 1.8 L container, monomer emulsion 2 was prepared by sequentially adding deionized water (201 g), DISPONIL FES 32 (33 g), SIPOMER PAM-4000 (9.8 g), VISIOMER MEEU 25M (13.6 g), methacrylic acid (8 g), 28 % ammonium hydroxide (4.6 g), dodecyl mercaptan (0.7 g), and a mixture of monomers (Table 2) under constant mixing with a
three-blade agitator. Prior to addition of monomer emulsion 1 to reactor, 70 % aqueous tert- butyl hydroperoxide (0.7 g), erythorbic acid (0.5 g), and 7 % aqueous DISSOLVINE E-FE-13 (0.2 g) were added to the reactor. Monomer emulsion 1 was fed into the reactor over 1.5 hr. Upon initiation of monomer emulsion 1 feed, an oxidizer solution containing 70 % aqueous tert- butyl hydroperoxide (4.3 g) in deionized water (90 g) and a reducer solution containing erythorbic acid (2.6 g) in deionized water (90 g) were fed separately and simultaneously into the reactor over 5.5 hr. Upon depletion of monomer emulsion 1, monomer emulsion 2 was fed into the reactor over 2.5 hr. At the end of monomer emulsion 2 feed, 70 % aqueous tert-butyl hydroperoxide (0.7 g) and erythorbic acid (0.5 g) were respectively added to the remaining oxidizer and reducer feed solutions. At the end of oxidizer and reducer feeds, the reactor solution was cooled to below 40 °C and neutralized with 28 % ammonium hydroxide (7.4 g). The resulting emulsion was diluted with deionized water (50 g) and filtered through a 100 micrometers (pm) filter.
LATEX PREPARATION PROCEDURE C — POWERFEED LATEX To a 3-L reactor, a 30 ± 5 nanometer (nm), 30 wt-% seed latex (182 g) and deionized water (459 g) were added. The reactor was fitted with a four-blade impeller, a condenser, and an internal temperature probe. The reactor assembly was heated to an internal temperature of 58-60 °C with constant agitation maintained throughout the synthetic process. In a separate 0.8 L container, monomer emulsion 1 was prepared by sequentially adding deionized water (113 g), DISPONIL FES 32 (16.5 g), SIPOMER PAM-4000 (5 g), VISIOMER MEEU 25M (6.8 g), methacrylic acid (4.3 g), 28 % ammonium hydroxide (2.3 g), dodecyl mercaptan (0.3 g), 2- ethylhexyl acrylate (53.3 g), styrene (154.4 g), and tert-butyl acrylate (100 g) under constant
mixing with a three-blade impeller. In a separate 1.8 L container, Monomer Emulsion 2 was prepared by sequentially adding deionized water (201 g), DISPONIL FES 32 (33 g), SIPOMER PAM-4000 (9.8 g), VISIOMER MEEU 25M (13.6 g), methacrylic acid (8 g), 28 % ammonium hydroxide (4.6 g), dodecyl mercaptan (0.7 g), 2-ethylhexyl acrylate (313 g), and styrene (261 g) under constant mixing with a three-blade agitator. Prior to addition of the monomer emulsion mixture to reactor, 70 % aqueous tert-butyl hydroperoxide (0.7 g), erythorbic acid (0.5 g), and 7 % aqueous DISSOLVINE E-FE-13 (0.2 g) were added to the reactor. Monomer emulsion 2 was set to feed over 3.5 hr into Monomer Emulsion 1 container under agitation, while the Monomer Emulsions mixture was simultaneous fed into the reactor over 4 hr. Upon initiation of monomer feed, an oxidizer solution containing 70 % aqueous tert-butyl hydroperoxide (4.3 g) in deionized water (90 g) and a reducer solution containing erythorbic acid (2.6 g) in deionized water (90 g) were fed separately and simultaneously into the reactor over 5.5 hr. At the end of monomer feed, 70 % aqueous tert-butyl hydroperoxide (0.7 g) and erythorbic acid (0.5 g) were respectively added to the remaining oxidizer and reducer feed solutions. At the end of oxidizer and reducer feeds, the reactor solution was cooled to below 40 °C and neutralized with 28 % ammonium hydroxide (7.4 g). The resulting emulsion was diluted with deionized water (50 g) and filtered through a 100 pm filter.
LATEX PREPARATION PROCEDURE D — SINGLE-STAGE LATEX To a 3 -liter (3-L) reactor, a 30 ± 5 nm, 30 wt-% seed latex (182 grams (g)) and deionized water (450 g) were added. The reactor was fitted with a four-blade impeller, a condenser, and an internal temperature probe. The reactor assembly was heated to an internal temperature of 58-60 °C with constant agitation maintained throughout the synthetic process. In a separate 0.8 L container, monomer emulsion was prepared by sequentially adding deionized water (340 g), DISPONIL FES 32 (49.5 g), SIPOMER PAM-4000 (14.8 g), VISIOMER MEEU 25M (20.4 g), methacrylic acid (12.2 g), 28 % ammonium hydroxide (7.5 g), and a mixture of monomers (TABLE 3) under constant mixing with a three-blade impeller. Prior to addition of monomer emulsion to reactor, 70 % aqueous tert-butyl hydroperoxide (0.7 g), erythorbic acid (0.5 g), and 7 % aqueous DISSOLVINE E-FE-13 (0.2 g) were added to the reactor. Monomer emulsion was fed into the reactor over 3 hours (hr). Upon initiation of monomer emulsion feed, an oxidizer solution containing 70 % aqueous tert-butyl hydroperoxide (4.3 g) in deionized water (90 g) and a reducer solution containing erythorbic acid (2.6 g) in deionized water (90 g) were fed separately and simultaneously into the reactor over 4.5 hr. At the end of monomer
emulsion feed, 70 % aqueous tert-butyl hydroperoxide (0.7 g) and erythorbic acid (0.5 g) were respectively added to the remaining oxidizer and reducer feed solutions. At the end of oxidizer and reducer feeds, the reactor solution was cooled to below 40 °C and neutralized with 28 % ammonium hydroxide (5.4 g). The resulting emulsion was diluted with deionized water (50 g) and filtered through a 100 pm filter.
MATERIALS
EXAMPLES 1-4 AND COMPARATIVE EXAMPLES 5-6 Examples 1-6 were 2-stage latexes prepared according to the Latex Preparation Procedure A for a two-stage latex, using the Example 1-6 components as indicated in TABLE 1 above. Examples 1-6 included 1 wt-%, 2 wt-%, 5 wt-%, 10 wt-%, 20 wt-%, and 30 wt-% of tBA, respectively, based on total weight of monomers.
COMPARATIVE EXAMPLES 7-9
Examples 7-9 were 2-stage latexes prepared according to the Latex Preparation Procedure B for a two-stage latex, using the Example 7-9 components as indicated in TABLE 2 above. Example 7 included 30 wt-% of tBA in monomer emulsion 1 and 10 wt-% of tBA in monomer emulsion 2, based on total weight of monomers. Example 8 included 30 wt-% of tBA in monomer emulsion 1 and 20 wt-% of tBA in monomer emulsion 2, based on total weight of monomers. Example 9 included 30 wt-% of tBA in monomer emulsion 1 and 32 wt-% of tBA in monomer emulsion 2, based on total weight of monomers.
EXAMPLE 10
Example 10 was a powerfeed latex prepared according to the Latex Preparation Procedure C for a powerfeed latex, using the Example 10 components (same as Example 4 components) as indicated in TABLE 1 above. Example 10 included 10 wt-% of tBA based on total weight of monomers.
EXAMPLES 11-12 AND COMPARATIVE EXAMPLES 13-14 Examples 11-14 were 2-stage latexes prepared according to the Latex Preparation Procedure A for a two-stage latex, using the Example 11-14 components as indicated in TABLE 1 above. Example 11 included 10 wt-% of iso-bomyl acrylate based on total weight of monomers. Example 12 included 10 wt-% of cyclohexyl acrylate based on total weight of monomers. Example 13 included 10 wt-% of iso-butyl acrylate based on total weight of monomers. Example 14 included 10 wt-% of t-butyl methacrylate based on total weight of monomers.
COMPARATIVE EXAMPLE 15
Example 15 was a 2-stage latex prepared according to the Latex Preparation Procedure A for a two-stage latex, using the Example 15 components as indicated in TABLE 1 above.
The volume average particle size, resin solids, and pH of each of the Examples 1-15 were recorded and are shown in TABLE 3 below.
EXAMPLES 16-17 AND COMPARATIVE EXAMPLES 18 Examples 16-18 were single-stage latexes prepared according to the Latex Preparation
Procedure D for a single-stage latex, using the Example 16-18 components as indicated in TABLE 3 above. Example 16 included 5 wt-% of tert-butyl acrylate based on total weight of monomers. Example 17 included 10 wt-% of tert-butyl acrylate based on total weight of monomers.
The volume average particle size, resin solids, and pH of each of the Examples 1-15 were recorded and are shown in TABLE 3 below.
Each of the Examples was prepared into a primer formulation (labelled “Example 1 Primer,” “Example 2 Primer,” etc. made with the respective Example latex above) and used for further testing.
General Procedure for Two-Stage Primer Formula
A flat primer formula was prepared by adding a pigment grind to a stirring Example latex, followed by the addition of let down ingredients. The pigment grind was prepared by sequentially adding, in the order listed and under constant mixing with a Cowles blade to maintain a vortex, 100 g of water, 5 g of ATTAGEL 50, 11 g of TAMOL 165A, 1 g of
STRODEX NB-20, 3 g of AMP-95, 3.5 g of DREWPLUS L-475, 150 g of Ti-Pure R-706, 150 g of CAMEL-WHITE, and 2 g of water. The grind was added to 498 g of stirring Example latex in a quart-size can and the mixture was agitated for 20 minutes. Let down ingredients were added, sequentially in the order listed, to the pigmented Example latex: EPS 9147 coalescent (see TABLE 4 for amounts), 1.5 g of NUOSEPT 498, 1.2 g of 4 % aqueous sodium nitrite, 112 g of water, 6 g of AQUAFLOW NHS-310, and ACRYSOL RM-8W (see TABLE 4 for amounts) to afford a flat primer formulation with a KU viscosity of 100 ± 3.
The amounts of the coalescent and rheology modifiers, TEXANOL coalescent and ACRYSOL RM-8W, were adjusted for each Example latex to achieve coalescence below 50 °F and a KE1 viscosity range of 100 ± 3. The levels used are listed in TABLE 4.
General Procedure for Single-Stage Primer Formula
A flat primer formula was prepared by adding a pigment grind to a stirring Example latex, followed by the addition of let down ingredients. The pigment grind was prepared by sequentially adding, in the order listed and under constant mixing with a Cowles blade to maintain a vortex, 100 g of water, 5 g of ATTAGEL 50, 11 g of TAMOL 165 A, 1 g of STRODEX NB-20, 3 g of AMP-95, 3.5 g of DREWPLUS L-475, 150 g of Ti-Pure R-706, 150 g of CAMEL-WHITE, and 2 g of water. The grind was added to 498 g of stirring Example latex in a quart-size can and the mixture was agitated for 20 minutes. Let down ingredients were added, sequentially in the order listed, to the pigmented Example latex: Texanol coalescent (see TABLE 6 for amounts), 1.5 g of NUOSEPT 498, 1.2 g of 4 % aqueous sodium nitrite, 112 g of water, 6 g of AQUAFLOW NHS-310, and ACRYSOL RM-8W (see TABLE 4 for amounts) to afford a flat primer formulation with a KU viscosity of 95 ± 3.
The amounts of the coalescent and rheology modifiers, EPS® 9147 coalescent and ACRYSOL RM-8W, were adjusted for each Example latex to achieve coalescence below 50 °F and a KU viscosity range of 95 ± 3. The levels used are listed in TABLE 6.
FLAT PAINT FORMULATION
A flat paint formulation was prepared for use in the Stainblocking Test. A pigment grind was added to a stirring EPS 2741 latex, followed by the addition of let down ingredients. The pigment grind was prepared by sequentially adding, in the order listed and under constant mixing with a Cowles blade to maintain a vortex, 75 g of water, 6 g of TAMOL 165A, 2 g of SURFYNOL 104 A, 2 g of DREWPLUS L-475, 3 g of ATTAGEL 50, 3 g of NUOSEPT 498, 327 g of KRONOS 4311, 115 g of MINEX 4, and 60 g of DIAFIL 525. The grind was added to 537 g of EPS 2741 latex stirring in a quart-size can and the mixture was agitated for 20 minutes. Let down ingredients were added, sequentially in the order listed, to the pigmented EPS 2741 latex : 1 g of ammonium hydroxide, 11 g of EPS 9147 coalescent, 1 g of DREWPLUS L-475,
10 g of 4 % aqueous sodium nitrite, 7.5 g of OPTIFLO L1400, 1 g of ACRYSOL RM-8W, and 7 g of DI water, to afford a flat primer formulation with a KU viscosity of 95.
STAINBLOCKING TEST
Preparation of Stained Samples. On a smooth, flat substrate (Leneta Scrub Test Panel, P-121-1 ON, available from Paul N. Gardner Company in Pompano Beach, FL), Flat Paint Formulation was applied as a 7 mil (0.1778 mm) wet film basecoat using a U-shaped applicator (#2230, available from BYK-Gardner USA in Columbia, MD). The applied basecoat was allowed to dry for at least 24 hr at room temperature. On the dried basecoat, various staining agents - water-washable black, blue, and green markers (MARKS-A-LOT marker in color black from Avery Products Corp. in Brea, CA; CRAYOLA Window Marker in colors blue and green from Crayola LLC in Forks Township, PA) were applied and allowed to dry for at least 12 hr.
Preparation of Unstained Sample. An unstained sample was prepared by applying the Flat Paint Formulation onto the substrate as a 6 mil (0.1524 mm) wet film, which was air dried at room temperature for at least 24 hr. This was used for standardizing the spectrophotometer.
Application of Primer and Paint. The Example primer formulations (Example Primer 1 - Example Primer 15) were applied over the stained areas using a 3 mil (0.0762 mm) square applicator (4 inch (101.6 mm) width, AP-B5356, Paul N. Gardner Company). The primer coat was allowed to dry for 6 hr at room temperature. A top coat of Flat Paint Formulation was applied over the dried primer coat using a 6 mil (0.1524 mm) square applicator (3 inch (0.0762
mm) width, AP-B5353, Paul N. Gardner Company). The top coat was allowed to dry for at least 1 day before colorimetric measurements were taken. The unstained sample was treated in the same way.
Measurements. The appearance of color in the top coat of the stained samples was compared to the unstained sample. A calibrated Datacolor Check III spectrophotometer
(Lawrenceville, NJ) was used to measure the baseline color of the unstained sample. A second measurement was performed over a stained area of interest to give the color difference (expressed in DE) between the stained and stain-free regions. The stainblocking results, shown in TABLE 5 below, are averages of at least two repeat measurements. A lower DE value indicates better stainblocking performance.
TABLE 7. Stainblocking Results.
GENERAL PROCEDURE FOR ADHESION TEST This adhesion test uses the ASTM 3359 cross-cut adhesion method. Each Example primer containing an Example latex was applied as a 3 mil (0.0762 mm) wet film on the following substrates: 3 foot (0.914 m) sanded cedar panel, and dull matte steel (R-48, 4 inch x 8 inch (101.6 mm x 203.2 mm), Q-Lab). The Example primers were applied on the cedar panels and the R-48 steel panels using a #5554 applicator from BYK-Gardner LISA. After air drying for 24 hr, each paint film was perpendicularly cross-cut using a 6-line, 2-millimiter (2 -mm) template with an OLFA Slimline Knife (available from OLFA Corp. in Rosemont, IL) with a fresh sharp blade. A 3-inch (76.2 mm) piece of ELCOMETER 99 adhesive test tape (available from Elcometer in Warren, MI) was applied to the cross-cut region and peeled off at 180° angle, and the resulting film removal was rated as specified in ASTM 3359 Method B. The adhesion results are shown in TABLE 6 below. The range of the adhesion test score is from 0 to 5, with higher numbers indicating higher adhesion.
KONIG PENDULUM HARDNESS TEST
Each primer containing an Example Latex was applied as a 10 mil (0.254 mm) wet film on a 4 inch x 6 inch x 0.25 inch (101.6 mm x 152.4 mm x 6.35 mm) smooth glass plate and allowed to air dry for 24 hr at ambient temperature. The one-day hardness was recorded on a BYK Konig pendulum hardness tester using a 3° angle. A second hardness value was measured after air drying at ambient temperature for 7 days. The Konig hardness data, shown in TABLE 6, are averages of three repeat measurements. A higher Konig hardness value indicates higher hardness.
The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. To the extent that there is any conflict or discrepancy between this specification as written and the disclosure in any document that is incorporated by reference herein, this specification as written will control. Various modifications and alterations to this disclosure will become apparent to those skilled in the art without departing from the scope and spirit of this disclosure. It should be understood that this disclosure is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are
presented by way of example only with the scope of the disclosure intended to be limited only by the claims set forth herein as follows.
Claims
1. A stain-blocking primer comprising: at least 10 wt-%, based on the total nonvolatile weight of the primer, of an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-% to less than 20 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; and R has 20 or fewer carbon atoms; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; an aqueous carrier; and optionally, one or more additives selected from a surfactant, thickener, coalescent, biocide, mildewcide, colorant, and combinations thereof.
2. The primer of claim 1 wherein R of Formula (I) is a branched alkyl group of 4 to 10 carbon atoms having a tertiary carbon atom.
3. The primer of claim 1 or 2 wherein the monomer of Formula (I) has a homopolymer Tg of 30 °C to 50 °C.
4. The primer of any of the previous claims wherein the one or more monomers of Formula (I) are selected from isobornyl acrylate, cyclohexyl acrylate, t-butyl acrylate, and a mixture thereof.
5. The primer of claim 4 wherein the one or more monomers of Formula (I) comprise t- butyl acrylate.
6. The primer of any of the previous claims comprising up to 50 wt-% of the emulsion latex polymer, based on the total nonvolatile weight of the primer.
7. The primer of any of the previous claims wherein the interpolymerized monomers comprise 10 wt-% to 99 wt-% of one or more (meth)acrylate monomers, based on the total weight of the interpolymerized monomers.
8. The primer of any of the previous claims wherein the interpolymerized monomers comprise styrene.
9. The primer of any of the previous claims wherein a hardened coating formed from the primer has a stain-blocking performance, based on the Stain-blocking Test, characterized by a DE value of: at most 20 for black water- washable marker; at most 16 for a blue water- washable marker; and/or at most 15 for a green water- washable marker.
10. The primer of claim 9 wherein a hardened coating formed from the primer has a stain blocking performance, based on the Stain-blocking Test, characterized by a DE value of: at most 14 for black water- washable marker; at most 7 for a blue water-washable marker; and/or at most 8 for a green water-washable marker.
11. The primer of any of the previous claims which has an adhesion performance of at least 2 based on the ASTM 3359 Cross-cut Adhesion Test, a pendulum hardness of at least 4 based on the Konig Pendulum Hardness Test, or both.
12. A stain-blocking polymer comprising: an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-% of one or more acrylic acid ester monomers of Formula
(I):
RO-C(0)-CH=CH2
wherein: R is a branched alkyl having a tertiary carbon atom; and R has 20 or fewer carbon atoms; at least 10 wt-% of one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; and at least 1 wt-% styrene; wherein the weight percentages are based on the total weight of the interpolymerized monomers; wherein a hardened coating formed from the stain-blocking polymer has one or more of the following properties: a stain-blocking performance, based on the Stainblocking Test, characterized by a DE value of: at most 20 for a black water- washable marker; at most 16 at most for a blue water-washable marker; and/or at most 15 for a green water- washable marker; an adhesion performance of at least 2 based on the ASTM 3359 Cross-cut Adhesion Test; and a pendulum hardness of at least 4 based on the Konig Pendulum Hardness Test.
13. A stained substrate having a stain-blocking polymer coated thereon, wherein the stain blocking polymer is an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-% to less than 20 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; and R has 20 or fewer carbon atoms; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
14. A kit for making a stain-blocking primer comprising: an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-% to less than 20 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; and R has 20 or fewer carbon atoms; optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene; and instructions for forming a stain-blocking primer, wherein a hardened coating formed from the primer has a stain-blocking performance, based on the Stain-blocking Test, characterized by a DE value of: at most 20 for a black water- washable marker; at most 16 for a blue water- washable marker; and/or at most 15 for a green water-washable marker.
15. A method comprising: causing a stain-blocking polymer to be applied to a stained substrate, the stain blocking polymer is an emulsion latex polymer comprising interpolymerized monomers comprising: at least 1 wt-% to less than 20 wt-%, based on the total weight of the interpolymerized monomers, of one or more acrylic acid ester monomers of Formula (I):
RO-C(0)-CH=CH2 wherein: R is a branched alkyl group having a tertiary carbon atom, a cycloaliphatic group, or a combination thereof; and R has 20 or fewer carbon atoms;
optionally, one or more (meth)acrylate monomers selected from n-butyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; optionally, one or more wet adhesion monomers; and optionally, styrene.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA3168208A CA3168208A1 (en) | 2020-02-21 | 2021-02-18 | Stain-blocking polymers, primers, kits, and methods |
EP21756266.9A EP4107229A4 (en) | 2020-02-21 | 2021-02-18 | Stain-blocking polymers, primers, kits, and methods |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US202062979931P | 2020-02-21 | 2020-02-21 | |
US62/979,931 | 2020-02-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021168062A1 true WO2021168062A1 (en) | 2021-08-26 |
Family
ID=77365863
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2021/018494 WO2021168062A1 (en) | 2020-02-21 | 2021-02-18 | Stain-blocking polymers, primers, kits, and methods |
Country Status (4)
Country | Link |
---|---|
US (2) | US11180665B2 (en) |
EP (1) | EP4107229A4 (en) |
CA (1) | CA3168208A1 (en) |
WO (1) | WO2021168062A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116082559A (en) * | 2022-12-26 | 2023-05-09 | 广东银洋环保新材料有限公司 | High-performance acrylic emulsion for textile printing finishing, preparation method of high-performance acrylic emulsion and printing finishing coating |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07148459A (en) * | 1993-04-26 | 1995-06-13 | Rohm & Haas Co | Improved coating method |
JPH08225767A (en) * | 1994-10-28 | 1996-09-03 | Hoechst Ag | Water-base dispersion for primer |
US20020004552A1 (en) * | 2000-04-26 | 2002-01-10 | Hai Deng | Aqueous stain-blocking coating composition |
WO2004018575A1 (en) * | 2002-08-22 | 2004-03-04 | Mitsubishi Rayon Co., Ltd. | Primer composition for coating |
WO2011073164A1 (en) * | 2009-12-17 | 2011-06-23 | Akzo Nobel Coatings International B.V. | Stain-blocking aqueous coating composition |
US20120121921A1 (en) * | 2009-07-22 | 2012-05-17 | Basf Se | Aqueous polymer dispersion as a binding agent for plasters and coating materials having improved fire behavior |
CN104341547A (en) * | 2013-07-29 | 2015-02-11 | 上海富臣化工有限公司 | Polyacrylic ester sealing emulsion and preparation method thereof |
JP2016535691A (en) * | 2013-11-08 | 2016-11-17 | ベーカー ギウリニ ゲゼルシャフト ミット ベシュレンクテル ハフツングBK Giulini GmbH | Means and method for preventing tannin migration from wood |
Family Cites Families (125)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2795564A (en) | 1953-05-13 | 1957-06-11 | Rohm & Haas | Aqueous paint bases and water-base paints and process for preparing them |
US3492252A (en) | 1963-10-07 | 1970-01-27 | Scm Corp | Emulsion coating comprising neutralized latex of acidic polymer and an epoxy component |
US4016127A (en) | 1971-07-06 | 1977-04-05 | Rohm And Haas Company | Emulsion copolymers of acrolein and their use in treating leather |
US3852087A (en) | 1972-03-22 | 1974-12-03 | J Nordyke | Composite pigment for blocking tannin |
US3969293A (en) | 1973-08-06 | 1976-07-13 | Nl Industries, Inc. | Basic zinc phosphites |
US4014838A (en) | 1973-09-17 | 1977-03-29 | Stauffer Chemical Company | Fire retardant polymeric additives |
US4021398A (en) | 1973-09-18 | 1977-05-03 | Armour Pharmaceutical Company | Aqueous latex emulsions containing basic aluminum compounds of wood-stain reducing agents |
US4075394A (en) | 1976-04-08 | 1978-02-21 | The Dow Chemical Company | Process of inhibiting tannin migration in tannin-containing wood substrates |
US4284740A (en) | 1978-11-30 | 1981-08-18 | American Cyanamid Co. | Acrylate copolymers grafted onto a polar, water-soluble backbone polymer |
US4218516A (en) | 1979-01-26 | 1980-08-19 | The Dow Chemical Company | Pigment for blocking tannin migration |
DE3151813A1 (en) | 1981-12-29 | 1983-07-07 | Hoechst Ag, 6230 Frankfurt | "METHOD FOR PRODUCING A POLYMER DISPERSION" |
DE3313922A1 (en) | 1983-04-16 | 1984-10-25 | Hoechst Ag, 6230 Frankfurt | EMULSION AND PROTECTIVE COLLOID-FREE EMULSION POLYMERISATES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
DE3333503A1 (en) | 1983-09-16 | 1985-04-18 | Röhm GmbH, 6100 Darmstadt | THICKENING AGENTS AND BINDERS GELLING IN GASOLINE |
US4582663A (en) | 1983-11-21 | 1986-04-15 | The Dow Chemical Company | Amphoteric latexes containing pH independent and pH dependent bound charges |
US4544697A (en) | 1983-11-21 | 1985-10-01 | The Dow Chemical Company | Amphoteric latexes containing pH independent and pH dependent bound charges |
US4686260A (en) | 1985-07-10 | 1987-08-11 | Sun Chemical Corporation | Printing ink composition |
US4708923A (en) | 1986-04-30 | 1987-11-24 | Eastman Kodak Company | Crosslinked vinyl polymer particles and electrographic elements and liquid developers containing such particles |
CA1333822C (en) | 1986-11-07 | 1995-01-03 | Robert S. Beyersdorf | Latex compositions useful as binders in composite board having dimensional stability and strength |
US4973670A (en) | 1988-08-12 | 1990-11-27 | The Dow Chemical Company | Method for preparing hollow latexes |
DE3827975A1 (en) | 1988-08-18 | 1990-03-01 | Basf Ag | METHOD FOR PREVENTING FLOWERS FROM MINERAL SUBSTRATES |
DE3832397A1 (en) | 1988-09-23 | 1990-03-29 | Bayer Ag | MOLDING MATERIALS FROM POLYAMIDES AND GRAFT POLYMERISATES CONTAINING TERT.-BUTYL ACRYLATE |
US5162413A (en) | 1989-02-01 | 1992-11-10 | Union Oil Company Of California | Salt-containing surface coating polymer compositions and substrates coated therewith |
US5312863A (en) | 1989-07-05 | 1994-05-17 | Rohm And Haas Company | Cationic latex coatings |
BR9104719A (en) | 1990-10-26 | 1992-06-16 | Buckman Labor Inc | INK FORMULATION AND METHOD TO REDUCE TANINE STAIN FORMATION |
US5268431A (en) | 1992-09-28 | 1993-12-07 | The Goodyear Tire & Rubber Company | Method for preparing ultra-low molecular weight toner resin |
DE4240744A1 (en) | 1992-12-03 | 1994-06-09 | Wacker Chemie Gmbh | Process for the preparation of a graft copolymer latex of core-shell dispersion particles with improved phase connection between core and shell |
US5306744A (en) | 1992-12-18 | 1994-04-26 | Rohm And Haas Company | Functionalized multistage polymers |
DE4302552A1 (en) | 1993-01-29 | 1994-08-04 | Wacker Chemie Gmbh | Graft and core-shell copolymers with improved phase connection between the graft base and the grafted-on polymer phase |
JP3297764B2 (en) | 1993-04-22 | 2002-07-02 | 鐘淵化学工業株式会社 | Room temperature curable composition |
US5527619A (en) | 1993-04-26 | 1996-06-18 | Rohm And Haas Company | Tannin stain blocking coated substrate |
DE4314305A1 (en) | 1993-04-30 | 1994-11-03 | Basf Ag | Hair fixatives |
US5714539A (en) | 1993-10-04 | 1998-02-03 | Ppg Industries, Inc. | Polymeric surfactant and latex made therefrom |
US5460644A (en) | 1993-12-14 | 1995-10-24 | The O'brien Corporation | Stain-blocking and mildewcide resistant coating compositions |
US5800873A (en) | 1994-10-03 | 1998-09-01 | Basf Lacke+Farben Ag | Process for the production of sealed packaging containers and the use of a sealing coating for coating plastics films |
DE4439459A1 (en) | 1994-11-04 | 1995-05-04 | Basf Ag | Aqueous polymer dispersion |
US5529811A (en) | 1994-12-30 | 1996-06-25 | Wayne Pigment Corp. | Tannin staining and fungus growth inhibitor pigment and manufacturing procedure |
US5747585A (en) | 1995-02-17 | 1998-05-05 | Eastman Kodak Company | Process for synthesizing latex polymers from solid monomer particles |
DE19512882A1 (en) | 1995-04-06 | 1996-10-10 | Basf Ag | Aqueous polymer dispersion |
US5759705A (en) | 1995-08-23 | 1998-06-02 | Wayne Pigment Corp. | Stain inhibiting pigment composition |
US5993534A (en) | 1996-07-03 | 1999-11-30 | Weyerhaeuser Company | Stain blocking treatment for wood based panels |
BR9711394A (en) * | 1996-09-09 | 1999-08-17 | Basf Ag | Process for preparing aqueous polymeric dispersions aqueous polymeric polymeric dispersion using a polymeric aqueous polymeric dispersion |
US5981058A (en) | 1996-09-13 | 1999-11-09 | Mannington Mills, Inc. | Stain blocking barrier layer |
AU714737B2 (en) | 1996-10-15 | 2000-01-13 | Rohm And Haas Company | Coating compositions containing ion exchange resins |
CA2276439A1 (en) | 1996-12-31 | 1998-07-09 | John Sinko | Aqueous paint additive for staining inhibition and procedure |
US6218012B1 (en) | 1998-03-11 | 2001-04-17 | The Sherwin-Williams Company | Primerless latex paint |
US6531223B1 (en) | 1998-03-11 | 2003-03-11 | The Sherwin-Williams Company | Primerless latex paint with tannin blocking |
DE19811314A1 (en) | 1998-03-16 | 1999-09-23 | Basf Ag | Aqueous, pigment containing composition useful for production of dispersion dyes |
US6103316A (en) | 1998-07-17 | 2000-08-15 | 3M Innovative Properties Company | Method of making electron beam polymerized emulsion-based acrylate pressure sensitive adhesives |
DE19857876A1 (en) | 1998-12-15 | 2000-06-21 | Basf Ag | Aqueous polymer dispersion, especially for adhesives, contains different polymers made by sequential polymerization of monomer mixtures containing acid monomers, with addition of base between stages |
TW510916B (en) | 1998-12-21 | 2002-11-21 | Bayer Ag | Aqueous reacitve filler compositions |
DE19908183A1 (en) | 1999-02-25 | 2000-08-31 | Basf Ag | Aqueous polymer dispersions |
FR2793801A1 (en) | 1999-05-21 | 2000-11-24 | Atofina | Protective-insulating coating for various surfaces is applied by treatment of surface to be coated with a dispersion containing hydro-dispersible polycondensate and acrylic, vinyl and-or styrene polymers |
FR2794971B1 (en) | 1999-06-18 | 2003-08-29 | Oreal | HAIR COSMETIC COMPOSITION IN THE FORM OF A WATER-IN-SILICONE EMULSION COMPRISING AT LEAST ONE FIXING POLYMER |
DE19939325A1 (en) | 1999-08-19 | 2001-02-22 | Basf Ag | Aqueous copolymer dispersion, useful for the production of adhesives, is prepared by radical, emulsion polymerization of at least two different monomers with a varied rate of initiator addition |
FR2797633A1 (en) | 1999-08-19 | 2001-02-23 | Atofina | Polymer preparation comprises radical polymerization in aqueous phase of hydrosoluble monomers |
US6245141B1 (en) | 1999-10-06 | 2001-06-12 | Joseph Kennedy Walker, Jr. | Tannin stain inhibiting coating composition |
US6534590B1 (en) | 1999-10-29 | 2003-03-18 | Dow Corning Toray Silicone Co., Ltd. | Silicone-grafted vinyl copolymer emulsion composition |
DE19962568C2 (en) | 1999-12-23 | 2002-06-20 | Wacker Polymer Systems Gmbh | Process for the preparation of polyvinyl alcohol-stabilized 1,3-diene (meth) acrylic acid ester copolymers |
ATE325136T1 (en) | 2000-02-16 | 2006-06-15 | Nuplex Resins Bv | AQUEOUS DISPERSIONS OF POLYMER PARTICLES WITH GLASS TRANSITION TEMPERATURE GRADIENT |
FR2806089B1 (en) | 2000-03-09 | 2002-05-24 | Atofina | USE OF A POLYMER BASED ON IMIDIZED MALEIC ANHYDRIDE IN SURFACE TREATMENT OR COATING COMPOSITIONS AND IN INKS AND VARNISHES |
WO2001070854A1 (en) | 2000-03-24 | 2001-09-27 | Daikin Industries, Ltd. | Seal ring |
EE200200691A (en) | 2000-06-13 | 2004-06-15 | Akzo Nobel N.V. | An aqueous binder composition |
JP2002088266A (en) | 2000-09-18 | 2002-03-27 | Nippon Shokubai Co Ltd | Aqueous resin composition |
KR100827902B1 (en) | 2000-11-10 | 2008-05-07 | 바스프 에스이 | Acrylate polymers based on tert-butyl acrylate and/or tert-butyl methacrylate |
US6461728B2 (en) | 2000-12-29 | 2002-10-08 | 3M Innovative Properties Company | Gamma radiation polymerized emulsion-based (meth)acrylate pressure sensitive adhesives and methods of making and using same |
WO2002081561A1 (en) | 2001-04-04 | 2002-10-17 | Kaneka Corporation | Thermoplastic resin composition and elastomer composition |
US6716949B2 (en) | 2001-09-20 | 2004-04-06 | Hewlett-Packard Development Company, L.P. | Amphipathic polymer particles and methods of manufacturing the same |
DE10132614A1 (en) | 2001-07-05 | 2003-01-16 | Polymerlatex Gmbh & Co Kg | Process for the preparation of protective colloid-stabilized, emulsifier-free, aqueous dispersions |
US6533856B1 (en) | 2001-08-29 | 2003-03-18 | Hammond Group, Inc. | Tannin stain inhibitor comprising an aluminate salt complexing agent |
EP1302515B1 (en) | 2001-10-01 | 2008-08-06 | Rohm And Haas Company | Coating composition based on a bimodal emulsion copolymer, methods of blocking stains, improving hiding, improving block resistance and improving shear stability |
US6930143B2 (en) | 2001-11-01 | 2005-08-16 | Arco Chemical Technology, L.P. | Acrylic latex composition |
EP1316591B1 (en) | 2001-11-28 | 2006-03-01 | Rohm And Haas Company | Aqueous coating composition containing ion exchange resins |
DE10158652A1 (en) | 2001-11-30 | 2003-06-12 | Basf Ag | Aqueous polymer dispersion and its use as a water vapor barrier |
NO20020846L (en) | 2002-02-21 | 2003-08-22 | Jotun As | Self-polishing antifouling paint |
DE10218570B4 (en) | 2002-04-26 | 2007-10-18 | Lohmann Gmbh & Co Kg | Acrylate copolymers and PSAs obtainable therefrom for bonding low-energy surfaces and their use |
AU2003281534A1 (en) | 2002-07-23 | 2004-02-09 | Kolon Industries Inc. | Preparation of acrylic polymer sol for coating |
US7183358B2 (en) | 2002-07-25 | 2007-02-27 | Wacker Polymer Systems Gmbh & Co. Kg | Hydrophobically modified polymers |
DE10248879A1 (en) | 2002-10-18 | 2004-04-29 | Basf Ag | Aqueous polymer dispersions containing alkyldiketenes, process for their preparation and their use |
MY134362A (en) | 2002-11-20 | 2007-12-31 | Efka Additives B V | Aqueous emulsion polymer as dipersant |
DE10260065A1 (en) | 2002-12-19 | 2004-07-01 | Röhm GmbH & Co. KG | Core-shell particles for toughening of poly (meth) acrylate molding compounds |
US7332046B2 (en) | 2003-09-26 | 2008-02-19 | Eastman Chemical Company | Methods of blocking stains on a substrate to be painted, and composites suitable for use in such methods |
KR100775564B1 (en) | 2003-09-30 | 2007-11-09 | 니폰 쇼쿠바이 컴파니 리미티드 | Aqueous emulsion for vibration damping materials |
ATE441676T1 (en) | 2003-12-09 | 2009-09-15 | Basf Se | ANIONIC AMPHOLYTIC COPOLYMERS |
EP1694728B1 (en) | 2003-12-09 | 2008-08-13 | Basf Se | Copolymers based on tert-butyl(meth)acrylate and use thereof in hairsprays |
DE102004002650A1 (en) | 2004-01-16 | 2005-08-11 | Basf Ag | Acrylate polymers based on tert-butyl acrylate for use in spray formulations |
AU2005206306B2 (en) | 2004-01-22 | 2011-09-29 | Nuplex Resins B.V. | Stain blocking water borne coating composition |
DE102004035937A1 (en) | 2004-07-23 | 2006-02-16 | Röhm GmbH & Co. KG | Plastisols with reduced water absorption |
DE102005000824A1 (en) | 2005-01-05 | 2006-07-13 | Consortium für elektrochemische Industrie GmbH | Nanoparticle-containing organocopolymers |
RU2007132228A (en) | 2005-01-28 | 2009-03-10 | БАСФ Акциенгезельшафт (DE) | APPLICATION OF EMULSION TYPE OF WATER IN WATER POLYMERS AS A THICKENER IN COSMETIC COMPOSITIONS |
US20060177649A1 (en) | 2005-02-07 | 2006-08-10 | Clark Mark D | Methods of blocking stains on a substrate to be painted, and composites suitable for use in such methods |
US20060235131A1 (en) | 2005-04-15 | 2006-10-19 | Hughes Kathleen A | Process for preparing aqueous dispersions of multistage emulsion polymers |
DE102005055793A1 (en) | 2005-11-21 | 2007-05-24 | Röhm Gmbh | Transparent TPU (thermoplastic polyurethanes) / PMMA (polymethyl (meth) acrylate) Blends with improved impact resistance |
DE102005062027A1 (en) | 2005-12-22 | 2007-06-28 | Basf Ag | Aqueous dispersions of polymers containing a fluorescent dye, process for their preparation and their use for marking materials |
FR2897870A1 (en) | 2006-02-27 | 2007-08-31 | Cray Valley S A Sa | Aqueous polymer nanocomposite dispersion, useful e.g. in coating composition, particularly protective coating composition e.g. as varnishes, comprises polymerized product of monomers and an aqueous dispersion of silica nanoparticles |
CN101501088B (en) | 2006-06-06 | 2011-11-30 | 道康宁公司 | A silicone acrylate hybrid composition |
FR2903409A1 (en) | 2006-07-04 | 2008-01-11 | Solvay | Polymer production comprises dispersion polymerization of an ethylenically unsaturated monomer in the presence of a radical generator, iodine and a water-soluble oxidizing agent |
US8303943B2 (en) | 2006-09-15 | 2012-11-06 | Basf Se | Ampholytic copolymer based on quaternized nitrogen-containing monomers |
JP5493248B2 (en) | 2007-04-25 | 2014-05-14 | 日油株式会社 | Method for producing core-shell fine particles and method for producing intermediates thereof |
US8153721B2 (en) | 2007-06-11 | 2012-04-10 | Basf Se | Process for the preparation of an aqueous polymer dispersion |
US8912273B2 (en) | 2008-06-17 | 2014-12-16 | Basf Se | Process for the preparation of an aqueous polymer dispersion |
US20100047598A1 (en) | 2008-08-25 | 2010-02-25 | Reichhold, Inc. | Coating compositions and methods of blocking tannin migration |
US9238747B2 (en) | 2008-11-17 | 2016-01-19 | Basf Se | Stain blocking compositions |
US8568750B2 (en) | 2009-03-30 | 2013-10-29 | Sekisui Plastics Co., Ltd. | Deformed shaped particles and method for producing the same |
WO2010142568A1 (en) | 2009-06-08 | 2010-12-16 | Basf Se | Method for producing a swelling nonwoven fabric |
EP2475692B1 (en) | 2009-09-09 | 2015-04-29 | Basf Se | Method for producing an aqueous binding agent dispersion |
CN102115630A (en) | 2009-12-31 | 2011-07-06 | 广东华润涂料有限公司 | Aqueous sealant system, wood product and method for sealing wood substrate |
EP2531567A2 (en) | 2010-02-03 | 2012-12-12 | Basf Se | Stain blocking compositions including an alkyl amide |
US8992708B2 (en) | 2010-04-09 | 2015-03-31 | Basf Se | Use of synthetic adhesives in the manufacture of corrugated fiberboard |
US8637160B2 (en) | 2010-06-14 | 2014-01-28 | Basf Se | Polymer dispersions of vinylaromatic compounds and acrylate monomers prepared in the presence of seed latex and carbohydrate compounds |
KR101984800B1 (en) | 2010-07-09 | 2019-05-31 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | Structured acrylate copolymer thickners |
TWI408147B (en) | 2010-10-15 | 2013-09-11 | Champward Chemical Ind Co Ltd | A polymerization method for acrylic latex without emulisifier |
US8691907B2 (en) | 2010-11-23 | 2014-04-08 | Valspar Sourcing, Inc. | Water-borne primer |
DE102011077510A1 (en) | 2011-06-14 | 2012-12-20 | Tesa Se | Primer for improving the adhesion of adhesive tapes to hard-to-bond plastics and metals |
CA2846825A1 (en) | 2011-08-30 | 2013-03-07 | Basf Se | Water-based polymer emulsions for opaque films and coatings applications on flexible substrates |
EP2794671B1 (en) | 2011-12-22 | 2021-04-21 | Celanese Sales Germany GmbH | Polymer dispersions, their preparation and use |
EP2814850B1 (en) | 2012-02-14 | 2017-04-12 | Basf Se | Aqueous polymer dispersion obtainable by free-radically initiated emulsion polymerization in the presence of lignosulfonate |
WO2013147701A1 (en) | 2012-03-29 | 2013-10-03 | Pcts Specialty Chemicals Pte Ltd | Aqueous cationic polyurethane dispersions and their uses |
US20130288067A1 (en) | 2012-04-25 | 2013-10-31 | Kop-Coat, Inc. | Compositions and methods for resisting discoloration of wood and treated wood |
EP2953982A1 (en) | 2013-02-07 | 2015-12-16 | Covestro Deutschland AG | Method for the production of abs compositions having an improved surface |
JP6359953B2 (en) | 2013-11-07 | 2018-07-18 | 株式会社日本触媒 | Film forming aid |
FR3031106B1 (en) | 2014-12-24 | 2017-02-03 | Arkema France | MULTIPHASE POLYMER COMPOSITION, PROCESS FOR PREPARING THE SAME, USE THEREOF, AND COMPOSITION COMPRISING THE SAME |
JP6443302B2 (en) | 2015-10-30 | 2018-12-26 | コニカミノルタ株式会社 | Method for producing porous resin particles |
EP3400268B1 (en) | 2016-02-12 | 2020-10-14 | Nanoco Technologies Ltd | Highly stable quantum dot-containing polymer films |
CN109071733B (en) * | 2016-03-18 | 2022-03-29 | 巴斯夫欧洲公司 | Finely divided aqueous multistage polymer dispersions, method for the production thereof and use thereof as adhesives |
CN110669161A (en) * | 2019-10-16 | 2020-01-10 | 佛山市顺德区巴德富实业有限公司 | Lasting self-cleaning core-shell acrylic emulsion for stone-like paint and preparation method thereof |
-
2021
- 2021-02-18 WO PCT/US2021/018494 patent/WO2021168062A1/en unknown
- 2021-02-18 EP EP21756266.9A patent/EP4107229A4/en active Pending
- 2021-02-18 CA CA3168208A patent/CA3168208A1/en active Pending
- 2021-02-18 US US17/179,007 patent/US11180665B2/en active Active
- 2021-10-22 US US17/508,881 patent/US11649361B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07148459A (en) * | 1993-04-26 | 1995-06-13 | Rohm & Haas Co | Improved coating method |
JPH08225767A (en) * | 1994-10-28 | 1996-09-03 | Hoechst Ag | Water-base dispersion for primer |
US20020004552A1 (en) * | 2000-04-26 | 2002-01-10 | Hai Deng | Aqueous stain-blocking coating composition |
WO2004018575A1 (en) * | 2002-08-22 | 2004-03-04 | Mitsubishi Rayon Co., Ltd. | Primer composition for coating |
US20120121921A1 (en) * | 2009-07-22 | 2012-05-17 | Basf Se | Aqueous polymer dispersion as a binding agent for plasters and coating materials having improved fire behavior |
WO2011073164A1 (en) * | 2009-12-17 | 2011-06-23 | Akzo Nobel Coatings International B.V. | Stain-blocking aqueous coating composition |
CN104341547A (en) * | 2013-07-29 | 2015-02-11 | 上海富臣化工有限公司 | Polyacrylic ester sealing emulsion and preparation method thereof |
JP2016535691A (en) * | 2013-11-08 | 2016-11-17 | ベーカー ギウリニ ゲゼルシャフト ミット ベシュレンクテル ハフツングBK Giulini GmbH | Means and method for preventing tannin migration from wood |
Non-Patent Citations (1)
Title |
---|
See also references of EP4107229A4 * |
Also Published As
Publication number | Publication date |
---|---|
CA3168208A1 (en) | 2021-08-26 |
EP4107229A1 (en) | 2022-12-28 |
EP4107229A4 (en) | 2024-03-06 |
US20220154008A1 (en) | 2022-05-19 |
US11649361B2 (en) | 2023-05-16 |
US20210261786A1 (en) | 2021-08-26 |
US11180665B2 (en) | 2021-11-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1302515B1 (en) | Coating composition based on a bimodal emulsion copolymer, methods of blocking stains, improving hiding, improving block resistance and improving shear stability | |
US9096753B2 (en) | Aqueous binder composition comprising oligomers | |
AU2016219641B2 (en) | High block, tack and scrub resistant coating composition | |
EP1926787B2 (en) | Method to increase resistance against stain penetration of aqueous coating compositions | |
CN110088150A (en) | Aqueous polymer dispersions and water-based paint compositions comprising it | |
EP3167020B1 (en) | Sequentially polymerized hybrid latex | |
CN104745011B (en) | Aqueous stain blocking coating compositions | |
EP3662022B1 (en) | Aqueous coating composition | |
CN109153876A (en) | Aqueous polymer dispersions and water-based paint compositions comprising it | |
US11649361B2 (en) | Stain-blocking polymers, primers, kits, and methods | |
EP3472250B1 (en) | Coating composition with improved liquid stain repellency | |
EP3688092B1 (en) | Aqueous polymer composition | |
EP3966260B1 (en) | Aqueous polymer latex | |
US8691907B2 (en) | Water-borne primer | |
BR112020025078A2 (en) | aqueous dispersion, aqueous dispersion preparation process, and aqueous coating composition | |
US9617447B2 (en) | Use of multi-stage polymerizate dispersions to coat metal sheets | |
US20240067830A1 (en) | Stain-blocking paints, kits, and methods | |
US20220275208A1 (en) | Aqueous dispersion of polymeric particles | |
EP4025644B1 (en) | Aqueous polymer dispersion |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21756266 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 3168208 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2021756266 Country of ref document: EP Effective date: 20220921 |