NZ614963B2 - Aqueous multistage polymer dispersion, process for its preparation and use thereof as binder for coating substrates - Google Patents
Aqueous multistage polymer dispersion, process for its preparation and use thereof as binder for coating substrates Download PDFInfo
- Publication number
- NZ614963B2 NZ614963B2 NZ614963A NZ61496312A NZ614963B2 NZ 614963 B2 NZ614963 B2 NZ 614963B2 NZ 614963 A NZ614963 A NZ 614963A NZ 61496312 A NZ61496312 A NZ 61496312A NZ 614963 B2 NZ614963 B2 NZ 614963B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- optionally
- acrylate
- stage
- atoms
- meth
- Prior art date
Links
- 239000004815 dispersion polymerization Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 22
- 239000011248 coating agent Substances 0.000 title claims description 13
- 238000000576 coating method Methods 0.000 title claims description 13
- 239000011230 binding agent Substances 0.000 title description 13
- 239000000758 substrate Substances 0.000 title description 8
- 238000002360 preparation method Methods 0.000 title description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 91
- -1 vinyl halides Chemical class 0.000 claims abstract description 72
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 125000004432 carbon atoms Chemical group C* 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- OMNKZBIFPJNNIO-UHFFFAOYSA-N N-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 31
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 17
- QYKIQEUNHZKYBP-UHFFFAOYSA-N vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002825 nitriles Chemical class 0.000 claims abstract description 13
- 150000001298 alcohols Chemical class 0.000 claims abstract description 12
- 230000002209 hydrophobic Effects 0.000 claims abstract description 12
- 125000003010 ionic group Chemical group 0.000 claims abstract description 12
- 229920001567 Vinyl ester Polymers 0.000 claims abstract description 11
- 150000003857 carboxamides Chemical class 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 11
- 230000005591 charge neutralization Effects 0.000 claims abstract description 11
- 230000001264 neutralization Effects 0.000 claims abstract description 11
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 11
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims abstract description 10
- GZFANJYDVVSIMZ-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCCCOC(=O)C(C)=C GZFANJYDVVSIMZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- YHSYGCXKWUUKIK-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C=C YHSYGCXKWUUKIK-UHFFFAOYSA-N 0.000 claims abstract description 9
- FHPDNLOSEWLERE-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCCOC(=O)C(C)=C FHPDNLOSEWLERE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004971 Cross linker Substances 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 8
- 230000003472 neutralizing Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- 238000006116 polymerization reaction Methods 0.000 claims description 70
- 239000006185 dispersion Substances 0.000 claims description 45
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 31
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 24
- 239000003973 paint Substances 0.000 claims description 21
- 239000000049 pigment Substances 0.000 claims description 19
- IBVAQQYNSHJXBV-UHFFFAOYSA-N Adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 14
- 239000002023 wood Substances 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 9
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N 2-cyanopropene-1 Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N Crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N Itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- ZUZSFMQBICMDEZ-UHFFFAOYSA-N prop-1-enylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CC=CC1=CC=CC=C1 ZUZSFMQBICMDEZ-UHFFFAOYSA-N 0.000 claims 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims 1
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 description 55
- 239000007864 aqueous solution Substances 0.000 description 48
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 37
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 37
- 235000011114 ammonium hydroxide Nutrition 0.000 description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 31
- 239000008240 homogeneous mixture Substances 0.000 description 31
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 27
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 27
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 26
- 239000007787 solid Substances 0.000 description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- 239000000523 sample Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000033228 biological regulation Effects 0.000 description 14
- 239000012456 homogeneous solution Substances 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 239000002562 thickening agent Substances 0.000 description 10
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 8
- 230000001681 protective Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- FQPSGWSUVKBHSU-UHFFFAOYSA-N Methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 230000000903 blocking Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tBuOOH Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 3
- TYQCGQRIZGCHNB-JLAZNSOCSA-N L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-Butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- RXBOCDZLKBPILN-UHFFFAOYSA-N 2-propylheptyl prop-2-enoate Chemical compound CCCCCC(CCC)COC(=O)C=C RXBOCDZLKBPILN-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N Aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N Antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229960003563 Calcium Carbonate Drugs 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N Glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L Magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N Propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- JXAZAUKOWVKTLO-UHFFFAOYSA-L Sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 241000282485 Vulpes vulpes Species 0.000 description 2
- XHTOIFCGKIBYRK-UHFFFAOYSA-M [O-]C(=O)C(C)=CNC(N)=O Chemical compound [O-]C(=O)C(C)=CNC(N)=O XHTOIFCGKIBYRK-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000460 iron oxide Inorganic materials 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000011776 magnesium carbonate Substances 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 239000002609 media Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000003638 reducing agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000087 stabilizing Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000002522 swelling Effects 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N t-BuOH Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229940071127 thioglycolate Drugs 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229920003176 water-insoluble polymer Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ATXLALDFCMZNHY-HTXNQAPBSA-N (1E)-1-[(4-methyl-2-nitrophenyl)hydrazinylidene]naphthalen-2-one Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N\N=C\1C2=CC=CC=C2C=CC/1=O ATXLALDFCMZNHY-HTXNQAPBSA-N 0.000 description 1
- ACHQDMGGRZPFAW-VLGSPTGOSA-N (1Z)-1-[(4-nitrophenyl)hydrazinylidene]naphthalen-2-one Chemical compound C1=CC([N+](=O)[O-])=CC=C1N\N=C/1C2=CC=CC=C2C=CC\1=O ACHQDMGGRZPFAW-VLGSPTGOSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- BSSNZUFKXJJCBG-OWOJBTEDSA-N (E)-but-2-enediamide Chemical compound NC(=O)\C=C\C(N)=O BSSNZUFKXJJCBG-OWOJBTEDSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- BSSNZUFKXJJCBG-UPHRSURJSA-N (Z)-but-2-enediamide Chemical compound NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 0.000 description 1
- QFXBYZKQOKCTQA-UHFFFAOYSA-N (carbamoylamino) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ONC(N)=O QFXBYZKQOKCTQA-UHFFFAOYSA-N 0.000 description 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-Dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-Propanediol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N 1,6-Hexanediol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N 1-(2-hydroxypropylamino)propan-2-ol Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
- DMADTXMQLFQQII-UHFFFAOYSA-N 1-decyl-4-ethenylbenzene Chemical compound CCCCCCCCCCC1=CC=C(C=C)C=C1 DMADTXMQLFQQII-UHFFFAOYSA-N 0.000 description 1
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical compound CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- QKWWDTYDYOFRJL-UHFFFAOYSA-N 2,2-dimethoxyethanamine Chemical compound COC(CN)OC QKWWDTYDYOFRJL-UHFFFAOYSA-N 0.000 description 1
- YVLHRYOHNHUVOA-UHFFFAOYSA-N 2,2-dimethylpropane-1,1-diamine Chemical compound CC(C)(C)C(N)N YVLHRYOHNHUVOA-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Acrylamido-2-methylpropane sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- BPGIOCZAQDIBPI-UHFFFAOYSA-N 2-ethoxyethanamine Chemical compound CCOCCN BPGIOCZAQDIBPI-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- SQVSEQUIWOQWAH-UHFFFAOYSA-N 2-hydroxy-3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCC(O)CS(O)(=O)=O SQVSEQUIWOQWAH-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N 2-mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- JGBOVFKUKBGAJQ-UHFFFAOYSA-N 2-methylidenebutanediamide Chemical compound NC(=O)CC(=C)C(N)=O JGBOVFKUKBGAJQ-UHFFFAOYSA-N 0.000 description 1
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical class [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- YOOSAIJKYCBPFW-UHFFFAOYSA-N 3-[4-(3-aminopropoxy)butoxy]propan-1-amine Chemical compound NCCCOCCCCOCCCN YOOSAIJKYCBPFW-UHFFFAOYSA-N 0.000 description 1
- ATBDZSAENDYQDW-UHFFFAOYSA-N 3-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=C)=C1 ATBDZSAENDYQDW-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- GICMHQJTKXNMGB-UHFFFAOYSA-N 4-(5-methoxy-1-benzofuran-2-yl)aniline Chemical compound C=1C2=CC(OC)=CC=C2OC=1C1=CC=C(N)C=C1 GICMHQJTKXNMGB-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- 230000035533 AUC Effects 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M Aliquat 336 Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N Benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- SCARZVOSYNHLGX-UHFFFAOYSA-N C(CC(=O)C)(=O)O[NH-] Chemical class C(CC(=O)C)(=O)O[NH-] SCARZVOSYNHLGX-UHFFFAOYSA-N 0.000 description 1
- 229960005069 Calcium Drugs 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M Cetrimonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 229960002887 Deanol Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N Diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N Dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N Dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 229940012017 Ethylenediamine Drugs 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N Glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 229940015043 Glyoxal Drugs 0.000 description 1
- 241000408710 Hansa Species 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N Hexamethylenediamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 241000282619 Hylobates lar Species 0.000 description 1
- 229940097275 Indigo Drugs 0.000 description 1
- 240000007871 Indigofera tinctoria Species 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229940118019 Malondialdehyde Drugs 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N Methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N N',N'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-Butylamine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229940117969 NEOPENTYL GLYCOL Drugs 0.000 description 1
- HTSABAUNNZLCMN-UHFFFAOYSA-F Paris Green Chemical compound [Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.CC([O-])=O.CC([O-])=O HTSABAUNNZLCMN-UHFFFAOYSA-F 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N Phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920001451 Polypropylene glycol Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N Semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 241000238370 Sepia Species 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N Thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N Tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N Trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N Vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N Vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- SEWSAELRCXMQGI-UHFFFAOYSA-N benzene-1,2-dicarbonyl azide Chemical compound [N-]=[N+]=NC(=O)C1=CC=CC=C1C(=O)N=[N+]=[N-] SEWSAELRCXMQGI-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000001419 dependent Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion media Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N ethyl amine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical class C(C1CO1)* 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- GCBGNGBXQQLAFD-UHFFFAOYSA-N hexanedioyl diazide Chemical compound [N-]=[N+]=NC(=O)CCCCC(=O)N=[N+]=[N-] GCBGNGBXQQLAFD-UHFFFAOYSA-N 0.000 description 1
- LTEQMZWBSYACLV-UHFFFAOYSA-N hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- VRWKTAYJTKRVCU-UHFFFAOYSA-N iron(6+);hexacyanide Chemical compound [Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] VRWKTAYJTKRVCU-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 229940113083 morpholine Drugs 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- VSVCAMGKPRPGQR-UHFFFAOYSA-N propan-2-one;sulfurous acid Chemical compound CC(C)=O.OS(O)=O VSVCAMGKPRPGQR-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- ZKODLPLYXXUCHB-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;hydrate Chemical compound O.[Na+].OCS([O-])=O ZKODLPLYXXUCHB-UHFFFAOYSA-M 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 201000009594 systemic scleroderma Diseases 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- KWXLCDNSEHTOCB-UHFFFAOYSA-J tetrasodium;1,1-diphosphonatoethanol Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P(=O)([O-])C(O)(C)P([O-])([O-])=O KWXLCDNSEHTOCB-UHFFFAOYSA-J 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- RRLMGCBZYFFRED-UHFFFAOYSA-N undecyl prop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C=C RRLMGCBZYFFRED-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
- B27K3/153—Without in-situ polymerisation, condensation, or cross-linking reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The disclosure relates to a process for preparing a polymer dispersion obtained by at least two-stage emulsion polymerization. The first stage comprises forming in an aqueous medium a first polymer having a glass transition temperature of more than 50°C and a weight-average molecular weight of between 5 and 100 kDa is prepared by free-radical emulsion polymerization from a first composition comprising hydrophilic and hydrophobic monomers, comprising (A1) at least one (meth)acrylic acid alkyl ester, (B1) optionally at least one vinylaromatic having up to 20 C atoms, (C1) optionally at least one free-radically polymerizable compound selected from the 15 group consisting of ethylenically unsaturated nitriles having up to 20 C atoms, vinyl esters of carboxylic acids comprising up to 20 C atoms, vinyl halides having up to 10 C atoms, and vinyl ethers of alcohols containing 1 to 10 C atoms, (D1) at least one a,B-ethylenically unsaturated carboxylic acid, or a vinyl monomer with latent ionic groups, (E1) optionally at least one crosslinker, (F1) at least one compound selected from the group consisting of 2-(2-oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureido(meth)acrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (OAAM), and 25 diacetonemethacrylamide, (G1) optionally at least one compound having a (meth)acrylate group and an epoxy group, and (H1) optionally at least one a,B-ethylenically unsaturated carboxamide, in the presence of at least one initiator, at least one emulsifier, and at least one chain transfer agent, neutralization to a pH of at least 4.5 of the particles thus formed, using a base (neutralizing agent), followed by free-radical polymerization of hydrophobic and hydrophilic monomers in a following stage, in the presence of the copolymer prepared in the first stage, from (A2) at least one (meth)acrylic acid alkyl ester, (B2) optionally at least one vinylaromatic having up to 20 C atoms, (C2) optionally at least one free-radically polymerizable compound selected from the group consisting of ethylenically unsaturated nitriles having up to 20 C atoms, vinyl esters of carboxylic acids comprising up to 20 C atoms, vinyl halides having up to 10 C atoms, and vinyl ethers of alcohols containing 1 to 10 C atoms, (02) optionally at least one a,B-ethylenically unsaturated carboxylic acid, or a vinyl monomer with latent ionic groups, (E2) optionally at least one crosslinker, and (F2) optionally at least one compound selected from the group consisting of 2-(2- 5 oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureido(meth)acrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (OAAM), anddiacetonemethacrylamide, (G2) optionally at least one compound having a (meth)acrylate group and an epoxy group, and (H2) optionally at least one a,B-ethylenically unsaturated carboxamide, with the proviso that the polymer of the 2nd stage is more hydrophobic than that of the 1st stage, and the glass transition temperature of the second stage is at least 50°C lower than that of the first stage. en 5 and 100 kDa is prepared by free-radical emulsion polymerization from a first composition comprising hydrophilic and hydrophobic monomers, comprising (A1) at least one (meth)acrylic acid alkyl ester, (B1) optionally at least one vinylaromatic having up to 20 C atoms, (C1) optionally at least one free-radically polymerizable compound selected from the 15 group consisting of ethylenically unsaturated nitriles having up to 20 C atoms, vinyl esters of carboxylic acids comprising up to 20 C atoms, vinyl halides having up to 10 C atoms, and vinyl ethers of alcohols containing 1 to 10 C atoms, (D1) at least one a,B-ethylenically unsaturated carboxylic acid, or a vinyl monomer with latent ionic groups, (E1) optionally at least one crosslinker, (F1) at least one compound selected from the group consisting of 2-(2-oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureido(meth)acrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (OAAM), and 25 diacetonemethacrylamide, (G1) optionally at least one compound having a (meth)acrylate group and an epoxy group, and (H1) optionally at least one a,B-ethylenically unsaturated carboxamide, in the presence of at least one initiator, at least one emulsifier, and at least one chain transfer agent, neutralization to a pH of at least 4.5 of the particles thus formed, using a base (neutralizing agent), followed by free-radical polymerization of hydrophobic and hydrophilic monomers in a following stage, in the presence of the copolymer prepared in the first stage, from (A2) at least one (meth)acrylic acid alkyl ester, (B2) optionally at least one vinylaromatic having up to 20 C atoms, (C2) optionally at least one free-radically polymerizable compound selected from the group consisting of ethylenically unsaturated nitriles having up to 20 C atoms, vinyl esters of carboxylic acids comprising up to 20 C atoms, vinyl halides having up to 10 C atoms, and vinyl ethers of alcohols containing 1 to 10 C atoms, (02) optionally at least one a,B-ethylenically unsaturated carboxylic acid, or a vinyl monomer with latent ionic groups, (E2) optionally at least one crosslinker, and (F2) optionally at least one compound selected from the group consisting of 2-(2- 5 oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureido(meth)acrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (OAAM), anddiacetonemethacrylamide, (G2) optionally at least one compound having a (meth)acrylate group and an epoxy group, and (H2) optionally at least one a,B-ethylenically unsaturated carboxamide, with the proviso that the polymer of the 2nd stage is more hydrophobic than that of the 1st stage, and the glass transition temperature of the second stage is at least 50°C lower than that of the first stage.
Description
PF 70891
, Aqueous multistage polymer sion, process for its ation, and use thereof as binder
for coating substrates
Description
The present invention provides multistage aqueous polymer dispersions which are film-forming
at. low temperatures, exhibit goOdfblocking ance in _a formulation, even at elevated
temperatures, display low foam propensity, and possess good wet adhesion and shelf life,
processes for their preparation, and the use thereof as binders for coating substrates.
Aqueous polymer dispersions are common knowledge.“ They are fluid systems which comprise,
in disperse distribution as a disperse phase in the aqueous dispersion medium, r coils '
which are ed of a ity of intertwined r chains, these coils being ed to as
the polymer matrix or polymer particles. The average diameter of the polymer les is
frequently in the range from 10 to 1000 nm, more preferably in the range from ,30 to 300 nm.
Aqueous polymer dispersions are used as binders across a host of industrial applications.
Where they are used as binders fOr coatings on substrates, one of the important requirements
.of such gs is that they possess high hardness and hence exhibit good scratch resistance
and blocking resistance. For environmental reasons, filming of the binder in the range from < 0
’to 40°C is desired, and so only small amounts of a film-forming assistant, or none, are required.
Another requirement is a high level of fine diviSion. This allows the preparation of transparent
aqueous stains and permits effective penetration of the stain into the substrate, particularly
when the substrate to be coated is wood. '
From EP-B 0 710 680 it is known that, by means of multistage emulsion polymerization, it is
possible to prepare polymer dispersions which have a low minimum film-forming temperature
(MFFT) and form films having high blocking resistance. Such polymer dispersions have an
average polymer particle diameter of < 100 nm. The fine division, however, is not enough in the
majority of cases for the formulation therewith in the wet state ofdesired transparent stains for
wood coatings. Wood stains form coatings on wood that are transparent or semitransparent in
the dry state. They comprise transparent ts (e.g., transparent, ultrafine iron oxide) in so
small an'amount that the structure of the wood is still visible.
Where the particle size of the polymer particles to be ed by means of the radically
initiated aqueous emulsion polymerization is to be set specifically, it is usual to use what is
called a polymer seed, which either has been prepared separately beforehand with-other
monomers (exogenous polymer seed) or which has been generated by partial rization of
the rsvto be rized, in situ; Particularly in the context of the preparation of finely
40 divided r dispersions, it is preferred to use this in sifu polymer seed.
The preparation of an aqueous polymer dispersion using an in situ polymer seed is familiar to
the skilled person (see, for example, DE—A 196 09 509, EP-A , EP—A 710 680, EP-A 1
125 949,'EP—A 1. 294 816, EP-A 1 614 732, WO-A 03/29300) and is generally accomplished by
45 introducing, before the emulsion rization proper, a small portion of one of the monomers
PF 70891
used for the emulsion polymerization, or of the monomer mixture used for the emulsion
polymerization, as an initial charge in the aqueous rization , and subjecting it to
free-radical polymerization in the presence of a relatively large ty of emulsifier. lf
especially finely divided polymer dispersions are needed, a ularly large quantity of
emulsifier is required. The foam-forming propensity of the polymer dispersions, which as a result
are very rich in emulsifier, is high.
One elegant way 0f saving on emulsifier during preparation and processing, while retaining the
stability, is to prepare "invert" or "inverted" hell polymers. Such polymers were described
1O as far back as in EP 338486, and in references cited therein. in these cases, a carboxyl-rich
monomer composition is first rized by means of a 'conventional' emulsion polymerization
procedure, often in the presence of a small amount of emulsifier and a chain transfer agent,
which, following a 'swelling step' with aqueous alkali (US 5,081,166) or complete neutralization
of the carboxyl groups and dissolution of the polymer particles (EP 758347), functions as a
’15 stabilizer for the next polymerization steps (see also EP 989163, EP 1978044, US
2008/0058473-A1). For polymers of this kind, in the first monomer composition, in general, fairly
high quantities of monomers 'which carry carboxyl groups, or monomers with latent carboxyl
onality, are used. In WO 05/121595, for example, 10% - 70% by weight of latent yl:
functional monomers are used in the first polymerstage, based on 100% by weight of the 1st
stage. If such polymers are used as binders in s formulations, which are often
formulated to a pH > 8 with thickeners, more ularly with te thickeners, in order to
e the desired flow behavidr in the formulations, such high carboxyl functionality results in
instability on the part of such formulations when they are stored, as manifested in an
uncontrolled viscosity increase or sedimentation.
It was an object of the present invention to provide stable polymer dispersions with little
emulsifier for coating compositions which exhibit very good film-forming even at low
temperatures and yet produce films having a high hardness and excellent blocking resistance
and distinguished, furthermore, by good wet adhesion and shelf life.
The object has been achieved by means of a polymer dispersion obtainable by at least two-
stage emulsion polymerization ,
- where first of all in a first stage in aqueous medium a firs-tpolymer in sion in water
and having a glass transition temperature of more than 50°C and a weight—average
molecular weight of n 5 and 100 kDa is prepared by free-radical emulsion
polymerization from a first composition sing hydrophilic and hydrophobic
comprising
(A1) at least one (meth)acrylic acid alkyl ester,
, (B1) optionally at least one vinylaromatic having up to 20 C atoms,
(C1) optionally at least one free-radically polymerizable compound selected from the
group consisting of ethylenically unsaturated nitriles having up to 20 C atoms, vinyl
PF 70891
esters of carboxylic acids comprising up to 20 C atoms, vinyl halides having up to 10
C atoms, and vinyl ethers of alcohols containing 1 to 10 C atoms,
. (D1) at least one a,B-ethylenically unsaturated carboxylic acid, or a vinyl monomer with
latent ionic groups,
(E1) optionally at least one crosslinker,
(F1) at least one compound selected from the group consisting of 2-(2-oxoimidazolidin41-
yl)ethyl (meth)acrylate, 24ureido(meth)acrylate, acetoacetoxyethyl acrylate,
f acetbacetoxypropyl'methacrylate, acetoacetoxybutyl methacrylate, 2-
(acetoacetoxy)ethyl ”methacrylate,, diacetoneacrylamide (DAAM), and
diacetonemethacrylamide,
(G1) optionally at least one nd having a (meth)acrylate group and an epoxy
group, and
(H1) optionally at least one or,B-ethylenically unsaturated carboxamide,
in the presence of at least one initiator, at least one emulsifier, and at least one chain transfer
agent
neutralization to a pH of at least 4.5, preferably greater than 5.5,. of the particles thus
formed, using a base (neutralizing ,
ed by free-radical rization of hydrophobic and hydrophilic monomers in a
following stage, in the presence of thevcopolymer prepared in the first stage, from
(A2) at least one (meth)acrylic acid alkyl ester,
(32) optionally at least one romatic having up to 20 C atoms,
(CZ) optionally at least one adically rizable compound selected from the
group consisting of ethylenically unsaturated nitriles having up to 20 C atoms, vinyl
esters of carboxylic acids comprising up to 20 C atoms, vinyl halides having up to 10
C atoms, and vinyl ethers of alcoholscontaining 1 to 10 C atoms,
(D2) optionally at least one (LB-ethylenically unsaturated carboxylic acid, or a vinyl
monomer with latent ionic groups,
3O (E2) optionally at least one crosSlinker, and
(F2) optionally at least one compOund ed from the group consisting of 2-(2-
oxoimidazolidinyl)ethyl (meth)acrylate, 2-ureido(meth.)acrylate, cetoxyethyl
acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-
(acetoacetoxy)ethyl methacrylate, diacetoneaCrylamide , and
diacetonemethacrylamide,
(G2) optionally at least one compound having a (meth)acrylate group and an epoxy
group, and _
(H2) optionally at least one hylenically unsaturated carboxamide, with the proviso
that the polymer of the 2nd stage is more hydrophobic than that of the 1st stage,
40 and the glass transition temperature of the second stage is at least 50°C lower than
that of the first stage.
PF 70891
The expression "more hydrophobic“ means that the polymer of the 2nd stage must have
significantly lower solubility parameters, as defined in Van Krevelen in rties of
Polymers" (Elsevier Scientific Publishing y, Amsterdam, 1990).
This folloWing stage may be carried out either contionuously, in the form of a single
monomer combination, or else in stages with different ations.
Optionally
_ it is possible subsequently to add, in additiOn, at least one further crosslinking agent.
1O The amount of the at least one emulsifier is 0.1% to 3.5% byweight, based on the total amount
of the free-radically polymerizable rs introduced into the free-radical polymerization in
all stages.
The vinyl monomers used comprise monomers having functional groups such as crosslinking
groups and hydrophilic, water-dispersible groups. Certain functional groups may have more
than one function. (Meth)acrylic acid, for example, is normally used as a water-dispersible
monomer, but here may also act as a crosslinking mondmer, and may react, for example, with
e compounds or carbodiimides.
The invention further provides a coating composition comprising the polymer dispersion of the
invenfion.
In the polymerization it is possible in accordance with the invention to use the following
monomers: .
(Meth)acrylic acid alkyl esters (A1) and (A2)
This encompasses preferably those (meth)acrylic acid alkyl esters whose linear or branched
alkyl radical has 1 to 20 carbon atoms, more preferably 1 to 10, very ably 1 to 8, and more
particularly 1 to 4 carbon atoms.
Examples of (meth)acrylic acid alkyl esters e methyl (meth)acrylate, ethyl acrylate,
n-propyl_(meth)acrylate, n-butyl acrylate, isobutyl (meth)acrylate, secfbutyl
(meth)acrylate, tert-butyl acrylate, yl (meth)acrylate, isopentyl (meth)acrylate, 2-
methylbutyl (meth)acrylate, amyl (meth)acrylate, n—hexyl (meth)acrylate, 2-ethylbutyl
(meth)acrylate, pentyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-
ethylhexyl (meth)acrylate, 2-propylheptyl acrylate, n-decyl (meth)acrylate, undecyl
acrylate, and n-dodecyl (meth)acrylate.
40 Preference is given to methyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-
butyl methacrylate, n—hexyl acrylate, n-octyl te, 2—ethylhexyl acrylate, and 3—propylheptyl
, acrylate.
Also suitable in particular are mixtures of the (meth)acrylic acid alkyl esters.
PF 70891
Vinylaromatics having up to 20 C atoms (B1) and (32)
These are ally substituted aromatic systems having a vinyl group which is in conjugation
to the aromatic ring system. '
Such substituted vinylaromatics have one or more, preferably 1, linear or branched alkyl group
or groups having 1 to 10 carbon atoms, preferably 1 to 6 and more ably 1 to 4 carbon
atoms, it being possible for this or these alkyl groups to be located on the arOmatic or on the
1O vinyl group. Where the substituent is on the ic, the substituent may be located preferably
in ortho- or para-position,” more preferably inpara—position to the vinyl group.
Suitable vinylaromatic nds include vinyltoluene, vinylnaphthalene, d- and p—
styrene, d-butylstyrene, 4—n—butylstyrene, 4—n—decylstyrene, and, preferably, styrene and
ylstyrene.
Free-radically polymerizable compound (C1) and (CZ)
The compounds (C1) and (CZ) are selected from the group consisting of ethylenically
unsaturated nitriles having up to 20 C atoms, vinyl esters of carboxylic acids comprising up to
C atoms, vinyl s having up to 10 C atoms, and vinyl ethers of alcohols comprising 1 to
C atoms, are preferably selected from the group consisting of ethylenically unsaturated
nitriles having up to 20 C atoms and vinyl ethers of alcohols comprising 1 to 10 C atoms, and
more ably are ethylenically unsaturated nitriles having up to 20 C atoms.
Ethylenically unsaturated nitriles having up to 20 C atoms
Examples of ethylenically unsaturated nitriles are fumaronitrile, acrylonitrile, and
methacrylonitrile, preferably acrylonitrile and methacrylonitrile, and more preferably acrylonitrile.
Vinyl esters of carboxylic acids comprising upto 20 C atoms
Vinyl esters of carboxylic acids having 1 to 20 C atoms are, for example, vinyl e, vinyl
stearate, vinyl propionate, Versatic acid vinyl esters, vinyl butyrate, and vinyl acetate, preferably
vinyl acetate.
Vinyl halides having up to 10 C atoms
The vinyl halides are ethylenically unsaturated compounds substituted by chlorine, fluorine or
40 bromine, preferably vinyl chloride and vinylidene chloride.
Vinyl ethers of ls comprising 1 to 10 C atoms
PF 70891
Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether,
isopropyl vinyl ether, n-butyl vinyl ether, tyl vinyl ether, isobutyl vinyl ether, tert—butyl vinyl
ether, and n-octyl vinyl ether. Vinyl ethers of alcohols sing 1 to 4 C atoms are preferred.
d,B-Ethylenically unsaturated carboxylic acid (D1) and (D2)
These are d,B-ethylenically unsaturated carboxylic acids having 3 to 10, preferably 3 to 6, more
preferably 3 to 4 carbon atoms.
1O Optionally the ionic groups may also be latent, as in maleic anhydride, for example, where the
acid functionality is present in the form of an anhydride group.
ence is given to acry|ic acid, crotonic acid or dicarboxylic acids, e.g., itaconic acid,
maleic acid or fumaric acid, more preferably methacrylic acid and acrylic acid.
(Meth)acrylic acid in this description stands for methacrylic acid and acrylic acid.
Crosslinkers (E1) and (E2)
Crosslinkers are those which have at least two free-radically polymerizable double bonds,
preferably 2 to 6, more preferably 2 to 4, very preferably 2 to 3, and more particularly exactly 2.
Examples of di- and poly(meth)acrylates include 1,2—, 1,3-, and 1,4-butanediol diacrylate, 1,2-
and 1,3-propylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,2-ethylene glycol
di(meth)acrylate, neopentylglycol di(meth)acrylate, lene glycoldi(meth)acrylate, triethylene
glycoldi(meth)acrylate, tetraethylene glycoldi(meth)acrylate, trimethylolpropane
tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and pentaerythritol tri- and
tetra(meth)acrylate.
Mention may also be made of divinylbenzene and allyl acrylate.
Compounds (F1) and (F2) are selected from the group consisting of 2-(2-oxolmidazolidin-1—
yl)ethyl (meth)acrylate, 2-ureido(meth)acrylate, N~[2—(2—oxooxazolidinyl)ethyl] methacrylate,
cetoxyethyl acrylate, acethcetoxypropyl methacrylate, acetoacetoxybutyl methacrylate,
2-(acetoacetoxy)ethyl methacrylate, oneacrylamide (DAAM), and
diacetonemethacrylamide.
Preference is given to xoimidazolidinyl)ethyl (meth)acrylate, (acetoacetoxy)ethyl
methacrylate, and diacetoneacrylamide, particular preference to diacetoneacrylamide.
If compounds (F1) and (F2) are used, they are used preferably in the first stage and not in the
second stage; in other words, if the amount of ((F1) + (F2)) 1 0, then preferably the amount of
(F1) at O and (F2) = 0.
PF 70891
(G1) und (G2)
These Compounds comprise at least one compound having a (meth)acrylate and an epoxy
group. Particularly noteworthy are glycidyl acrylate and glycidyl methacrylate, preferably glycidyl
methacrylate.
(H1) and (H2)
These compounds comprise at least one d,B-ethylenically-unsaturated carboxamide.
Particular ence is given to (meth)acrylamide, crotonamide or amides of dicarboxylic acids,
for example, itaconamide, maleamide or fumaramide, more preferably methacrylamide and
acrylamide.
If compounds (H1) and (H2) are used, they are used preferably in thefirst stage and not in the
second stage; in other words, if the amount of ((H1) + (H2)) =4: 0, then preferably the amount of
(H1) at O and (H2) = 0.
It is additionally possible to use in minor amounts, as for e at less than 5% by weight,
preferably less than 3% by weight, more preferably less than 1% by weight, monomers other
than those recited above.
es of these further monomers are phosphorus-containing monomers, examples being
vinylphosphonic acid and allylphosphonic acid. Also suitable are the monoesters and diesters of
phosphonic acid and phosphoric acid with yalkyl (meth)acrylates, especially the
monoesters. Also suitable are diesters of onic acid and phosphoric acid .which are
esterified singly with a hydroxyalkyl acrylate and also singly with a different alcohol, such
as an alkanol. Suitable hydroxyalkyl (meth)acrylates for these esters are those specified as
separate monomers below, especially 2—hydroxyethyl‘ (meth)acrylate, 3-hydroxypropyl
(meth)acrylate, oxybutyl acrylate, etc. Corresponding dihydrogenphosphate ester
monomers comprise phosphoalkyl acrylates, such as 2—phosphoethyl (meth)acrylate,
2—phosphopropyl (meth)acrylate, 3-phosphopropyl (meth)acrylate, obutyl (meth)acrylate,
and 3-phospho—2—hydroxypropyl (meth)acrylate. Also suitable are the esters of phosphonic acid
and phosphoric acid with alkoxylated hydroxyalkyl (meth)acrylates, examples being the
ethylene oxide condensates of (meth)acrylates, such as H20:C(CH3)COO(CH2CH20)nP(OH)2
and H2C;C(CH3)COO(CH20H20),1P(=O)(OH)2, in which n is 1 to 50. Also suitable are phospho-
alkyl crotonates, phosphoalkyl maleates, phosphoalkyl fumarates, phosphodialkyl (meth)-
tes, phosphodialkyl ates, and allyl phosphates. Other suitable monomers containing
phosphorus groups are bed in WO 99/25780 and US 4,733,005, hereby incorporated by
reference. '
Also suitable are vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl
methacrylate, sulfopropyl acrylate, ropyl methacrylate, 2-hydroxy—3-
yloxypropylsulfonic acid, 2-hydroxy-S—methacryloyloxypropylsulfonic acid, styrenesulfonic
acids, and 2-acrylamido—2-methylpropanesulfonic acid. Suitable styrenesulfonic acids and
PF 70891
derivatives thereof are styrenesulfonic acid and styrene-3—sulfonic acid and the alkali metal or
alkaline earth metal salts thereof, e.g., sodium styrenesulfonate and sodium styrene
sulfonate, poly(allyl glycidyl ethers) and es thereof, in the form of varioUs products with
the name Bisomer ® from Laporte Performance Chemicals, UK. These e, for example,
Bisomer ® MPEG 350 MA, a methoxypolyethylene glycol monomethacrylate.
' The functional
groups of the monomers contribute to mediating the latent inkability of the
composition. inking in this case takes place either by reaction with one another or by
addition of a further crosslinking agent. Crosslinking preferably takes place only after actual film
ion. '
in this context it is important not to use too much additional crosslinking agent, since this may
lead to residual crosslinking agent leftovers. Too little crosslinking agent, on the other hand,
’ may lead to a soluble coating.
Functional inker groups are, for example, keto groups, aldehyde groups and/or
acetoacetoxy carbonyl groups, and the formulated crosslinking agents added subsequently may
comprise a polyamine or polyhydrazide such as adipic dihydrazide (ADDH), oxalic dihydrazide,
phthalic azide, terephthalic dihydrazide, isophoronediamine, and 4,7—dioxadecane-1,1-O-
diamine, or a crosslinking agent which carries semicarbazide or hydrazine—functional groups.
Alternatively the polymer could carry hydrazide—functional groups and the subsequently
formulated crosslinking agent could comprise keto-functional groups.
The functional groups may also be carboxyl functions, and the subsequently formulated
crosslinking agent could comprise aziridine groups, epoxide groups or carbodiimide-functional
groups, or the onal groups may be silane-functional groups and the subsequently
formulated crosslinking agent may likewise se silane-functional groups. Functional
groups can also be ureido groups, and the subsequently added crosslinking agent may be a
polyaldehyde, as for example an ialdehyde having one to ten C atoms, such as glyoxal,
glutardialdehyde or malondialdehyde, and/or their s and hemiacetals. See EP 0789724.
Also possible, of course, are ations of the various functional groups and crosslinking
mechanisms.
Examples of vinyl monomers comprising crosslinking groups are allyl, glycidyl or acetoacetoxy
esters, acetoacetoxyamides, .keto— and aldehyde—functional vinyl monomers, ontaining
amides such as diacetoneacrylamide, (meth)acrylic silane monomers.
Preferred vinyl monomers which carry crosslinking groups are acetoacetoxyethyl methacrylate
(AAEM), diacetoneacrylamide (DAAM), and acrylic silane monomers; DAAM is the most
40 preferred.
Preferred crosslinking mechanisms comprise crosslinking of -functional groups and
crosslinking of keto-functional with hydrazide—functional groups.
The most preferred is the combination of DAAM and ADDH crosslinking.
PF 70891
The polymer of the first stage is not soluble but dispersed in water at low pH levels of, for
example, 2 to 3 and with acid groups not neutralized. If base is added during or before and
during the polymerization of the second stage, the hilicity and water-solubility of the first—
stage polymer increases successively in line with the increasing degree of neutralization of the
acid groups. As the hydrophilicity and water-solubility go up, the polymer of the first stage is
able to act increasingly as a protective colloid for the polymer of the second stage and, toward
the end of the polymerization, to stabilize the polymer dispersion with high polymer solids
content. Protective colloids are polymeric compounds which bind large quantities of water on
solvation and arecapable of stabilizing dispersions of water-insoluble polymers.
The polymers of the first stage which become active as protective colloids on neutralization are
used preferably in an amount of 5% to 95%, more ably 7% to 80% and very preferably
% to 50%, by weight, based on 100% by weight of the monomers to be polymerized.
In one red ment the polymer of the first stage is a copolymer
(i) which is used in an amount of 7% to 80% by weight, based on 100 parts by
weight of the total monomers for rization in the first and second stages,
(ii) which is synthesized to an extent of at least, e.g., 50% or' 60% by weight and up to
99% by weight of principal monomers which are selected from the group of the
monomers A1 and B1 and
(iii) 0.1% to 1.0% by weight of at least one d,B-ethylenically unsaturated carboxylic acid,
or vinyl monomer with latent ionic groups (monomers D1),
(iv) 0.1% to 10% by weight of at least one compound selected from the group consisting
of 2-(2—oxoimidazolidin—1-yl)ethyl (meth)acrylate, 2—ureido(meth)acrylate,
acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl
rylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (DAAM) and
onemethacrylamide (monomers F1),
(v) 0% to 10% by weight of at least one compound selected from the group of an 0,8-
ethylenically' rated carboxamide (monomers H1),
,1 E1,
. (vi) 0% to 10% by weight of at least one compound, ed from the monomers C1
and G1,
the ty figures (ii)'to (vi) being based in each case on 100% by weight of the monomers for
polymerization in the first stage.
in one preferred embodiment of the invention at least one molecular weight regulator (chain
transfer agent) is used in the polymerization of the first stage. By this means it is possible to
reduce the molar mass of the emulsion polymer, through a chain termination reaction. The
regulators here are attached to the polymer, generally to the chain end. The amount of the
40 regulators is in particular 0.05 to 4 parts by weight, more preferably 0.05 to 2 parts by ,
per 100 parts by weight of the total monomers for polymerization in the first and second stages.
Suitable regulators are, for example, compounds with a thiOl group such as utyl
mercaptan, alkyl esters of thioglycolic acid, mercaptoethanol, mercaptopropionic acid,
mercaptopropyltrimethoxysilane, and n- or tert-dodecyl mercaptan. The regulators are generally
PF 70891
compounds of low lar weight, having a molar weight of less than 2000, more particularly
less than 1000 g/mol.
The neutralization med Subsequent to the first stage takes place with a base. The base
leads to partial or complete neutralization of the ionic or latently ionic groups of the polymer of
the first stage; it can lead to swelling of the polymer particles, but may also convert them
completely into solution. It is preferred to carry out only a partial neutralization, of up to 80%, for
example, ofthe ionic or_latently ionic groups present. Examples of bases which can be used
include alkali metal or alkaline earth metal compounds such as sodium ide, potassium
1O ide, m hydroxide, magnesium 'oxide,'sodium carbonate; ammonia; primary,
secondary, and tertiary , such as ethylamine, propylamine, opropylamine,
monobutylamine, mine, lamine, dimethylamine, diethylamine, di-n-propylamine,
tributylamine, anolamine, dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine,
dimethylethanolamine, diisopropanolamine, morpholine, ethylenediamine, 2-
diethylaminoethylamine, 2, 3-d-i,aminopropane 1 ,-2Hpropylenediamine
dimethylaminopropylamine, neopentanediamine, hexamethylenediamine, 4,9-dioxadodecane-
1 ,-12diamine, polyethyleneimine or polyvinylamine.
The acid groups of the polymer of the first stage may be neutralized lly or completely with
sUitable bases. It is preferred to use aqueous sodium hydroxide solution, aqueous potassium
hydroxide on or ammonia as neutralizing agent.
In one embodiment of the ion the polymerization of the first stage takes place by means of
the method of the in situ seed mode. For this method, a portion of a monomer or of the
monomer mixture of the first stage, < 35% by weight for example, preferably < 20% by ,
based on the total weight of the rs of the first stage, is included in the initial charge
together with emulsifier, for example < 10% by weight, preferably < 3% by weight, based on the
total weight of the monomers of the first stage, and subjected to initial polymerization by means
of an initiator, after which the remainder of the first stage is metered in.
The monomers used for the polymerization of the second stage comprise preferably to an
extent, of at least 60% by weight, more preferably at least 80% by weight, e.g., from 80% to
100% by weight, more preferably at least..9.0.% by weight, or 100% by , based on the total
amount of the monomers of the second stage, of the principal monomers A2 and/or 82.
Especially preferred are methyl acrylate, methyl methacrylate, ethyl acrylate, n—butyl acrylate, n—
butyl methacrylate, n-hexyl acrylate, octyl acrylate, 2—ethylhexyl acrylate, 2-propylheptyl
acrylate, styrene, and mixtures of these monomers.
The addition of the monomers of the second stage may take placein accordane with a gradient
40 mode. By the gradient mode for the purposes of the present invention is meant an emulsion
polymerization in which one or more monomers are metered in at a nonconstant rate. For
reasons of ease of apparatus operation, in the case of the‘experiments described here, the
rates were varied not continuously (i.e., true gradient) but rather in stages (i.e., interpolated
nt) (in the mathematical sense, therefore, the plot of the metering rate against time
PF 70891
represents a noncontinuous function). Continuous rate changes, however, are in ple also
operable without substantial extra effort or complexity.
In one embodiment, the monomer with at least one acid group that is used in the first stage, D1,
is methacrylic acid; the monomer F1 used is diacetoneacrylamide; and the further monomers
used in the first stage, A1 and/or B1, are selected from 2-ethylhexyl acrylate, n-butyl acrylate, n-
butyl methacrylate, methyl acrylate, methyl methacrylate, e, and a mixture thereof; and at
least 80% by weight of the monomers A2 and/or 82 used in the second. stage are selected from
the group consisting of C1 to C10 alkyl acrylates, C1 to C10 alkyl methacrylates, e, and a
mixture thereof-Subsequently adipic dihydrazide is added as additional crosslinking agent.
The weight-average molecular weight of the monomers of the polymerization of the first stage is
between 5 and 100 kDa, preferably between 10 and 50 kDa. The monomers of the
polymerization of the first stage are selected such that the glass transition temperature
calculated for a polymer prepared from the monomers of the first stage is greater than 50°C,
more particularly in the range from 50°C to 150°C or in the range from 70°C to 125°C.
Through skilful variation in nature and amount of the monomers it is possible in accordance with
the invention for the skilled person to prepare aqerus polymer compositions whose polymers
have a glass transition temperature within the desired range. Rangefinding is possible by
means of the Fox equation. According to Fox (T.G. Fox, Bull. Am. Phys. Soc. 1956 [Ser. ll] 1,
page 123 and in accordance with Ullmann’s EnCyclopadie der technischen Chemie, vol. 19,
page 18, 4th n, Verlag Chemie, Weinheim, 1980), for a calculation of the glass tion
temperature of copolymers, the following holds in good approximation:
1n, = X1/Tg1 + x2/T92 + xnrrgn,
where x1, x2, xn are the mass fractions of monomers 1, 2, n, and T91, T92, Tgn are the
glass transition temperatures of the polymers synthesized in each case only from one of the
monomers 1, 2, n, in degrees . The T9 values for the homopolymers of the majority of
rs are known and are listed in, for example, Ullmann’s Encyclopedia of Industrial
Chemistry, 5th edn., vol. A21, page 169, VCH Weinheim, 1992; other'sources of homopolymer
glass transition temperatures e, for example, J. up,_E..H..lmmergut, Polymer
Handbook, 1St edn., J. Wiley, New York 1966, 2"d edn. J. Wiley, New York 1975, and 3rd edn., J.
Wiley, New York 1989. For ethyl acrylate a figure of -13°C is used.
The rs of the polymerization of the second stage are selected such that the glass
tion temperature calculated for a polymer prepared from the monomers of the second
stage is at least 50°C lower than that of the first stage, preferably in the region of less than
40 10°C, more particularly in the region from 0°C to -80°C.
The weight ratio of the amount of the monomers used in the first stage to the amount of the
monomers used in the second stage is preferably from 5:95 to 95:5 or from 7:93 to 80:20, more
preferably from 10:90 to 50:50.
PF 70891
The polymer dispersion of the invention is prepared by emulsion polymerization. In emulsion
polymerization, ethylenically unsaturated compounds (monomers) are polymerized in water,
lly using ionic and/or nonionic fiers and/or protective colloids, or stabilizers, as
interface-active nds to stabilize the monomer droplets and the polymer particles
subsequently formed from the monomers. In ance with the invention, however, both the
first-stage polymerization and the second-stage polymerization take place with low emulsifiers
content or with complete or virtual absence of emulsifier. Overall, preferably, less than 2.5% by
weight or |eSs than 2.0% by weight of emulsifiers is used, more'particularly less than 1.5% by
1O , based on the solids content of the polymer dispersion. For stabilizing the r
dispersion formed in the second-stage polymerization, the polymer of the first stage is used,
which is converted in situ, by on of neutralizing agent, from a Water-insoluble polymer with
no protective colloid activity into a water-soluble or water-swollen polymer which is active as a
protective colloid. '
The polymer dispersion is prepared typically in the presence of at least one interface-active
compound. A comprehensive description of le protective colloids is found in Houben—
Weyl, Methoden der organischen Chemie, volume XIV/1, Makromolekulare Stoffe
[Macromolecular compounds],.Georg Thieme Verlag, Stuttgart, 1961, pp. 411 to 420. Suitable
fiers are also found in Houben-Weyl, Methoden der organischen Chemie, Band 14/1,
Makromolekulare Stoffe [Macromolecular compounds], Georg Thieme Verlag, Stuttgart, 1961,
pages 192 to 208.
Suitable emulsifiers include anionic, cationic, and nonionic emulsifiers. As interface—active
substances it is red to use emulsifiers, whose relative molecular weights are typically
below those of protective colloids. More particularly it has been found appropriate to use
exclusively anionic emulsifiers, or a combination of at least one anionic fier and at least
one nonionic emulsifier.
Useful nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, examples being
ethoxylated mono-, di-, and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C4-C1o),
ethoxylates of long-chain alcohols (EO : 3 to 100, alkyl l: ), and polyethylene
oxide/polypropylene oxide homopolymers and copolymers. These polymers mprise the
copolymerized alkylene oxide units in random distribution or in the form of blocks. EO/PO block
mers, for example, are very suitable. Preference is given to ethoxylates of long-chain
alkanols (alkyl radical 01-030, average degree of ethoxylation 5 to 100) and, of these, ular
preference to those having a linear C12-C20 alkyl radical and an average degree of ethoxylation
of 10 to 50, and also to lated monoalkylphenols, for use.
40 es of suitable anionic emulsifiers are alkali metal salts and ammonium salts of alkyl
sulfates (alkyl radical: C8-C22), of sulfuric monoesters with ethoxylated alkanols (EO degree: 2 to
50, alkyl radical: 8) and with ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical:
04-09), of alkylsulfonic acids (alkyl radical: C12-C18) and of alkylarylsulfonic acids (alkyl radical:
C9-C18). Other suitable emulsifiers are found in Houben-Weyl, Methoden der organischen
PF 70891
Chemie, volume XIV/1, Makromolekulare Stoffe {Macromolecular nds], Georg-Thieme-
Verlag, Stuttgart, 1961, pp. 192-208. Suitable anionic emulsifiers are likewise
bis(phenylsulfonic acid) ethers and their alkalimetal salts or ammonium salts which carry a C4—
C24 alkyl group on one or both aromatic rings. These compounds are Common knowledge, from
US—A—4,269,749, for example, and are available commercially, in the form, for example, of
Dowfax® 2A1 (Dow Chemical Company).
Suitable cationic emulsifiers are preferably quaternary ammonium halides, examples being
trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium
1O chloride or quaternary compounds of N-C64C2gealkyl7pyridines, —morpholines or -imidazoles, e.g.
N-laurylpyridinium de.
The polymer dispersions may additionally be admixed with customary auxiliaries and additives.
These include, for example, pH modifiers, reducing agents, and bleaches, such as the alkali
metal salts of hydroxymethanesulfinic acid (e.g., Rongalit® C from BASF Aktiengesellschaft),
xing agents, deodorants, odorants, and viscosity modifiers, such as alcohols, e.g.,
glycerol, methanol, ethanol, tert—butanol, glycol, etc. These auxiliaries and ves may be
added to the polymer sions in the initial charge, in one of the feeds, or after the end of the
polymerization.
The neutralization of acid groups in the first polymer is accomplished preferably by at least
partial feed addition of a neutralizing agent before and/or during the polymerization of the
second stage. The lizing agent here may be added in a joint feed with the monomers to
be polymerized, or in a separate feed. After all of the 2nd—stage monomers have been fed in,
there is preferably the amount of neutralizing agent needed to neutralize at least 10%,
preferably 25% to 100% or 50% to 95% acid equivalents present in the polymerization vessel.
The emulsion polymerization of the first and second stages may be initiated using water-soluble
initiators. Water—soluble initiators are, for example, ammonium salts and alkali metal salts of
perododisulfuric acid, e.g., sodium 'peroxodisulfate, hydrogen peroxide or organic peroxides, .
e.g., tert—butyl eroxide. Also suitable as initiators are what are called reduction-oxidation
(redox) tor systems. The redox initiator systems consist of at least one, usually inorganic,
ng agent and one organic or nic oxidizing agent. The oxidizing component '
comprises, for example, the initiators already referred to above for the emulsion polymerization.
The reducing component ses, for e, alkali metal salts of sulfurous acid, such as
sodium sulfite, for example, sodium hydrogensulfite, alkali metal salts ofdisulfurous acid such
as sodium disulfite, bisulfite addition nds of tic aldehydes and ketones, such as
acetone bisulfite, or reducing agents such as ymethanesulfinic acid and its salts, or
ascorbic acid. The redox initiator systems may be used er with e metal compounds
40 whose metallic component is able to occur in a plurality of valence states, Typical redox initiator
systems are, for example, ascorbic acid/iron(ll) e/sodium peroxydisulfate, tert—butyl
hydroperoxide/sodium disulfite, tert-butyl hydroperoxide/Na—hydroxymethanesulfinic acid. The
individual components, the reducing component for example, may also be mixtures, an example
being a e of the sodium salt of hydroxymethanesulfinic acid and sedium disulfite.
PF 70891
The stated initiators are used usually in the form of s solutions, with the lower
concentration being ined by the amount of water acceptable in the dispersion and the
upper concentration-by the lity of the respective compound in water. In general the
concentration of the initiators is 0.1% to 30% by weight, preferably 0.2 to 20% by , more
preferably 0.3% to 10% by weight, based onthe monomers 'to be polymerized. It is also
possible for two or more different initiators to be used for the emulsion polymerization.
In the polymerization of the second stage, the molecular weight regulators (chain transfer,
1O agents) identified above can be used. Preferably, however, the polymerization of the second
stage takes place withoutaddition of further molecular weight tors.
The emulsion polymerization takes place in general at 30 to 130°C, preferably at 50 to 90°C.
The polymerization medium may consist either only of water, or else of mixtures of water and
water-miscible liquids such as methanol. It is red to'use just water. The emulsion
polymerization of the first stage may be carried out as a batch ion or in the form of a feed
process, including stage or gradient regimes.
The emulsion polymerization of the second stage as well may be carried out either as a batch
operation or in the form of a feed process, including stage or nt regimes.
The manner in which the initiator is added to the polymerization vessel in the course of the free-
radical aqueous emulsion polymerization is familiar to a person of ordinary skill in the art. It may .
either be included in its entirety in the initial charge to the polymerization vessel, or else used
continuously or in stages at the rate at which it is ed in the course of the free-radical
aqueous emulsion rization. In each individual case, this will be dependent on the
chemical nature of the initiator system and also on the polymerization temperature. It is
preferred to include part in the initial charge and to supply the remainder at the rate of its
consumption to the polymerization zone. For the removal of residual monomers, it is common
even after the end of the emulsion polymerization proper, in other words after a r
conversion of at least 95%, to add initiator. In the case of the feed process, the individual
components may be added to the. reactor from the top, in the side or from below, h the
reactor bottom. '
Frequently it is advantageous if the aqueous polymer dispersion obtained after the end of the
polymerization stages is subjected to an aftertreatment for the purpose of reducing the residual
monomer content. This aftertreatment takes place chemically, as for example by completion of
the polymerization reaction through the use of a more effective free-radical initiator system
(referred to as post polymerization), and/or physically, as for example by stripping of the
aqueous polymer dispersion using steam or inert gas. Corresponding chemical and/or physical
40 methods are familiar to the skilled person [see, for e, EP-A 771 328, DE-A 196 24 299,
DE-A 196 21 027, DE-A 197 41 184, DE-A197 41 187, DE-A 198 05 122, DE-A198 28 183,
DE-A 198 39 199, DE-A 198 40 586, and 198 47 115]. The ation of chemical and
’ physical after-treatment here affords the advantage that not only the ted ethylenically
unsaturated monomers but also other disruptive VOCs [volatile organic compounds] are
PF 70891
removed from the aqueous polymer dispersion. The dispersions of the ion are preferably
not chemically reated.
’The aqueous polymer dispersions obtainable in accordance with the process of the invention
have polymer particles which possess a weight-average particle diameter DW in the range 3 10
and f 500 nm, preferably 3 20 and f 20.0 nm, and with particular preference 3 20 nm to
S 100 nm. The determination of the -average particle diameters is known to the skilled
person and is accomplished, for example, by the method of the ical ultracentrifuge. The
weight-average le diameter in this specification refers to the weight-average Dwso value as
1O determined by the method of the analytical Ultracentrifuge (in this regard cf. S.E. Harding et al.,
Analytical Ultracentrifugation in Biochemistry and Polymer e, Royal Society of Chemistry,
Cambridge, Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with an Eight-Cell
AUC Multiplexer: High Resolution Particle Size Distribution and Density Gradient Techniques,
W. Machtle, pages 147 to 175).
The aqueous polymer dispersions with weight-average particle diameters DW 5 100 nm that are
accessible in accordance with the process of the invention t a singly good blocking
ance and are therefore ularly suitable as binders for the coating of substrates,
’ especially in transparent aqueous formulations for wood coatings.
Advantages frequently become apparent here, such as a reduced need for thickeners in order
to set a particular viscosity, and also good and deep coloring when using color pigments, high
of the formulation into the wood surface, or good "highlighting" of the wood
, penetration ty
grain. Moreover, the aqueous polymer dispersions of the invention exhibit improved filterability
as compared with corresponding noninventive aqueous polymer dispersions.
The aqueous polymer dispersion typically has a solids content of 20% to
70% by weight, preferably 35% to 60% by .
The aqueous polymer dispersion obtained can be used, as it is or mixedeith further, lly
film-forming, polymers, as a binder composition in aqueous coating als, such as paint or
varnish es.
Of , the aqueous polymer dispersions of the invention that are obtainable by the process
of the invention can also be used as a component in the production of adhesives, sealants,
synthetic renders, paper coating slips, fiber webs, and coating materials for organic substrates,
and also for ing mineral binders.
The invention further provides a coating material in the form of an aqueous composition
comprising
40 — at least one polymer dispersion of the invention, as defined above,
— optionally at least one (in)organic filler and/or at least one (in)organic pigment,
_ optionally at least one customary auxiliary, and
- water.
PF 70891
The binder compositions of the invention are employed preferably in aqueous . These
paints take the form, for example, of an unpigmented system (transparent varnish) or a
pigmented system. The-fraction of the pigments can be described by the pigment volUme
concentration (PVC). The PVC describes the ratio of the volume of pigments (Vp) and fillers (VF)
to the total volume, composed of the volumes of binder (VB), pigments, and fillers in a dried
coating film in percent: PVC = (Vp + VF) x 100/ (Vp + VF + VB). Paints can be fied on the
basisof the PVC, for e, as s: '
highly filled or paint, wash resistant, white/matt about 85
interior paint, scrub resistant, white/matt ’
. about 80
silk-matt - about 35
, semigloss paint,
semigloss paint, silk-gloss about 25
loss paint ‘ about 15—25
exterior masonry paint, White about 45—55
clear varnish < 5
These dispersions are used preferably at a PVC<50, more preferably PVC<35, and even more
preferably in systems with low filler content (PVC<23) and arent varnishes (PVC<5).
Suitable fillers in transparent varnish ms are, for example, matting agents, which
accordingly, as desired, significantly negatively affect the gloss. Matting agents are generally
transparent and may be both organic and inorganic. Inorganic s based on silica are most
suitable and are widely available commerCially. Examples are the Syloid® products from W.R.
Grace & Company, and their Acematt® products from Evonik GmbH. Organic matting agents
are available, for example, from BYK—Chemie GmbH under the Ceraflour® and Ceramat® brand
names, and from Deuteron GmbH under the Deuteron MK® brand name. Other suitable fillers
for emulsion paints are aluminosilicates, such as feldspars, silicates, such as kaolin, talc, mica,
magnesite, alkalin earth carbonates, such as calcium carbonate, in the form of calcite or chalk,
for example, magnesium carbonate, dolomite, alkaline earth metal sulfates, such as calcium
sulfate, n dioxide, etc. In paints, of course, finely divided fillers are preferred. The fillers can
be used as individual components. In practice, however, it has been found particularly
appropriate to have filler mixtures, examples being calcium ate/kaolin and calcium
carbonate/talc. Glossy paints generally contain only small amounts of very fine fillers, or contain
no fillers at all.
Finely divided fillers may also be used in order to increase the hiding power and/or to save on
the use of white pigments. For ing the hiding power, the hue and the depth of color it is
red to use blends of color pigments and fillers.
40 Examples of suitable pigments are inorganic white pigments such as titanium dioxide, .
preferably in the rutile form, barium sulfate, zinc oxide, zinc e, basic lead carbonate,
antimony trioxide, 'lithopones (zinc sulfide + barium sulfate) or colored pigments, examples
being iron oxides, carbon black, te,» zinc yellow, zinc green, Ultramarine, ese
black, antimony black, manganese , Paris blue or Schweinfurt green. Besides the
PF 70891
inorganic pigments, the emulsion paints of the invention may also comprise organic color
pigments, examples being sepia, e, Cassel brown, toluidine red, para red, Hansa
yellow, indigo, azo dyes, anthraquinonoid and indigoid dyes, and also dioxazine, quinacridone,
phthalocyanine, isoindolinone, and metal-complex pigments. Also suitable are synthetic white
pigments with air inclusions to increase light scattering, such as the Ropaque® and AQACell®
dispersions. Additionally suitable are the Luconyl® products from BASF SE, such as l®
yellow, Lyconyl® brown, and Luconyl® red, for example, especially the arent varieties.
The coating material of the invention (aqueous paint) may optionally comprise additional film-
forming polymers, pigment, and further auxiliaries, as well as the polymer dispersion.
The customary auxiliaries include wetting. agents or dispersants, such as sodium, potassium or
um polyphosphates, alkali metal salts and ammonium salts of acrylic acid copolymers or
maleic anhydride copolymers, polyphosphonates, such as sodium 1-hydroxyethane—1,1-
diphosphonate, and also salts of alenesulfonic acids, especially their sodium salts.
More important are the orming assistants, the thickeners, and defoamers. Suitable film-
forming assistants are, for example, Texanol® from Eastman Chemicals, and the glycol ethers
and , available commercially from BASF SE, for example, under the names Solvenon®
and Lusolvan®, and from Dow under the tradename Dowanol®. The amount is preferably <10%
by weight and more preferably < 5% by , based on the total ation. it is also possible
to formulate entirely t solvents. '
Other suitable auxiliaries are flow control agents, defoamers, biocides, and thickeners. Suitable
thickeners are, for example, associative thickeners, such as polyurethane thickeners. The
amount of the} thickener is preferably less than 2.5% by weight, more preferably less than 1.5%
by weight thickeners, basedon paint solids content. Further formulating information for wood
paints is described at length in 'water—based tes for decorative gs' by. the authors M.
Schwartz and R. Baumstark, ISBN 3726-6.
The paints of the invention are ed in a known way by ng the components in mixing
equipment customary for the purpose. It has been found appropriate pare an aqueous
paste or dispersion from the pigments, water, and optionally the auxiliaries, and only then to mix
the polymeric binder, i.e., in general, the aqueous dispersion of the polymer, with the pigment
paste or pigment dispersion. 4
The paint of the invention can be applied to ates in a customary way, as for example by
spreading, spraying, dipping, rolling or knife coating.
PF 70891
‘ 18
The paints} of the invention are notable for ease of handling and good processing properties.
Their pollutant content is low. They have good performance properties, es being high
water resistance, effective wet on, and good blocking resistance, good recoatability, and
good flow on application. The equipment used is easily cleaned with water.
The invention will be illustrated by the nonlimiting es which follow.
1O a) Preparation of the aqueous polymer dispersions
In this text, the -average molecular weight Mw, unless indicated othen/vise, is determined
via size eXclusion tography (SEC) using tetrahydrofuran + 0.1% by weight trifluoroacetic
acid as eluent, with a flow rate of 1 ml/min and a column temperature of 35°C. The sample is
diluted to a concentration of 2 mg/ml in the eluent, and 100 pl of this diluted sample is injected,
after the sample solution has been filtered through a 0.2 pm filter rius Minisart SRP 25) in
order to remove any gel fraction. The columns used were three columns in combination, with an
internal diameter of 7.5 mm, as follows: 5 cm preliminary column (Plgel 10p Guard preliminary
column), followed by two 30 cm separating columns (each Plgel 10p Mixed B). Detection took
place using a differential refractometer of type Agilent 1100, and a
UV photometer of type Agilent 1100 VWD, PSS SLD7000—Bl-MwA (UV/254 nm/Agilent).
Calibration took place using narrow-range polystyrene standards from Polymer Laboratories,
with molecular weights of M = 580 to M = 7 500 000, and also hexylbenzene (M = 162). The
values outside of the elution range were extrapolated.
The filtration prior to molecular weight determination removes any gel fraction in the polymer,
and so the reported values refer to the sol fraction.
The insoluble fraction of polymer can be determined by four-hour extraction with tetrahydrofuran
in a Soxhlet apparatus and weighing of the residue which remains after the extraction residue
has been dried to constant weight. .
. ‘.
The solids content (SC) was determined lly by drying a d amount of the aqueous
polymer dispersion (approximately 1 g) to constant weight on an aluminum crucible having an
internal diameter of approximately 5 cm in a drying cabinet at 140°C. Two separate
measurements were carried out. The values reported in the es represent the average of
the two results in each case.
The minimum film—forming temperature (MFFT) was determined in accordance with Ullmanns
opadie der technischen Chemie, 4th edn., vol. 19, Verlag Chemie, Weinheim (1980), p.
40 17. The instrument used was a film—forming bench (a metal plate to which a ature
nt is applied). Filming took place at a wet film thickness of 1 mm. The minimum film-
forming temperature reported is the temperature at which the film begins to p cracks.
ComparativeExample 1 (CE 1)
PF 70891
' 19
A polymerization vessel equipped with metering s and temperature regulation was
charged at 20 to 25°C (room temperature) under a nitrogen atmosphere with
200.8 g of zed water and
.0 g of a 15% th by weight aqueous solution of sodium lauryl sulfate,
and this initial charge was heated to 87°C with stirring. When this temperature had been
reached, 29.8 g of feed 1 and subsequently, with the temperature maintained, 2.0 g of feed 3
1O were added, and polymerization took place for 5 minutes. Thereafter, beginning simultaneously,
the remainder of feed 1 was metered in continuously over the course of 120 minutes, and, in
parallel with this, the remainder of feed 3 was metered in uously over the course of 165
minutes, at constant flow rates. After the end of feed 1, feed 2 was commenced and was
d in continuously over the course of 45 minutes at a constant fldw rate.
Feed 1 (homogeneous mixture of):
329.1, g of zed water
23.3 g of a 15% strength by weight aqueous solution of sodium laurylsulfate
.7 g of a 50% strength by weight aqueous solution of acrylamide
5.1 g of acrylic acid
27.0 g of a 25% strength by weight solution of ureido rylate in methyl methacrylate a)
199.2 g of methyl methacrylate and
285.5 g of 2—ethylhexyl acrylate
Feed 2 eneous mixture of):
174.4 g of deionized water
8.9 g of a 15% strength by weight aquedus solution of sodium lauryl sulfate
.1 g of acrylic acid
27.0 g of a 25% strength by weight solution of ureido methacrylate in methyl methacrylate a)
and
148.2 g of methylmethacrylate.
Feed 3 (homogeneous solution of):
13.0 g of zed'water and
1.0 g of sodium peroxodisulfate
After the end of feeds 2 and 3, the rization mixture was reacted for 30 minutes more at
87°C. Following this, beginning simultaneously but via separate feed lines, 22.4 g of a 5%
strength by weight aqueous hydrogen peroxide solution, and a solution of 1.0 g of ascorbic acid
40 and 26.5 g of deionized water, were metered in to the polymerization mixture continuously over
the course of 60 minutes at constant flow rates.
The aqueous r dispersion obtained was subsequently cooled to room temperature,
neutralized with 5.9 g of a 25% strength by weight aqueous ammonia solution, and filtered
PF 70891
h a 125 um filter.
The resulting 1544 g of the aqueous polymer dispersion had a solids content of 45.2% by
weight. The MFFT was 13°C. d with deionized water, the aqueous polymer dispersion has
a weight-average le diameter of 82 nm. .
6’ Plex® 6844-0 from Rohm GmbH.
Example 1 (E1)
A polymerization vessel equipped with metering devices and temperature regulation was
charged at 20 to 25°C (room temperature) under a nitrogen atmosphere with
567.3 g of deionized water and
8.3 g of a 15% strength by weight aqueous Solution of sodium Iauryl sulfate,
and this initial charge was heated to 80°C with stirring. When this temperature had been
reached, all of feed 1 was added, and the mixture was d for 2 minutes. Thereafter feed 2
was commenced and was metered in over the course of 32 minutes. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added over 10 minutes. The
weight-average molecular weight of the polymer, from a sample taken at this point in time, was
23.1 kDa. Subsequently feed 4 was ced and was metered in continuously over the
course of 104 minutes, at a constant flow rate. 52 s after the start of feed 4, 10 9 Of a 3%
strength by weight ammonia solution were added.
Feed 1 (homogeneous solution of):
26.6 g of deionized water and
2.0 g of sodium peroxodisulfate
3O Feed 2 (homogeneous mixture of):
8,1 g of methacrylic acid
1,9 g of c acid
12,5 9 of styrene
80,0 9 of methyl methacrylate
12,5 9 of n-butyl acrylate
,0 '9 of diacetoneacrylamide and
2,0 g of lhexyl thioglycolate
Feed 3 (homogeneous mixture of):
4O 7.0 g of deionized water and
1.0 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
260.0 g of n-butyl acrylate and
45 115.0 g of methyl methacrylate
PF 70891
After theend of feed 4, the polymerization e was reacted for 90 minutes more at 80°C.
Then 18.2 g of a 5% strength by weight ammonia on were added over 5 minutes.
uently the s polymer dispersion obtained was cooled to room temperature. At a
temperature below 40°C, 41.7 g of a 12% strength by weight aqueous solution of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 um filter.
The resulting 1184.1 9 of the aqerus polymer dispersion had a solids content of 43.2% by
1O weight. The MFFT was s 0°C. Diluted with deionized water, the aqueous polymer dispersion
has a weight-average particle diameter of 70 nm.
Example 2 (E2)
A polymerization vessel ed with metering devices and temperature regulation was
charged at 20 to 25°C (room temperature) under a nitrogen atmosphere with
567.2 g A of deionized water and
.0 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
and this initial charge was heated to 80°C with stirring-When this temperature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter feed 2
was commenced and was metered in over the course of 38 s. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added over 10 minutes. The
weight-average molecular weight of the polymer, from a sample taken at this point in time, was
23.8 kDa. Subsequently feed 4 was commenced and was metered in continuously over the
course of 96 minutes, at a constant flow rate. 48 s after the start of feed 4, 12 g of a 3%
th by weight ammonia solution were added.
Feed 1 (homogeneous solution of):
26.6 g of deionized water and
2.0 g of sodium disulfate
Feed 2 (homogeneous mixture of):
9.8 g of methacrylic acid
2.3 g of acrylic acid
.0 g of styrene
96.0 g of methyl methacrylate
.0 g of n-butyl acryiate
40 12.0 g of diacetoneacryiamide and
2,4 g of 2-ethyihexyi thiogiycolate
Feed 3 (homogeneous mixture of):
8.4 g of deionized water and
PF 70891
1.1 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
242.0 g of n-butyl acrylate and
108.0 g of methyl methacryiate
After the end of feed 4, the rizatiOn e was reacted for 90 minutes more at 80°C.
Then 21.8 g of a 5% strength by weight ammonia solution were added over 5 minutes.
1O Subsequently the aqueous polymer dispersion obtained was cooled to room temperature. At a
temperature below 40°C, 50.0 g of a 12% strength by weight aqueous on of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 um .
The resulting 1199.1 9 of the aqueous polymer dispersion had a solids content of 42.6% by
weight. The MFFT was s 0°C. Diluted with deionized water, the aqueous polymer dispersion
has a weight—average le diameter of 66 nm.
Example 3 (E3)
A polymerization vessel equipped with metering devices and temperature regulation was
charged at 20 to 25°C (room ature) under a nitrogen here with
566.4 g of deionized water and
11.7 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
and this initial charge was heated to 80°C with stirring. When this ature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter feed 2
was commenced and was metered in over the Course of 45 minutes. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added Over 10 minutes. The
weight-average molecular weight of the polymer, from a sample taken at this point in time, was
22.1 kDa. Subsequently feed 4 was commenced and was metered in continuously over the
course of 90 minutes, at a constant flow rate. 45 minutes after the start of feed 4, 13.9 g of a 3%
strength by weight ammonia solution were added.
Feed 1 (homogeneous solution of):
26.6 g of zed water and
2.0 g of sodium peroxodisulfate
Feed 2 (homogeneous mixture of):
40 11.4 g of rylic acid
2.6 g of acrylic acid
17.5 g of styrene
112.0 g of.methyl methacryiate
17.5 g of n‘-butyl acrylate
PF 70891
14.0 g of diacetoneacrylamide and
2.8 g of 2-ethylhexyl thioglycolate
Feed 3 (homogeneous mixture of):
9.8 g of deionized water and
1.3 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
225.0 g of n-butyl acrylate and
‘10 100.0 g of methyl methacrylate
After the end of feed 4, the polymerization mixture was reacted for 90 minutes more at 80°C.
Then 25.42 g of a 5% strength by weight ammonia solution were added over 5 minutes.
Subsequently the aqueous polymer dispersion obtained Was cooled to room temperature. At a
ature below 40°C, 58.3 g of a 12% strength by weight aqueous solution of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 um filter.
The resulting 1215.4 9 of the aqueous polymer dispersion had a solids content of 41.8% by
weight. The MFFT was s 1°C. Diluted with deionized water, the aqueous r dispersion
has a weight-average particle er of 62 nm.
Example 4 (E4)
A polymerization vessel equipped with ng devices and ature regulation was
d at 20 to 25°C (room temperature) under a nitrogen atmosphere with
1198.1 9 of deionized water and
26.0 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
and this initial charge was heated to 80°C with ng. When this temperature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter feed 2
was commenced and was metered in over the course of 40 minutes. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added over 10 minutes. The
-average molecular weight of the polymer, from a sampletaken at this point in time, was
23.0 kDa. uently feed 4 was ced and was metered in continuously over the
course of 90 minutes, at a constant flow rate. 45 minutes after the start of feed 4, 31.2 g of a 3%
strength by weight ammonia solution were added.
40 Feed 1 (homogeneous solution of):
69.1 g of deionized water and
.2 g of sodium peroxodisulfate
Feed 2 (homogeneous mixture of):
PF 70891
164.7 g of deionized water
8.7 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
.4 g of methacrylic acid
.9 g of acrylic acid
39.0 g of styrene .
249.6 g of methyl methacrylate
39.0 g. of n-butyl acrylate
156.0 g of a 20% th aqueous solution of diacetoneacrylamide and
6.2 g of 2-‘ethylhexyl thioglycolate
Feed 3 (homogeneous mixture of):
21.7 g of zed water and
3.0 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
629.2 g of n-butyl te and
280.8 g of methyl methacrylate
After the end of feed 4, the polymerization mixture was reacted for 90 minutes more at 80°C.
’20 Then 56.7 g of a 5% strength by weight ammonia solution were added over 5 minutes.
Subsequently the aqueous r dispersion obtained was cooled to room temperature. At a .
temperature below 40°C, 130 g of a 12% strength by weight aqueous solution of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 pm filter.
The resulting 3145.3 9 of the aqueous polymer dispersion had a solids content of 42.8% by
weight. The MFFT was s 1°C. d with deionized water, the s polymer dispersion
has a weight-average le diameter of 60 nm.
Example 5 (E5)
A polymerization vessel equipped with metering devices and temperature regulation was
d at 20 to 25°C (room ature) under a nitrogen atmosphere with
840.5 g of deiOn‘ized water and
34.7 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
and this initial charge was heated to 80°C with stirring. When this temperature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter feed 2
40 was commenced and was metered in over the course of 40 minutes. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added over 10 s. The
weight-average molecular weight of the sample taken at this point in time, was 22.0 kDa.
Subsequently feed 4 was commenced and was metered in continuously over the course of 90
minutes, at a constant flow rate. 45 minutes after the start of feed 4, 31.2 g of a 3% strength by
PF 70891
weight ammonia solution were added.
Feed 1 (homogeneous solution of):
69.1 g of deionized water and
.2 g of sodium peroxodisulfate
Feed 2 (homogeneous mixture of):
130.0 g of deionized water
8.7 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
25.4 g of methacrylic acid
.9 g of acrylic acid
39.0 g of styrene
249.6 g of methyl methacrylate
39.0 g of n-butyl acrylate
156.0 g of a 20% strength s solution of diacetoneacrylamide and
6.2 g of 2-ethylhexyl thioglycolate
Feed 3 (homogeneous mixture of):
21.7 g of deionized water and
3.0 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
451.5 g of deionized water
17.3 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
629.2 g of n-butyl acrylate and
280.8 g of methyl methacrylate
After the end of feed 4, the polymerization mixture was reacted for 90 minutes more at 80°C.
Then 56.7 g of a 5% strength by weight ammonia solution were added over 5 minutes.
uently the aqueous pOIymer dispersion obtained was cooled to room temperature. At a
temperature below 40°C, 130 g of a 12% strength by weight aqueous solution of adipic
d-ihydrazide were added. Finally, the dispersion was filtered through a 125 pm filter.
The resulting 3230.4 9 of the s polymer sion had a solids content of 41 .7% by
weight. The MFFT was s 1°C. Diluted with zed water, the s polymer dispersidn
has a weight-average particle diameter of 64 nm.
Comparative example 2 (CE2)
A polymerization vessel equipped with ng devices and temperature regulation was
d at 20 to 25°C (room temperature) Under a en atmosphere with
1474.8 g of deionized water and
PF 70891
26.0 g of a 15% strength by weight aqueous on of sodium lauryl sulfate
and this initial charge was heated to 80°C with stirring. When this temperature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter feed 2
was commenced and was metered in over the course of 38 s. After the end of feed 2,
rization was continued for 10 minutes, then feed 3 was added over 10 minutes. The
weight-average molecular weight of the polymer, from a sample taken at this point in time, was
23.0 kDa. Subsequently feed 4 was commenced and was metered in continuously over the
course of 96 minutes, at a constant flow rate. 48 minutes after the start of feed 4, 31.2 g of a 3%
1O th by weight ammonia solution were added.
Feed 1 (homogeneous solution of):
69.1 g of deionized water and
.2 g of sodium peroxodisulfate
Feed 2 (homogeneous mixture of):
.4 g of methacrylic acid
.7 g of acrylic acid
39.0 g of styrene
249.6 g of methyl methacrylate
39.0 g of n-butyl acrylate
31.2 g of oneacrylamide and
6.2 g of 2-ethylhexyl thioglycolate
Feed 3 (homogeneous mixture of):
21.7 g of deionized water and
3.0 g of a 25% strength by weight ammonia solution
Feed 4 eneous mixture of):
629.2 g of n-butyl acrylate. and
280.8 g 'of methyl methacrylate
Afterthe end of feed 4, the rization mixture was reacted for 90 minutes more at 80°C.
Then 56.7 g of a 5% strength by weight ammonia solution were added over 5 minutes.
Subsequently the aqueous polymer dispersion ed was cooled to-room ature. At a
temperature below 40°C, 130 g of a 12% strength byweight aqueous solution of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 um filter.
40 The resulting 3123.8 9 of the aqueous polymer dispersion had a solids content of 41 .3% by
weight. The MFFT was s 1°C. d with deionized water, the aqueous polymer dispersion
has a weight-average particle diameter of 65 nm.
Example 6 (E6)
PF 70891
A polymerization vessel ed with metering devices and temperature regulation was
charged at 20 to 25°C (room temperature) under a nitrogen atmosphere with
884.6 g of deionizedwater and
.6 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
and this initial charge was heated to 80°C with stirring. When this ature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter feed 2
was commenced and was metered in over the course of 38 minutes. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added over 10 minutes. The
weight-average molecular weight of a sample taken at this point in time was 22.5 kDa.
Subsequently feed‘4 was commenced and was metered in continuously over the course of 96
minutes, at a nt flow rate. 45 minutes after the start of feed 4, 18.7 g of a 3% strength by
weight ammonia solution were added.
Feed 1 (homogeneous solution of):
41.5 g of deionized water and
3.1 g of sodium peroxodisulfate
Feed 2 (homogeneous mixture of):
.2 g of methacrylic acid
3.5 g of acrylic acid
23.4 g of styrene
140.4 g of methyl rylate
23.4 g of n-butyl acrylate
9.4 g of a 25% strength by weight solution of ureidomethacrylate in methyl methacrylatea)
18.7 g of diacetoneacrylamide and
3.7 g of 2-ethylhexyl thioglycolate
Feed 3 (homogeneous mixture of):
13.0 g of deionized water and
1.8 g of a 25% strengthby weight ammonia solution
Feed 4 eneous mixture of):
377.5 g of n-butyl acrylate and
168.5 g of methyl methacrylate
After the end of feed 4, the polymerization e was reacted for 90 minutes more at 80°C.
40 Then 34.0 g of a 5% strength by weight ammonia solution were added over 5 minutes.
uently the aqueous polymer dispersion ed was cooled to room ature. At a
temperature below 40°C, 78 g of a 12% strength by weight aqueous solution of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 um filter.
PF 70891
The resulting 1874 g of the aqueous polymer dispersion had a solids content of 41.6% by
weight. The MFFT was s 1°C. Diluted with deionized water, the s polymer dispersion
has a weight-average particle er of 64 nm.
a) Plex® 6844-0 from Rohm GmbH.
Example 7 (E7)
1O A polymerization vessel equipped with metering devices and temperature regulation was
charged at 20 to 25°C (room temperature) under a nitrogen atmosphere with
884.6 g of deionized water and
.6 g of a 15% strength by weight aqueous on of sodium lauryl sulfate
and this initial charge was heated to 80°C with stirring. When this temperature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter feed 2
was commenced and was metered in over the course of 38 s. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added over 10 s. The
weight-average molecular weight of the polymer, from a sample taken at this point in time, was
33.6 kDa. Subsequently feed 4 was commenced and was metered in continuously over the
course of 96 minutes, at a constant flow rate. 45 minutes after the start of feed 4, 18.7 g of a 3%
strength by weight ammonia solution were added.
Feed 1 (homogeneous solution of):
41.5 g of deionized water and
3.1 g of sodium peroxodisulfate
Feed 2 (homogeneous e of):
15.2 g of methacrylic acid
3.5 g of acrylic acid
23.4 g of styrene
118.69 of methyl methacrylate
23.4 g of n-butyl acrylate
31.2 g of a 25% strength by weight solution of ureidomethacrylate in methyl methacrylatea)
18.7 g of diacetoneacrylamide and
3.7 g of 2—ethylhexyl ycolate
Feed 3 (homogeneous mixture of):
4O 13.0 g of deionized water and
1.8 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
377.5 g of n-butyl acrylate and
45 168.5 g of methyl methacrylate
PF 70891
After the end of feed 4, the rization mixture was reacted for 90 minutes more at 80°C.
Then 34.0 g of a 5% strength by weight ammonia solution were added over 5 minutes.
Subsequently the aqueous polymer dispersion obtained was cooled to room temperature. At a
temperature below 40°C, 78 g of a 12% strength by weight aqueous solution of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 pm filter.
The resulting 1874 g of the s polymer sion had a solids content of 41.5% by
weight. The MFFT was s 1°C. Diluted with zed water, the aqueous polymer dispersion
has a weight-average particle diameter of 87 nm.
8’ Plex® 6844-0 from Rohm GmbH.
Comparative example 3 (CE3)
A polymerization vessel equipped with metering devices and temperature regulation was
charged at 20 to 25°C (room temperature) under a nitrogen atmosphere with
323.1 g of deionized water and
13.3 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
and this initial charge was heated to 80°C with ng. When this temperature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter feed 2
was commenced and was d in over the course of 40 minutes. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added, the e was stirred for
minutes, and subsequently feed 4 was commenced and was metered in continuously over
the course of 90 minutes, at a constant flow rate. 45 minutes after the start of feed 4, 1.1 g of a
% strength by weight ammonia solution were added.
Feed 1 (homogeneous solution of):
26.6 g of deionized water and
2.0 g of sodium disulfate
Feed 2 (homogeneous mixture of):
47.8 g of deionized water
3.3 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
9.8 g of methacrylic acid
4.5 g of a 50% th by weight aqueous solution of acrylamide
40 15.0 g of styrene
92.0 g of methyl methacrylate
.0 g of n-butyl acrylate
60.0 g of a 20% strength by weight aqueous solution of diacetoneacrylamide and
2.4 g of 2-ethylhexyl thioglycolate
PF 70891
'Feed 3:
0.9 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
147.3 g of~deionizedwater
6.7 g of a 15% strength by weight aqueous SolutiOn of sodium lauryl sulfate
242.0 g of n-butyl acrylate and '
108.0 g of methyl methacrylate
1O After the end of feed 4, the polymerization e was reacted for 90 minutes more at 80°C.
Then 3.4 g of a 25% strength by weight a solution were added.
Subsequently the aqueous polymer dispersion obtained was cooled to room temperature. At a
temperature below 40°C, 50 g of a 12% strength by weight aqueous solution of adipic
dihydrazide were added. Finally, the sion was filtered through a 125 pm .
The weight-average molecular weight of the polymer of a sample taken before the start of
feed 4 was 22.5 kDa.
The resulting 1174 g of the aqueous polymer dispersion had a solids content of 42.5% by
weight. The MFFT was s 1°C. Diluted with deionized water, the aqueous polymer dispersion
has a weight-average particle diameter of 75 nm.
Example 8 (E8)
A polymerization vessel equipped with ng s and temperature regulation was
d at 20 to 25°C (room temperature) under a en atmosphere with
840.2 g of deionized water and
34.7 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
and this initial charge was heated to 80°C with stirring. When this temperature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter—feed 2
was commenced and was metered in over the course of 40 minutes. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added, the mixture was stirred for
minUtes, and subsequently feed 4 was commenced and was metered in continuously over
the course of 90 minutes, at a nt flow rate. 45 minutes after the start of feed 4, 2.6 g of a
% strength by weight a solution were added.
40 Feed 1 (homogeneous solution of):
69.1 g of deionized water and
.2 g of sodium peroxodisulfate
Feed 2 (homogeneous mixture of):
PF 70891
109.4 g of deionized water
8.7 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
22.8 g of Imethacrylic acid
17.3 g of a 15% strength by weight aqueous solution of methacrylamide
11.7 g of a 50% strength by weight aqueous solution of acrylamide
39.0 g. of styrene _
249.6 g of methyl methaCrylate
39.0 g of n-butyl acrylate
156.0 g of a 20% strength by weight aqueous solution of diacetoneacrylamide and
6.2 g of 2-ethylhexyl thioglycolate
Feed 3:
2.1 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
382.9 g of deionized water ‘
17.3 g of a 15% strength. by Weight aqueous solutiOn of sodium lauryl sulfate
629.2 g of n-butyl acrylate and '
280.8 g of methyl methacrylate
After the end of feed 4, the polymerization mixture was reacted for 90 minutes more at 80°C.
Then 8 g of a 25% strength by weight ammonia solution were added. «
Subsequently the aqueous polymer sion obtained was cooled to room temperature. At a
temperature below 40°C, 130 g of a 12% strength by weight aqueous solution of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 um filter.
The —average molecular weight of the polymer of a sample taken before the start of
feed4 was 23.2 kDa. '
The ing 3060 g of the aqueous polymer dispersion had a solids content of 41 .9% by
weight. The MFFT was S 1°C. d with zed water, the s polymer dispersion
has a weight-average particle diameter of 71 nm.
Example 9 (E9)
A polymerization vessel equipped with ng devices and temperature regulation was
charged at 20 to 25°C (room temperature) under a nitrogen atmosphere with
4O 840.2 g of zed water and
34.7 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
and this initial charge was heated to 80°C with stirring. When this temperature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 s. Thereafter feed 2
PF 70891
was commenced and was d in over the course of 40 minutes. After the end of feed 2,
polymerization was continued for 10 minutes, then feed 3 was added, the mixture was stirred for
minutes, and subsequently feed 4 was commenced and was metered in continuously over
the course of 90 minutes, at a constant flow rate. 45 minutes after the start of feed 4, 2.3
g of a
% strength by weight ammonia solution were added.
Feed 1‘ (homogeneousgsolution of):
69.1 g - of deionized water and
.2 g of sodium peroxodisulfate
Feed 2 (homogeneous mixture of):
91.0 g of deionized water
8.7 g of a 15% strength by weight aqueous on of sodium lauryl sulfate
19.5 g of methacrylic acid
39.0 g of a 15% strength by weight s solution of methacrylamide
11.7 g of a 50% strength by weight aqueous on of acrylamide
39.0 g of styrene
249.6 g of methyl methacrylate
39.0 g of n-butyl acrylate
156.0 g of a 20% th by weight s solution of diacetoneacrylamide and-
6.2 g of 2-ethylhexyl thioglycolate
Feed 3:
1.8 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
382.9 g of deionized water
17.3 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
629.2 g of n-butyl acrylate and
, 280.8 g of methyl methacrylate
.After the end of feed 4, the polymerization mixture was reacted for 90 minutes more at 80°C.
Then 6.8 g of a 25% th by weight ammonia solution were added.
Subsequently the s polymer dispersion obtained was cooled to room temperature. At a
temperature below 40°C, 130 g of a 12% strength by weight aqueous solution of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 um filter.
The weight-average molecular weight of the polymer of a sample taken before the start of
40 feed 4 was 22.8 kDa.
The resulting 3059 g of the s polymer dispersion had a solids content of 42.2% by
weight. The MFFT was S 1°C. Diluted with deionized water, the aqueous polymer sion
has a weight-average particle diameter of 71 nm.
PF 70891
’ 33
Example 10 (E10) '
A polymerization vessel equipped with metering devices and temperature regulation was
charged at 20 to 25°C (room temperature) under a nitrogen atmosphere with
840.2 g of deionized water and .
34.7 g _
- of a 15% strength by weight aqueous solution of- sodium ‘lauryl sulfate
and this initial charge was heated to 80°C with stirring. When this temperature had been
d, all of feed 1 was added, and the e was stirred for 2 minutes. fter feed 2
was commenced and was metered in over the course of 40 minutes. After the end of feed 2,
rization was continued for 10 s, then feed 3 was added, the mixture was stirred for
minutes, and subsequently feed 4 was ced and was metered in continuously over .
the course of 90 minutes, at a constant flow rate. 45 s after the start of feed 4, 1.9 g of a
% strength by weight ammonia solution were added.
Feed 1 (homogeneous solution of):
69.1 g of deionized water and
5.2 g of sodium peroxodisulfate
Feed 2 (homogeneous mixture of):
72.6 g of zed water
8.7 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
16.3 g of methacrylic acid
60.7 g of a 15% strength by weight aqueous solution of methacrylamide
11.7 g of a 50% strength by weight aqueous solution of acrylamide
39.0 g of styrene
249.6 g of methyl methacrylate
39.0 g of n-butyl acrylate
156.0 g of a 20% th by weight aqueous solution 0f diacetoneacrylamide and
6.2 g of 2-ethylhexyl thioglycolate
Feed 3:
1.5 g of a 25% strength by weight ammonia solution
Feed 4 (homogeneous mixture of):
382.9 g of deionized water
17.3 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
40 629.2 g of n-butyl acrylate and
280.8 g of methyl methacrylate
After the end of feed 4, the polymerization mixture was reacted for 90 minutes more at 80°C.
Then 5.7 g of a 25% strength by weight ammonia solution were added.
PF 70891
‘ 34
Subsequently the aqueous polymer dispersion‘obtained was cooled to room temperature. At a
temperature below 40°C,'130 g of a 12% strength by weight aqueous solution of adipic
azide were added. Finally, the dispersion was filtered h a 125 pm filter.
The weight-average molecular weight of the polymer of a sample taken before the start of
feed 4 was 22.9 kDa.
The ing 3058 g of the aqueous polymer dispersion had a solids t of 42.1 % by
1O . The MFFT was s 1°C. Diluted with deionized water, the aqueous polymer dispersion
has a_ weight-average particle diameter of 71 nm.
Example 11 (E11)
A polymerization vessel ed with metering devices and temperature regulation was
charged at 20 to 25°C (room temperature) under a nitrogen atmosphere with
840.2 g of deionized water and
34.7 g of a 15% strength by weight aqueous on of sodium lauryl sulfate
and this initial charge was heated to 80°C with stirring. When this temperature had been
reached, all of feed 1 was added, and the mixture was stirred for 2 minutes. Thereafter feed 2
was commenced and was metered in over the course of 40 minutes. After the end of feed 2,
rization was continued for 10 minutes, then feed 3 was added, the mixture was stirred for
10 minutes, and subsequently feed 4 was commenced and was d in continuously over
the course of 90 minutes, at a constant flow rate. 45 minutes after the start of feed 4, 1.5 of a
% strength by weight ammonia solution were added.
Feed 1 (homogeneous solution of):
3O 69.1 g of deionized water and
.2 g of sodium peroxodisulfate
Feed 2 (homogeneous mixture of):
54.2 g of deionized water
8.7 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
13.0 g of methacrylic acid
82.3 g of a 15% strength by weight aqueous solution of methacrylamide
11.7 g of a 50% strength by weight aqueous solution of acrylamide
39.0 g of styrene
40 249.6 g of methyl methacrylate
39.0 g of n—butyl acrylate
156.0 g of a 20% strength by weight aqueous on of diacetoneacrylamid and
6.2 g of 2-ethylhexyl thioglycolate
PF 70891
Feed 3:
1.2 g of a 25% strength by weight ammonia solution
Feed 4 ehebus mixture of):
382.9 g of deionized water
17.3 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate
629.2 g of l te and
280.8 g of methyl methacrylate
After the end of feed 4, the polymerization mixture was reaCted for 90 minutes more at 80°C.
Then 4.6 g of a 25% strength by weight ammonia solution were added.
Subsequently the aqueous polymer dispersion obtained was cooled to room temperature. At a
ature below 40°C, 130 g of a 12% strength by weight aqueous solution of adipic
dihydrazide were added. Finally, the dispersion was filtered through a 125 um filter.
The weight—average molecular weight of the polymer of a sample taken before the start of
feed 4 was 23.3 kDa.
The resulting 3056.8 g of the aqueous polymer dispersion had a solids t of 42.1 % by
weight. The MFFT was s 1°C. Diluted with deionized water, the aqueous polymer dispersion
has a weight-average particle diameter of 75 nm.
b) Performance investigations
Performance investigations were carried out on a clear varnish formulation according to the
formula indicated below:
B k® 348 o aent from BYK-Chemie GmbH
Te- 0 Airex® 901 W Defoamer from. Evonik GmbH
Solvenon® DPM Film-forming assistant from BASF SE '
Solvent and Tinuvm. .
Butyl glycol Film-forming assnstant. . .
were premixed
Tinuvin®"’1"130 Li-ht stabilizer from BASF SE
Te- 0 Glide® 482 Flow control additive from Evonik GmbH
-—-l
_l-l—m
Te- 0 ® 810 Defoamer from Evonik GmbH m
The Components dded in succession and mix'ed homogeneous'after each step; The
following tests were carried out:
PF 70891
Storage stability test
The formulation was subjected to a storage test. Closed 100 ml sample vials were stored at
50°C for 14 days and tested for increase in viscosity. The Krebs ity of the coating was
ined at 23°C, using a Brookfield KU 1 viscometer (in accordance with ASTM D562),
before and after 14 days of storage at 50°C. In the event of viscosity differences of more than
KU units, coatings are ed to as not storage-stable.
Wet adhesion tests, wood stain on pine
The stain under test (300 um wet) was applied using the Erichsen film applicator to the pine
strip. After a drying time of 7 days at RT, the test area was prepared Using the cross-cut tester
and cutter (45° to the grain of the wood, 7 cuts, 2 mm cut spacing). The cross-cutting was
carried out in accordance with EN lSO 2409, with a ce of 2 mm between the cuts. Then
about 2.5 ml of DI water were pipetted into the Petri dish, which was centered on the lattice of
cuts, made hand, for a period of 2 hours (strip was placed on the Petri dish and then
rotated by 180°). The Petri dish was removed and the remaining DI water was taken up with a
cloth. After a further 10 minutes, a strip of Tesa adhesive tape with a length of approximately
50 mm was adhered, (45° to all of the cuts and in the direction of the wood grain) and smoothed
out, and then peeled from the en at a uniform speed.
Evaluation: Assessment of the damage patterns
0 = No square damaged, cut edges smooth
I = No delaminations, < 5% of the area
2 = Delaminations of the edge and at cuts, 5 — 15%
3 = Delaminations at corners, parts of the squares, 15 - 35%
4 = g can be peeled off in long strips, whole squares delaminated, 35 - 65%
= Delaminated area > 65%
Pendulum hardness of stain on glass
The stain under test was knife-coated using an Erichsen film applicator (300 pm wet) to a glass
plate measuring 38 x 7 cm. After 3 days of drying at room temperature, three pendulum
measurements were taken at three points on theglass plate. Measurement took place by the
method of Konig (DIN EN ISO 1522).
Table 1
Amount of Pendulum
samp'e SC“)o MFFT° Dw (hm)
emulsifiermphm)
--—&—o—2IA :53(s)
-m-—“—IA
-- ..
-42 ——
— . 21
The data from table 1‘show that the inventive dispersions with little emulsifier are nevertheless
PF 70891
finely divided and have a low film-forming temperature. At the same time they exhibit a high
pendulum hardness.
Table 2
Adhesion monomer” Wet adhesion
Sample
(% by weight) (school grade)
E—-__
" 1|)E Based on.100 parts by weight of the total monomers for polymerization0in first and second
stages and optionally further stages.
The data from table 2 show very clearly the effect of an onal adhesion monomer on the
wet adhesion of the g of the corresponding polymer sion.
Table 3
Methacrylic acid 1) Methacrylamide 1’ pH of KU
Samp e| after 14 d
(% by Wt) (% by wt.) wood stain instantaneous
50°C
1.95 8.3
measurable
——_m——
——_——-I3._——_II_
—_——_—
1) Based on 100 parts by weight of the total monomers for polymerization'In first and second
stages and optionally further stages.
The data from table 3 show clearly the increase in viscosity after 14 days of e of the
formulation at 50°C. This increase is the lowest in the case of example 11.
Claims (19)
1. A process for preparing a polymer dispersion which comprises carrying out an at least two-stage emulsion polymerization, where first in a first stage in s medium a first polymer in dispersion in water and having a glass transition temperature of more than 50°C and a weight-average molecular weight of between 5 and 100 kDa is prepared by free-radical emulsion 10 polymerization, comprising hydrophilic and hydrophobic monomers, comprising (A1) at least one (meth)acrylic acid alkyl ester, (B1) optionally at least one vinylaromatic having up to 20 C atoms, 15 (Cl) optionally at least one free-radically polymerizable nd selected from the group consisting of ethylenically unsaturated nitriles having up to 20 C atoms, vinyl esters of ylic acids comprising up to 20 C atoms, vinyl halides having up to 10 C atoms, and vinyl ethers of alcohols containing 1 to 10 C atoms, (D1) at least one a,B-ethylenically unsaturated carboxylic acid, or a vinyl monomer with 20 latent ionic groups, (E1) optionally at least one inker, (F1) at least one compound selected from the group consisting of 2—(2-oxoimidazolidin y|)ethyl (meth)acrylate, 2-ureido(meth)acrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2- 25 (acetoacetoxy)ethyl rylate, diacetoneacrylamide (DAAM), and diacetonemethacrylamide, (G1) optionally at least one compound having a (meth)acrylate group and an epoxy group, and (H1) optionally at least one o,B-ethylenically unsaturated carboxamide, in the ce of at least one initiator, at least one emulsifier in an amount of 0.1% to 3.5% by weight, and at least one chain er agent, - neutralization to a pH of at least 4.5 of the particles thus formed, using a base 35 (neutralizing agent), - followed by adical polymerization of hobic and hydrophilic monomers in a following stage, in the presence of the copolymer prepared in the first stage, from 40 (A2) at least one (meth)acrylic acid alkyl ester, (32) optionally at least one vinylaromatic having up to 20 C atoms, (CZ) optionally at least one free-radically polymerizable compound selected from the group consisting of nically unsaturated nitriles having up to 20 C atoms, vinyl esters of carboxylic acids comprising up to 20 C atoms, vinyl halides having up to 10 C atoms, and vinyl ethers of alcohols containing 1 to 10 C atoms, (D2) optionally at least one d,B-ethylenically unsaturated carboxylic acid, or a vinyl r with latent ionic , (E2) optionally at least one crosslinker, and (F2) optionally at least one nd selected from the group consisting of 2-(2- oxoimidazolidinyl)ethyl (meth)acry|ate, 2-ureido(meth)acrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2- (acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (DAAM), and 10 diacetonemethacrylamide, (G2) optionally at least one compound having a (meth)acry|ate group and an epoxy group, and (H2) optionally at least one a,B-ethylenically unsaturated carboxamide, with the proviso that the polymer of the 2nd stage is more hydrophobic than that of the 1st stage, 15 and the glass transition temperature of the second stage is at least 50°C lower than that of the first stage.
The process according to claim 1, wherein the following stage is followed by further addition of at least one additional crosslinking agent.
The process according to claim 2, wherein the r (F1) and/or (F2) is selected from diacetoneacrylamide (DAAM) and as crosslinking agent adipic dihydrazide (ADDH).
The process according to any one of claims 1 to 3, wherein the monomer (A1) and/or (A2) 25 is ed from the group consisting of methyl methacrylate, methyl acrylate, ethyl te, n—butyl acrylate, n-butyl methacrylate, 2—ethylhexyl acrylate, and ylheptyl
The process according to any one of the preceding claims, wherein the r (B1) 30 and/or (B2) is ed from the group consisting of styrene and a-methylstyrene.
The process according to any one of the preceding claims, wherein the monomer (C1) and/or (C2) is selected from the group consisting of fumaronitrile, acrylonitrile, and methacrylonitrile.
The s according to any one of the preceding , wherein the monomers (D1) and/or (D2) are selected from the group of (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid.
40 The process according to any one of the preceding claims, wherein the polymer of the first stage is a copolymer (i) which is used in an amount of 7% to 80% by weight, based on 100 parts by weight of the total monomers for polymerization in the first and second stages, (ii) which is synthesized to an extent of at least, e.g., 50% or 60% by weight and up to 99% by weight of principal monomers which are selected from the group of the monomers A1 and B1 and (iii) 0.1% to 10% by weight of at least one d,B-ethylenically unsaturated ylic acid, or vinyl monomer with latent ionic groups (monomers D1), (iv) 0.1% to 10% by weight of at least one compound selected from the group consisting of 2-(2-oxoimidazolidinyl)ethy| acrylate, 2-ureido(meth)acrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl rylate, oneacrylamide (DAAM) and 10 diacetonemethacrylamide (monomers F 1), (v) 0% to 10% by weight of at least one compound selected from the group of an d,B- ethylenically unsaturated carboxamide ers H1), (vi) 0% to 10% by weight of at least one compound selected from the monomers C1, E1, and G1, 15 the quantity s (ii) to (vi) being based in each case on 100% by weight of the monomers for polymerization in the first stage.
The process according to any one of the preceding claims, wherein the weight-average molecular weight of the copolymer of the first stage is between 10 and 50 kDa.
10 The process according to any one of the preceding claims, wherein the copolymer obtained from the first stage has a glass transition temperature of 50 to 150°C and the product obtained from the second stage has a glass transition temperature which is lower by at least 50°C.
11. The process according to any of claims 1 to 10, wherein the weight ratio of the monomers used in the first stage to the amount of the monomers used in the second stage is 10:90 to 50:50. 30
12. A polymer produced in a process according to any one of claims 1 to 13.
13. A coating material in the form of an aqueous composition comprising at least one polymer dispersion according to claim 12, - optionally at least one (in)organic filler and/or at least one ganic pigment, 35 - optionally at least one customary auxiliary, and - water.
14. The use of a r dispersion according to claim 12 for coating compositions. 4O
15. The use of a polymer dispersion according to claim 12 for paints.
16. The use of a polymer dispersion according to claim 12 as paints for wood coatings.
17. A process according to claim 1, substantially as herein described with reference to any one of the accompanying examples thereof.
18. A polymer according to claim 12, substantially as herein described with reference to any one of the accompanying examples thereof.
19. Use according to any one of claims 14 to 16, substantially as herein bed with reference to any one of the accompanying es thereof.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11160443 | 2011-03-30 | ||
EP11160443.5 | 2011-03-30 | ||
PCT/EP2012/055068 WO2012130712A1 (en) | 2011-03-30 | 2012-03-22 | Aqueous multistage polymer dispersion, process for its preparation and use thereof as binder for coating substrates |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ614963A NZ614963A (en) | 2014-11-28 |
NZ614963B2 true NZ614963B2 (en) | 2015-03-03 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2012234476B2 (en) | Aqueous multistage polymer dispersion, process for its preparation and use thereof as binder for coating substrates | |
US20120252972A1 (en) | Aqueous multistage polymer dispersion, process for its preparation, and use thereof as binder for coating substrates | |
CN107429084B (en) | Water-based paint composition and preparation method thereof | |
US6348528B1 (en) | Aqueous polymer dispersion containing an emulsifier with phosphate groups | |
US9382442B2 (en) | Aqueous binder compositions | |
CA2961590C (en) | Finely divided aqueous emulsion polymers and use thereof for hydrophobic coatings | |
EP2825575B1 (en) | Latex binders useful in zero or low voc coating compositions | |
EP2009072B1 (en) | Aqueous polymeric composition | |
AU2017234180B2 (en) | Finely divided aqueous multistage polymerizate dispersion, method for the production thereof, and use thereof as a binder | |
US9169380B2 (en) | Use of aqueous polymer dispersions for improving resistance to chemical influences | |
KR20200037260A (en) | Aqueous coating composition | |
JP2023536076A (en) | Aqueous polymer latices of film-forming copolymers suitable as binders in aqueous coating compositions | |
EP3580293B1 (en) | Environmentally friendly aqueous coating composition | |
US20230348633A1 (en) | Process for producing an aqueous polymer dispersion | |
WO2020154888A1 (en) | Aqueous coating composition | |
NZ614963B2 (en) | Aqueous multistage polymer dispersion, process for its preparation and use thereof as binder for coating substrates | |
TW202344531A (en) | Polymer binder based on 2-octyl acrylate, n-butyl acrylate and methyl methacrylate for aqueous coating compositions containing titanium dioxide |