EP3814433A1 - Aqueous dispersions and emulsion paints comprising ethylhexyl acrylate-butyl acrylate-styrene copolymers - Google Patents
Aqueous dispersions and emulsion paints comprising ethylhexyl acrylate-butyl acrylate-styrene copolymersInfo
- Publication number
- EP3814433A1 EP3814433A1 EP19730823.2A EP19730823A EP3814433A1 EP 3814433 A1 EP3814433 A1 EP 3814433A1 EP 19730823 A EP19730823 A EP 19730823A EP 3814433 A1 EP3814433 A1 EP 3814433A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- monomers
- parts
- range
- aqueous emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 74
- 239000003973 paint Substances 0.000 title claims abstract description 64
- 239000000839 emulsion Substances 0.000 title claims abstract description 50
- 229920001577 copolymer Polymers 0.000 title description 6
- 239000000178 monomer Substances 0.000 claims abstract description 95
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 30
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims abstract description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000049 pigment Substances 0.000 claims abstract description 16
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 239000011256 inorganic filler Substances 0.000 claims abstract description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- QGMRQYFBGABWDR-UHFFFAOYSA-M Pentobarbital sodium Chemical compound [Na+].CCCC(C)C1(CC)C(=O)NC(=O)[N-]C1=O QGMRQYFBGABWDR-UHFFFAOYSA-M 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- 150000004760 silicates Chemical class 0.000 claims description 8
- 150000007529 inorganic bases Chemical class 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001023 inorganic pigment Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 abstract 1
- -1 ethylhexyl Chemical group 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005553 polystyrene-acrylate Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-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
- 238000013112 stability test Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- UIFZRVHZTAYMBC-UHFFFAOYSA-N (1-hydroxy-1-phosphonoethyl)phosphonic acid;sodium Chemical compound [Na].OP(=O)(O)C(O)(C)P(O)(O)=O UIFZRVHZTAYMBC-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- ZLPXFBBKYQYQEA-UHFFFAOYSA-N 1-(prop-2-enoylamino)ethanesulfonic acid Chemical compound OS(=O)(=O)C(C)NC(=O)C=C ZLPXFBBKYQYQEA-UHFFFAOYSA-N 0.000 description 1
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- KWVPFECTOKLOBL-KTKRTIGZSA-N 2-[(z)-octadec-9-enoxy]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCO KWVPFECTOKLOBL-KTKRTIGZSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- RXBOCDZLKBPILN-UHFFFAOYSA-N 2-propylheptyl prop-2-enoate Chemical compound CCCCCC(CCC)COC(=O)C=C RXBOCDZLKBPILN-UHFFFAOYSA-N 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- HTWRFCRQSLVESJ-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC(=O)C(C)=C HTWRFCRQSLVESJ-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- ZGLJYJVYUYQOHR-UHFFFAOYSA-N 3-oxobutanoyl 4-hydroxy-2-methylidenebutanoate Chemical compound CC(=O)CC(=O)OC(=O)C(=C)CCO ZGLJYJVYUYQOHR-UHFFFAOYSA-N 0.000 description 1
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 1
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 1
- 108050001922 30S ribosomal protein S17 Proteins 0.000 description 1
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- FIWRUIQDDCPCOQ-UHFFFAOYSA-N C=CC(=O)OC1C=CC=C1 Chemical compound C=CC(=O)OC1C=CC=C1 FIWRUIQDDCPCOQ-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
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- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical class C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
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- VSVCAMGKPRPGQR-UHFFFAOYSA-N propan-2-one;sulfurous acid Chemical compound CC(C)=O.OS(O)=O VSVCAMGKPRPGQR-UHFFFAOYSA-N 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
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- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
-
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F220/10—Esters
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
Definitions
- the present invention relates to aqueous dispersions and emulsion paints, in particular interior paints, containing ethylhexyl acrylate-butyl acrylate-styrene copolymers as binders, a process for the preparation of the aqueous dispersion and the dispersion paint, the use of the aqueous dispersion paint and the use of ethylhexyl acrylate-buytlacrylate-styrene.
- Copolymers as binders for basic aqueous emulsion paints.
- Substrates are often coated with two-component silicate paints or with one-component dispersion silicate paints according to DIN 18363, which, in addition to water glass and water glass-resistant pigment, also contain up to 5% by weight of organic components, based on the total amount of dispersion silicate paint.
- Synthetic resin dispersions are usually used as organic constituents.
- Emulsion paints which contain polymer dispersions as binders are advantageous because of their easier handling. To ensure adequate storage stability, dispersions and emulsion paints usually contain preservatives and / or biocides. It is therefore a goal to provide a biocide-free dispersion and emulsion paint.
- WO 02/0078 describes a preservative-free emulsion paint containing both a polymer dispersion as an organic binder, pigment and / or filler and up to 2% by weight of water glass as an inorganic binder.
- Polystyrene acrylates are mentioned as polymer dispersions and only various monomer classes are listed in general.
- the polymeric binders are often not stable over a long period of time at high pH values, which also affects the dispersion paint.
- the object of the invention was to find a dispersion paint whose binder polymer has good storage stability even at high pH values. Furthermore, a dispersion with a high pH was sought, in which the physical properties such as pH, viscosity and stability of the dispersion or color do not change over a long period of time.
- an aqueous emulsion paint comprising a) 5 to 50% by weight, preferably 8-30% by weight, of an aqueous polymer dispersion having a solids content in the range from 40 to 60% by weight, obtainable by free-radical aqueous emulsion polymerization Monomer mixture containing ethylhexyl acrylate, butyl acrylate and one or more vinyl aromatics, preferably styrene, b) 0.1 to 5% by weight of alkali alkyl siliconate (solid) and / or water-soluble silicate (solid,) c) 20 to 70% by weight of inorganic fillers,
- the pH of the emulsion paint having a value in the range from 10 to 12, preferably 10.5 to 12, particularly preferably 11 to 12.
- the invention comprises aqueous dispersions, a process for their preparation and their use as organic binders in emulsion paints with a high pH.
- an aqueous polymer dispersion (component a) having a solids content in the range from 40 to 60% by weight are obtainable from radical aqueous emulsion polymerization of a monomer mixture containing ethylhexyl acrylate, butyl acrylate and one or more vinyl aromatics.
- the binder polymer contained in the polymer dispersion used according to the invention contains in copolymerized form
- sulfonic acids preferably 0.1 to 5 parts by weight, based on the total monomers, of one or more monomers selected from sulfonic acids, carboxylic acids, their alkali metal or ammonium salts, carboxylic acid anhydrides, amides and hydroxyalkyl esters, and
- 2-ethylhexyl acrylate is preferably suitable as ethylhexyl acrylate.
- both n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate and n-butyl acrylate are suitable as butyl acrylate.
- N-Butyl acrylate is preferred.
- Styrene, a-methylstyrene, o- or p-vinyltoluene are suitable as vinyl aromatics. Styrene is preferably used.
- the polymer can be constructed, ie the monomer mixture up to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on the total monomers, of one or more monomers selected from sulfonic acids, carboxylic acids, their alkali metal or ammonium salts - Contain zen, carboxylic acid anhydrides, amides and hydroxyalkyl esters.
- Examples include monoethylenically unsaturated alkyl or arylsulfonic acids such as vinylsulfonic acid, methallylsulfonic acid, vinylbenzenesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate and a, b-unsaturated C3-C6-carboxylic acids, a, b-Unsaturated C 4 -C 8 dicarboxylic acids or their anhydrides such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride as well as the alkali metal or ammonium salts of the monomers mentioned, in particular their sodium salts.
- the amides and the hydroxyalkyl esters of ⁇ , ⁇ -unsaturated C3-C6 carboxylic acids are suitable - net. These monomers are monomers with stabilizing groups.
- the monomer mixture can contain monomers containing siloxane groups, preferably in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 2 parts by weight, based on the total monomers.
- Suitable monomers containing siloxane groups are, for example, vinyl trialkoxysilanes, e.g. Vinyltrimethoxysilane, vinyltriethoxysilane, alkylvinyldialkoxysilanes or (meth) acryloxyalkyltrialkoxysilanes, e.g. (Meth) acryloxyethyltrimethoxysilane,
- (Meth) acryloxypropyltrimethoxysilane or mixtures thereof are particularly preferred, the monomer mixture of which contains (meth) acryloxyalkyltrialkoxysilanes, preferably in an amount of 0.01 to 5 parts by weight, in particular 0.01 to 2 parts by weight, based on the total monomers.
- the binder polymers according to the invention can also contain further ethylenically unsaturated monomers in copolymerized form in an amount of up to 10 parts by weight, based on the binder polymer. So it can be contained in the monomer mixture up to 10 parts by weight of these other monomers.
- the monomer mixture preferably contains up to 5 parts by weight of other monomers.
- the monomer mixture consists of ethylhexyl acrylate, butyl acrylate, vinyl aromatics and one or more monomers selected from sulfonic acids, carboxylic acids, their alkali metal or ammonium salts, carboxylic acid anhydrides, amides and hydroxyalkyl esters and optionally one or more siloxane-containing monomers.
- Suitable other monomers are, for example, branched and unbranched ethylenically unsaturated C3-cio-olefins, ethyl acrylate, n-propyl acrylate, n-hexyl acrylate, 2-ethylhexylmethac- rylate, or 2-propylheptylacrylate, Cs-C-io-alkyl methacrylates such as n-hexyl methacrylate and 2-ethyl-hexyl methacrylate, C5-Cio-cycloalkyl (meth) acrylates, Ci-Cio-Dialkylmaleinate and / or Ci-C-io-Di - alkyl fumarates.
- Suitable other monomers are furthermore, for example, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile and (C 1 -C 4) -alkyl esters or cycloalkyl esters of methacrylic acid, for example methyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and tert-butyl methacrylate,
- N-vinylpyrolidone N- (2-methacryloyloxyethyl) ethylene urea
- N- (2-acryloyloxyethyl) ethylene urea N- (2-acryloyloxyethyl) ethylene urea
- 2-acetoacetoxyethyl acrylate 2-acetoacetoxyethyl methacrylate
- diacetone acrylamide N-vinylpyrolidone
- N- (2-methacryloyloxyethyl) ethylene urea N- (2-acryloyloxyethyl) ethylene urea
- 2-acetoacetoxyethyl acrylate 2-acetoacetoxyethyl methacrylate
- diacetone acrylamide diacetone acrylamide
- Suitable other monomers are also monomers which give the respective emulsion paints higher strength. These monomers normally have at least one epoxy group or at least two non-conjugated ethylenically unsaturated double bonds. Examples of these are two monomers having vinyl residues, two monomers having vinylidene residues and two monomers having alkenyl residues.
- the di-esters of dihydric alcohols with a, b-monoethylenically unsaturated monocarboxylic acids are particularly advantageous, among which acrylic and methacrylic acid are preferred.
- Examples of such monomers having two non-conjugated ethylenically unsaturated double bonds are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate,
- the binder polymers used according to the invention generally have minimum film-forming temperatures in the range from -5 to 30 ° C. Binder polymers with a minimum film-forming temperature of ⁇ 10 ° C., preferably ⁇ 8 ° C. and particularly preferably ⁇ 5 ° C. are preferred.
- the mean particle size of the binder polymer particles contained in the polymer dispersions, as determined by light scattering, is preferably in the range from 50 to 300 nm, particularly preferably in the range from 50 to 200 nm.
- the aqueous polymer dispersion used according to the invention is obtained by radical emulsion polymerization of the abovementioned monomers in the presence of 0.01 to 1 part by weight, preferably 0.01 to 0.5 part by weight and in particular 0.01 to 0.4 part by weight. Parts, each based on the amount of total monomers carried out at least one radical polymerization initiator.
- Free radical polymerization initiators are all those which are capable of initiating a free radical aqueous emulsion polymerization.
- Peroxides, hydroperoxides, e.g. Alkylimetallperoxodisulfate act as azo compounds.
- Combined systems are also used, which are composed of at least one organic reducing agent and at least one peroxide and / or hydroperoxide, e.g. tert-butyl hydroperoxide with the sodium salt of hydroxymethanesulfonic acid, hydrogen peroxide with ascorbic acid or sodium peroxodisulfate with sodium disulfite.
- Preferred combined systems also contain a small amount of a metal compound soluble in the polymerization medium, the metallic component of which can occur in several valence levels, e.g. Ascorbic acid / iron (II) sulfate / hydrogen peroxide, the sodium salt of hydroxymethanesulfinic acid, sodium sulfite, sodium hydrogen sulfite or sodium bisulfite and, instead of hydrogen peroxide, tert-butyl hydroperoxide or alkali peroxodisulfates and / or ammonium peroxodisulfate being used instead of ascorbic acid.
- a water-soluble iron (II) salt a combination of water-soluble iron and vanadium salts is often used.
- Preferred initiators are the ammonium or alkali metal salts of peroxosulfates or peroxodisulfates, especially sodium or potassium peroxodisulfate.
- At least one nonionic emulsifier in amounts of preferably 0.5 to 10% by weight, in particular 1 to 8% by weight and especially, is optionally used in addition to the surface-active substances customary for emulsion polymerization preferably 2 to 4% by weight, based in each case on the total amount of monomers used.
- Usable nonionic emulsifiers are aromatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO grade: 3 to 50, alkyl radical: C4-C9), ethoxylates of long-chain alcohols (EO degree: 3 to 50, alkyl radical) : C8-C36) as well as polyethylene oxide / polypropylene oxide block copolymers.
- aromatic or aliphatic nonionic emulsifiers for example ethoxylated mono-, di- and trialkylphenols (EO grade: 3 to 50, alkyl radical: C4-C9), ethoxylates of long-chain alcohols (EO degree: 3 to 50, alkyl radical) : C8-C36) as well as polyethylene oxide / polypropylene oxide block copolymers.
- Ethoxylates of long-chain alkanols (alkyl radical C10-C22, average degree of ethoxylation 10 to 50) and, particularly preferably, those with a linear Ci2-Ci8-alkyl radical and average degree of ethoxylation 10 to 50 are used as sole, nonionic emulsifiers.
- alkali and ammonium salts of alkyl sulfates include alkali and ammonium salts of alkyl sulfates (alkyl radical: C8-C12), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 2 to 50, alkyl radical: C12 to Cie) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical : C4-C9), of alkylsulfonic acids (alkyl radical: C12-C18) and of alkylarylsulfonic acids (alkyl radical: Cg to Cis).
- Preferred anionic surfactants are also compounds of the following general formula wherein R 1 and R 2 are hydrogen or C 4 -C24 alkyl and are not simultaneously hydrogen, and X and Y can be alkali metal ions and / or ammonium ions.
- R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 C atoms or hydrogen, and in particular having 6, 12 and 16 C atoms, where R 1 and R 2 are not both hydrogen at the same time
- X and Y are preferably sodium, potassium or ammonium, sodium being particularly preferred.
- Compounds I in which X and Y are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is hydrogen or R 1 are particularly advantageous.
- emulsifiers can be found, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pp. 192 to 208.
- Suitable emulsifiers are commercially available, for example under the tradenames of Dowfax ® 2 A1, Emulan ® NP 50, Dextrol ® OC 50, 825 emulsifier, emulsifier 825 S, Emulan ® OG, Texapon ® NSO, Nekanil ® 904 S, Lumiten ® l-RA, Lumiten ® l-SC, Lumiten ® E 3065, Disponil ® FES 77, Lutensol ® AT 18, Steinapol ® VSL, Emulphor ® NPS 25.
- Suitable protective colloids such as, for example, polyvinyl alcohols, cellulose derivatives or copolymers containing vinyl pyrolidone, can also be used.
- a detailed description of further suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 41 1 -420.
- the total amount of surface-active substances (solid) usually makes up to 30% by weight, preferably 0.3 to 10% by weight and particularly preferably 0.5 to 5
- the molecular weight of the binder polymers can be adjusted by adding small amounts, generally up to 2% by weight, based on the monomers to be polymerized, of one or more substances which regulate the molecular weight, for example organic thio compounds or allyl alcohols. However, preference is given to those binder polymers which have been prepared in the absence of such compounds.
- the emulsion polymerization can be carried out either continuously or according to the batch procedure, preferably according to a semi-continuous process.
- the monomers to be polymerized can be added continuously, including step or gradient procedures, to the polymerization batch.
- a feed process with short feed times is preferred, ie the monomers, preferably as an aqueous emulsion, are metered into the reaction mixture within 1 to 4 hours, preferably within 1.5 to 3 hours.
- the emulsion polymerization can be carried out by the seed latex process or in the presence of a seed latex produced in situ to adjust the polymer particle size. Methods for this are known and can be found in the prior art (see EP-B 40 419 and 'Encyclopedia of Polymer Science and Technology', vol. 5, John Wiley & Sons Inc., New York, 1966, p. 847 ).
- the prior art thus recommends that a defined, finely divided seed polymer dispersion be placed in the polymerization vessel in the feed process and then polymerize the monomers in the presence of the seeds.
- the seed polymer particles act as 'polymerization nuclei' and decouple the polymer particle formation and the polymer particle growth.
- Further seed dispersion can be added during the emulsion polymerization.
- wide size distributions of the polymer particles are achieved, which are often desirable in particular in the case of polymer dispersions with a high solids content (cf. DE-A 42 13 965).
- this can also be generated in situ.
- part of the monomers and the initiator are initially introduced together with the emulsifier and heated to the reaction temperature, a relatively finely divided latex being formed.
- the actual polymerization is then carried out in the same polymerization vessel using the feed process (see also DE-A 42 13 965).
- the manner in which the initiator of the emulsion polymerization is metered in is not critical.
- the initiator can either be completely introduced into the polymerization vessel or, depending on its consumption, can be added continuously or in stages during the course of the emulsion polymerization.
- the procedure depends both on the chemical nature of the initiator and on the polymerization temperature and can be chosen by the person skilled in the art as required. A continuous or stepwise addition to the reaction mixture is preferred.
- the polymerization pressure and the polymerization temperature are also of minor importance. In general, temperatures between room temperature and 120 ° C, preferably at temperatures of 50 to 95 ° C and particularly preferably between 70 and 90 ° C.
- aqueous polymer dispersions largely free of odorants, such as residual monomers and other organic volatile constituents. This can be done physically in a manner known per se by removal by distillation (in particular by steam distillation) or by stripping with an inert gas.
- the lowering of the residual monomers can also be carried out chemically by radical postpolymerization, in particular under the action of redox initiator systems, such as those e.g. in the
- Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide or alkali peroxide sulfates are particularly suitable as oxidizing agents for redox-initiated postpolymerization.
- the post-polymerization with the redox initiator system is carried out in the temperature range from 10 to 100 ° C., preferably at 20 to 90 ° C.
- the redox partners can be added to the dispersion completely, in portions or continuously over a period of 10 minutes to 4 hours, independently of one another.
- soluble salts of metals of varying valency such as iron, copper or vanadium salts, can also be added to the dispersion.
- Complexing agents are also frequently added, which keep the metal salts in solution under the reaction conditions.
- the polymer dispersion is usually finally neutralized with a base, such as alkali metal or alkaline earth metal hydroxides, alkaline earth metal oxides or volatile or nonvolatile amines.
- a base such as alkali metal or alkaline earth metal hydroxides, alkaline earth metal oxides or volatile or nonvolatile amines.
- non-volatile amines include mine especially ethoxylated diamines or polyadenylation, as are commercially available, for example under the name Jeffamine ® (Texaco Chemical Co.). Polymer dispersions produced by this process are generally known.
- Such polymer dispersions can now be adjusted together with alkali alkyl siliconate and / or water-soluble silicate to a pH value in the range from 10 to 12, preferably 11 to 12. According to an embodiment of the invention, this adjustment of the pH can be carried out when formulating the emulsion paint of the invention.
- the present invention therefore also relates to the use of an aqueous polymer dispersion having a solids content in the range from 40 to 60% by weight, obtainable by radical aqueous emulsion polymerization of a monomer mixture comprising ethylhexyl acrylate, butyl acrylate and one or more vinyl aromatics as organic binders, in combination with an alkali alkyl siliconate and / or water-soluble silicate in a coating agent, preferably an emulsion paint, with a pH in the range from 10 to 12.
- Suitable inorganic bases are the above-mentioned alkali or alkaline earth metal hydroxides and alkaline earth metal oxides. The order of addition is arbitrary.
- the present invention therefore also relates to aqueous polymer dispersions which are obtainable by free radical aqueous emulsion polymerization of a monomer mixture comprising ethylhexyl acrylate, butyl acrylate and one or more vinyl aromatics, preferably styrene, and subsequent adjustment of the pH to a value in the range from 10 to 12 with at least at least 0.5% by weight of alkali alkyl siliconate and / or water-soluble silicates based on the aqueous polymer dispersion and, if appropriate, with an inorganic base.
- Aqueous polymer dispersions are preferably obtainable by free-radical aqueous emulsion polymerization of a monomer mixture comprising 10 to 30 parts by weight, based on the total monomers, ethylhexyl acrylate, 25 to 50 parts by weight based on the total monomers, butyl acrylate and 30 to 50 parts by weight .
- the preferred polymer dispersions mentioned above which are obtained by free-radical aqueous emulsion polymerization and then the pH to a value in the range from 10 to 12 with at least 0.5, preferably with 0.5 to 10% by weight of alkali metal alkyl silicone and / or water-soluble Silicates based on the aqueous polymer dispersion and, if appropriate, with an inorganic base.
- the present invention therefore also relates to a process for the preparation of an aqueous polymer dispersion, in which a monomer mixture comprising ethylhexyl acrylate, butyl acrylate and one or more vinylaromatics, preferably styrene, is radically polymerized and then the pH of the dispersion obtained thereafter with an alkali alkyl siliconate and / or a water-soluble silicate and optionally an inorganic base to a value in the range 10 to 12.
- Alkali metal alkyl siliconates according to the invention are in particular compounds with the formula MOSi (R) (OH) z, where M is an alkali metal and R is an alkyl radical.
- Alkali metal alkyl siliconates can be obtained, for example, by reacting alkylsilanetriol with an alkali metal hydroxide. The preparation of solutions of alkali metal alkyl silicates, in particular aqueous solutions, is described for example in DE 1 031 910.
- the alkali metal M can in particular be selected from the group consisting of lithium, sodium, potassium and mixtures thereof.
- the alkyl radical R is preferably selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl , tert-pentyl, neopentyl, phenyl, aryl, and cyclohexyc
- the alkyl radical is preferably methyl.
- the alkali metal alkyl silicone of the emulsion paint according to the invention is more preferably selected from the group consisting of lithium methyl siliconate, sodium methyl siliconate and potassium methyl siliconate. Most preferably, the alkali metal alkyl siliconate is potassium methyl siliconate. These alkali metal alkyl silicates, in particular potassium methyl siliconate, result in homogeneous surfaces and are easy to handle.
- the alkali metal alkyl siliconate is contained in the emulsion paint according to the invention in an amount of 0.1 to 5 wt .-%, based on the total weight of the emulsion paint.
- the emulsion paint according to the invention preferably contains 0.1 to 2% by weight, in particular 0.3 to 2% by weight or 0.5 to 1.5% by weight, of alkali metal alkyl siliconate, in each case based on the total weight of the emulsion paint. Dispersion paints with these contents show good processability and good storage stability.
- the water-soluble alkali silicate is present in the emulsion paint according to the invention in an amount of 0.1 to 5% by weight (solid), based on the total weight of the emulsion paint. Based on the Si0 2 content, the proportion of water-soluble alkali silicates in the dispersion paint is preferably 0.06 to 3.3% by weight, calculated as silicon dioxide.
- Water-soluble silicates suitable according to the invention are water-soluble alkali silicate, also referred to as water glass, such as lithium-sodium or preferably potassium silicate (potassium water glass).
- water glass such as lithium-sodium or preferably potassium silicate (potassium water glass).
- K 2 0 content ISO 1692
- Si0 2 content Si0 2 content
- aqueous polymer dispersions according to the invention are preferably suitable for the formulation of emulsion paints, in particular interior paints, with a pigment volume concentration> 50, preferably 60 to 90.
- the emulsion paints also contain 20 to 70% by weight of inorganic fillers.
- suitable fillers are e.g. B. aluminosilicates, such as feldspar, silicates, such as kaolin, talc, mica, magnesite, alkaline earth carbonates, such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates, such as calcium sulfate, silicon dioxide, etc.
- the fillers can be used as individual components. In practice, however, Grestoffmi mixtures have proven particularly useful, e.g. B. calcium carbonate / kaolin, calcium carbonate / talc.
- Finely divided fillers can also be used to increase opacity and / or to save white pigments. Mixtures of color pigments and fillers are preferably used to adjust the opacity of the color and depth of color.
- the emulsion paints can also contain up to 30% by weight of at least one pigment.
- Suitable pigments are, for example, inorganic white pigments such as titanium dioxide. preferably in the rutile form, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopone (zinc sulfide + barium sulfate) or colored pigments, for example iron oxides, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, Paris blue or Schweinfurt green.
- the emulsion paints according to the invention can also contain organic color pigments, e.g. B.
- the emulsion paints also contain 0.1 to 10% by weight of other auxiliaries, as are customary in emulsion paints based on aqueous polymer dispersions.
- the customary auxiliaries also include wetting or dispersing agents, such as sodium, potassium or ammonium polyphosphates, alkali metal and ammonium salts of acrylic or maleic anhydride copolymers, polyphosphonates, such as 1-hydroxyethane-1, 1-diphosphonic acid sodium and naphthalenesulfonic acid salts, in particular their sodium salts.
- Suitable auxiliaries are leveling agents, defoamers, biocides and thickeners.
- Suitable thickeners are e.g. B. associative thickeners, such as polyurethane thickeners.
- the amount of the thickener is preferably less than 1% by weight, particularly preferably less than
- PVK (VP + VF) x 100 / ( VP + VF + VB) (see Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 15, p. 667).
- Aqueous emulsion paints containing a) 5 to 30% by weight, preferably 8 to 15% by weight of the aqueous polymer dispersion with a solids content in the range from 40 to 60% by weight are particularly preferred,
- the pH of the emulsion paint having a value in the range from 10 to 12, preferably 11 to 12.
- Another object of the present invention is the use of an aqueous polymer dispersion, as previously defined, in emulsion paints, preferably for highly filled interior paints.
- the emulsion paints according to the invention with a pH> 10 have good pH stability, so that they are not or only slightly susceptible to attack by microorganisms. This very good stability makes it possible to formulate without or with significantly smaller amounts of preservatives and / or biocides.
- new dispersions according to the invention which have been adjusted to a pH of 10 to 12, preferably 11 to 12, with alkali alkyl siliconate and / or water-soluble silicate and optionally with an alkaline base. They also have good pH stability and are not prone to attack by microorganisms.
- dispersions according to the invention do not form a coagulum at a high pH. Coagulates generally lead to filtration problems. Dispersions with coagulate or tendency to coagulate are usually also problematic in use.
- the particle size (Z mean) of the polymer particles was determined by dynamic light scattering on a 0.01% strength by weight dispersion at 23 ° C. using an Autosizer IIc from Malvern Instruments, England. The average diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function is given.
- the pH value was determined using a Knick pH meter (model: Portamess 913 (X) ph).
- Solid contents of the polymer dispersions were determined by distributing 0.5 to 1.5 g of the polymer dispersion in a metal lid with a 4 cm diameter and then using a dryer (Mettler Toledo HR 83 halogen dryer) at 140 ° C. to constant weight were dried. The ratio of the mass of the sample after drying to the mass during sampling gives the solids content of the polymer.
- the viscosity was determined using two different methods:
- ICI is measured with an I.C.I Cone & Plate Viscosimeter from Epprecht Instruments & Controls AG and specified in the unit Poises [P]
- KU is measured using a Brookfield viscometer (from Brookfield) measured at 200rpm and in cancer units [KU] Examination of the polymer dispersion for stability against coagulum formation:
- a stored dispersion was applied thinly to a glass plate (using a glass rod) and the defects were assessed visually (specks / semolina). The less speck formation or semolina formation over the storage period, the lower the tendency of the dispersion to coagulate and the more stable the colloidal stability of the dispersion.
- Polymer dispersions were produced by means of semi-continuous emulsion polymerization. The particle sizes were checked using a polystyrene seed in the reactor template and adjusted to 100-300 nm. The quantitative ratios of the monomers used are summarized in Table 1. The water distribution was chosen so that the theoretical solids content of the polymerized dispersion was at the values given in Table 1.
- the dispersions B1 and B2 according to the invention or comparative dispersions V1, V2 and V3 not according to the invention were prepared using the monomers specified in Table 1 and in the amounts stated.
- SILRES® BS 16 was used as the potassium methyl siliconate.
- the measurement results show that the dispersion D2B1 produced according to the invention maintains the pH even over prolonged storage and does not weaken.
- the pH falls below a value of 1 1
- an increased infestation with microorganisms is generally to be expected.
- the drop in the pH value can already be recognized as a trend in the storage of sample D1V1.
- the dispersions D2B1 according to the invention thus have better storage stability.
- reaction products B1 and B2 were first made neutral with sodium hydroxide solution (pH 7) and then with Trasol ® KH-K (potassium water glass, from BASF) in a mass ratio of 80 to 20 (polymer dispersion / T rasol KW-K) with stirring offset and homogenized.
- pH values given in Table 4 resulted
- dispersions produced by the process claimed are very stable to a high pH. This can be seen from the fact that the physical properties such as pH, viscosity or stability (coagulum formation) are very constant.
- B1 and V3 were adjusted to neutral (pH 7) with sodium hydroxide solution and then Trasol® KW-N (potassium water glass with a solids content of 28% in a mass ratio of 80 to 20 (polymer dispersion / T rasol KW-N) was added with stirring Dispersions D8B1 and D9V3 with an initial pH of 10.9 are obtained. Both dispersions have low viscosity and are flowable. Again, stability tests were carried out.
- a dispersion paint was produced with the following compositions:
- the above formulation has a solids content of 48.9% by weight and a PVC of 71.7. After production, the color had a pH of 10 and was adjusted to a pH of 11.3 with 20% strength by weight potassium hydroxide solution.
- the dispersion D2B1 which is adjusted to pH> 11 with potassium methyl siliconate and potassium hydroxide solution, can be used as a binder in the formulation as a color and shows a stable pH after storage.
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Abstract
Description
Wässrige Dispersionen und Dispersionsfarben enthaltend Ethylhexylacrylat-Butylacrylat-Styrol- Copolymere Aqueous dispersions and emulsion paints containing ethylhexyl acrylate-butyl acrylate-styrene copolymers
Die vorliegende Erfindung betrifft wässrige Dispersionen und Dispersionsfarben, insbesondere Innenfarben, enthaltend Ethylhexylacrylat-Butylacrylat-Styrol Copolymere als Bindemittel, ein Verfahren zur Herstellung der wässrigen Dispersion sowie der Dispersionsfarbe, die Verwen- dung der wässrigen Dispersionsfarbe sowie die Verwendung von Ethylhexylacrylat-Buytlacrylat- Styrol-Copolymere als Bindemittel für basische wässrige Dispersionsfarben. The present invention relates to aqueous dispersions and emulsion paints, in particular interior paints, containing ethylhexyl acrylate-butyl acrylate-styrene copolymers as binders, a process for the preparation of the aqueous dispersion and the dispersion paint, the use of the aqueous dispersion paint and the use of ethylhexyl acrylate-buytlacrylate-styrene. Copolymers as binders for basic aqueous emulsion paints.
Die Beschichtung von Untergründen erfolgt oftmals mit zweikomponentigen Silikatfarben oder mit einkomponentigen Dispersions-Silikatfarben nach DIN 18363, die neben Wasserglas und wasserglasbeständigen Pigment noch bis zu 5 Gew.-% organische Bestandteile, bezogen auf die Gesamtmenge an Dispersions-Silikatfarbe, enthalten. Als organische Bestandteile werden üblicherweise Kunstharzdispersionen verwendet. Substrates are often coated with two-component silicate paints or with one-component dispersion silicate paints according to DIN 18363, which, in addition to water glass and water glass-resistant pigment, also contain up to 5% by weight of organic components, based on the total amount of dispersion silicate paint. Synthetic resin dispersions are usually used as organic constituents.
Vorteilhaft aufgrund ihrer leichteren Handhabung sind Dispersionsfarben, die als Bindemittel Polymerdispersionen enthalten. Um eine ausreichende Lagerstabilität zu gewährleisten, enthal- ten Dispersionen und Dispersionsfarben üblicherweise Konservierungsmittel und/oder Biozide. Es ist daher ein Ziel eine biozidfreie Dispersion und Dispersionsfarbe zur Verfügung zu stellen. Emulsion paints which contain polymer dispersions as binders are advantageous because of their easier handling. To ensure adequate storage stability, dispersions and emulsion paints usually contain preservatives and / or biocides. It is therefore a goal to provide a biocide-free dispersion and emulsion paint.
Die WO 02/0078 beschreibt eine konservierungsmittelfreie Dispersionsfarbe enthaltend sowohl eine Polymerdispersion als organische Bindemittel, Pigment und/oder Füllstoff sowie bis zu 2 Gew.-% Wasserglas als anorganisches Bindemittel. Als Polymerdisperisonen werden Polystyro- lacrylate genannt sowie nur allgemein verschiedene Monomerklassen aufgezählt. Oftmals sind die polymeren Bindemittel bei hohen pH-Werten nicht langzeitstabil, was sich auch auf die Dis- persionsfarbe auswirkt. WO 02/0078 describes a preservative-free emulsion paint containing both a polymer dispersion as an organic binder, pigment and / or filler and up to 2% by weight of water glass as an inorganic binder. Polystyrene acrylates are mentioned as polymer dispersions and only various monomer classes are listed in general. The polymeric binders are often not stable over a long period of time at high pH values, which also affects the dispersion paint.
Die DE 10 2014 013 455 sowie die WO2017/144694 lehren konservierungsmittelfreie Dispersi- onsfarben, die einen hohen pH-Wert aufweisen und denen zusätzlich Alkalimetallalkylsiliconate zugesetzt wurden. Auch diese Schrift lehrt als Polymerdispersionen Reinacrylat bzw. Polystyro- lacrylat sowie nur ganz allgemein verschiedene Monomerklassen. DE 10 2014 013 455 and WO2017 / 144694 teach preservative-free emulsion paints which have a high pH and to which alkali metal alkyl silicone silicates have additionally been added. This publication also teaches pure acrylic or polystyrene acrylate as polymer dispersions and only very generally different monomer classes.
Der Erfindung lag die Aufgabe zugrunde, eine Dispersionsfarbe zu finden, deren Bindemittelpo- lymer auch bei hohen pH-Werten eine gute Lagerstabilität aufweisen. Weiterhin wurde eine Dis- persion mit hohem pH-Wert gesucht, bei der sich über einen möglichst langen Zeitraum die physikalischen Eigenschaften wie pH-Wert, Viskosität und Stabilität der Dispersion bzw. der Farbe nicht ändern. The object of the invention was to find a dispersion paint whose binder polymer has good storage stability even at high pH values. Furthermore, a dispersion with a high pH was sought, in which the physical properties such as pH, viscosity and stability of the dispersion or color do not change over a long period of time.
Die Aufgabe wird erfindungsgemäß gelöst durch eine wässrige Dispersionfarbe enthaltend a) 5 bis 50 Gew.-%, bevorzugt 8-30 Gew.-% einer wässrigen Polymerdispersion mit einem Feststoffgehalt im Bereich von 40 bis 60 Gew.-% erhältlich durch radikalische wässrige Emulsionspolymerisation einer Monomermischung enthaltend Ethylhexylacrylat, Butylac- rylat und einen oder mehrere Vinylaromaten, bevorzugt Styrol, b) 0,1 bis 5 Gew.-% Alkalialkylsilikonat (fest) und/oder wasserlösliches Silikat (fest,) c) 20 bis 70 Gew.-% anorganischer Füllstoffe, The object is achieved according to the invention by an aqueous emulsion paint comprising a) 5 to 50% by weight, preferably 8-30% by weight, of an aqueous polymer dispersion having a solids content in the range from 40 to 60% by weight, obtainable by free-radical aqueous emulsion polymerization Monomer mixture containing ethylhexyl acrylate, butyl acrylate and one or more vinyl aromatics, preferably styrene, b) 0.1 to 5% by weight of alkali alkyl siliconate (solid) and / or water-soluble silicate (solid,) c) 20 to 70% by weight of inorganic fillers,
d) 0 bis 30 Gew.-%, wenigstens eines Pigments, d) 0 to 30% by weight of at least one pigment,
e) 0,1 bis 10 Gew.-% übliche Hilfsmittel, sowie e) 0.1 to 10% by weight of conventional auxiliaries, and
f) Wasser f) water
jeweils bezogen auf die Gesamtmenge der Dispersionsfarbe wobei der pH-Wert der Dispersi- onsfarbe einen Wert im Bereich von 10 bis 12, bevorzugt 10,5 bis 12, besonders bevorzugt 11 bis 12 aufweist. in each case based on the total amount of the emulsion paint, the pH of the emulsion paint having a value in the range from 10 to 12, preferably 10.5 to 12, particularly preferably 11 to 12.
Weiterhin umfasst die Erfindung wässrige Dispersionen, ein Verfahren zu ihrer Herstellung so- wie ihre Verwendung als organische Bindemittel in Dispersionsfarben mit hohem pH-Wert. Furthermore, the invention comprises aqueous dispersions, a process for their preparation and their use as organic binders in emulsion paints with a high pH.
Erfindungsgemäß werden 5 bis 50 Gew.-%, bevorzugt 8 bis 30 Gew.-% insbesondere 10 bis 20 Gew.-% einer wässrigen Polymerdispersion (Komponente a) mit einem Feststoffgehalt im Be- reich von 40 bis 60 Gew.-% erhältlich durch radikalische wässrige Emulsionspolymerisation ei- ner Monomermischung enthaltend Ethylhexylacrylat, Butylacrylat und einen oder mehrere Vi- nylaromaten eingesetzt. According to the invention, 5 to 50% by weight, preferably 8 to 30% by weight, in particular 10 to 20% by weight, of an aqueous polymer dispersion (component a) having a solids content in the range from 40 to 60% by weight are obtainable from radical aqueous emulsion polymerization of a monomer mixture containing ethylhexyl acrylate, butyl acrylate and one or more vinyl aromatics.
Das in der erfindungsgemäß eingesetzten Polymerdispersion enthaltenen Bindemittelpolymer enthält in einpolymerisierter Form The binder polymer contained in the polymer dispersion used according to the invention contains in copolymerized form
10 bis 30 Gew.-Teile, bevorzugt 12 bis 20 Gew.-Teile bezogen auf die Gesamtmonomere, 10 to 30 parts by weight, preferably 12 to 20 parts by weight, based on the total monomers,
Ethylhexylacrylat, ethylhexyl acrylate,
25 bis 50 Gew.-Teile, bevorzugt 30bis 45 Gew.-Teile bezogen auf die Gesamtmonomere, Buty- lacrylat 25 to 50 parts by weight, preferably 30 to 45 parts by weight, based on the total monomers, butyl acrylate
30 bis 50 Gew.-Teile, bevorzugt 35 bis 45 Gew.-Teile bezogen auf die Gesamtmonomere, eines oder mehrere Vinylaromaten 30 to 50 parts by weight, preferably 35 to 45 parts by weight, based on the total monomers, of one or more vinyl aromatics
0 bis 10 Gew.-Teile, bevorzugt 0,1 bis 5 Gew.-Teile bezogen auf die Gesamtmonomere, eines oder mehrerer Monomere ausgewählt unter Sulfonsäuren, Carbonsäuren, deren Alkalimetall- oder Ammoniumsalzen, Carbonsäureanhydriden, Ami- den und Hydroxyalkylester, und 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on the total monomers, of one or more monomers selected from sulfonic acids, carboxylic acids, their alkali metal or ammonium salts, carboxylic acid anhydrides, amides and hydroxyalkyl esters, and
0 bis 10 Gew.-Teile, bevorzugt 0,1 bis 5 Gew.-Teile bezogen auf die Gesamtmonomere, sons- tige Monomere 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on the total monomers, other monomers
wobei die Summe aller Monomere 100 Gew.-Teile ergibt. where the sum of all monomers is 100 parts by weight.
Als Ethylhexylacrylat ist erfindungsgemäß bevorzugt 2-Ethylhexylacrylat geeignet. According to the invention, 2-ethylhexyl acrylate is preferably suitable as ethylhexyl acrylate.
Als Butylacrylat sind erfindungsgemäß sowohl n n-Butylacrylat, Isobutylacrylat, sec-Butylacrylat und n-Butylacrylat geeignet. Bevorzugt wird n-Butylacrylat. According to the invention, both n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate and n-butyl acrylate are suitable as butyl acrylate. N-Butyl acrylate is preferred.
Als Vinylaromaten eignen sich Styrol, a-Methylstyrol, o- oder p-Vinyltoluol. Bevorzugt wird Styrol eingesetzt. Weiterhin kann das Polymer aufgebaut sein, also die Monomermischung bis zu 10 Gew.-Teile, bevorzugt 0,1 bis 5 Gew.-Teile bezogen auf die Gesamtmonomere, eines oder mehrerer Mono- mere ausgewählt unter Sulfonsäuren, Carbonsäuren, deren Alkalimetall- oder Ammoniumsal- zen, Carbonsäureanhydriden, Amiden und Hydroxyalkylester enthalten. Beispielhaft seien mo- noethylenisch ungesättigte Alkyl- oder Arylsulfonsäuren wie Vinylsulfonsäure, Methallylsulfon- säure, Vinylbenzolsulfonsäure, Acrylamidoethansulfonsäure, Acrylamidopropansulfonsäure, 2- Sulfoethyl(meth)acrylat, Sulfopropyl(meth)acrylat sowie a,b-ungesättigte C3-C6-Carbonsäuren, a,b-ungesättigte C4-C8-Dicarbonsäuren oder deren Anhydride wie Acrylsäure, Methacrylsäure, Crotonsäure, Fumarsäure, Maleinsäure, Maleinsäureanhydrid, Itaconsäure und Itaconsäurean- hydrid sowie die Alkalimetall- oder Ammoniumsalze der genannten Monomere, insbesondere deren Natriumsalze genannt. Weiterhin sind die Amide und die Hydroxyalkylester der a,ß-un- gesättigten C3-C6-Carbonsäuren, bevorzugt Acrylamid, Methacrylamid, 2-Hy-droxyethylacrylat, 2-Hydroxyethylmethacrylat, 2-Hydroxypropyl(meth)acrylat oder 1 ,4-Butandiolmonoacrylat geeig- net. Bei diesen Monomeren handelt es sich um Monomere mit stabilisierende Gruppen. Styrene, a-methylstyrene, o- or p-vinyltoluene are suitable as vinyl aromatics. Styrene is preferably used. Furthermore, the polymer can be constructed, ie the monomer mixture up to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on the total monomers, of one or more monomers selected from sulfonic acids, carboxylic acids, their alkali metal or ammonium salts - Contain zen, carboxylic acid anhydrides, amides and hydroxyalkyl esters. Examples include monoethylenically unsaturated alkyl or arylsulfonic acids such as vinylsulfonic acid, methallylsulfonic acid, vinylbenzenesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate and a, b-unsaturated C3-C6-carboxylic acids, a, b-Unsaturated C 4 -C 8 dicarboxylic acids or their anhydrides such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride as well as the alkali metal or ammonium salts of the monomers mentioned, in particular their sodium salts. Furthermore, the amides and the hydroxyalkyl esters of α, β-unsaturated C3-C6 carboxylic acids, preferably acrylamide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate or 1,4-butanediol monoacrylate, are suitable - net. These monomers are monomers with stabilizing groups.
Weiterhin kann die Monomermischung Siloxangruppen enthaltende Monomere enthalten, vor- zugsweise in einer Menge von 0,01 bis 5 Gew.-Teilen, bevorzugt 0,01 bis 2 Gew.-Teile bezo- gen auf die Gesamtmonomere. Geeignete Siloxangruppen enthaltende Monomere sind bei- spielsweise Vinyltrialkoxysilane, z.B. Vinyltrimethoxysilan, Vinyltriethoxysilan, Alkylvinyldialkoxy- silane oder (Meth)acryloxyalkyltrialkoxysilane, z.B. (Meth)acryloxyethyltrimethoxysilan, Furthermore, the monomer mixture can contain monomers containing siloxane groups, preferably in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 2 parts by weight, based on the total monomers. Suitable monomers containing siloxane groups are, for example, vinyl trialkoxysilanes, e.g. Vinyltrimethoxysilane, vinyltriethoxysilane, alkylvinyldialkoxysilanes or (meth) acryloxyalkyltrialkoxysilanes, e.g. (Meth) acryloxyethyltrimethoxysilane,
(Meth)acryloxypropyltrimethoxysilan oder Gemische davon. Besonders werden wässrige Poly- merdispersion bevorzugt, deren Monomermischung (Meth)acryloxyalkyltrialkoxysilane enthält, vorzugsweise in einer Menge von 0,01 bis 5 Gew.-Teilen, insbesondere 0,01 bis 2 Gew.-Teile bezogen auf die Gesamtmonomere. (Meth) acryloxypropyltrimethoxysilane or mixtures thereof. Aqueous polymer dispersions are particularly preferred, the monomer mixture of which contains (meth) acryloxyalkyltrialkoxysilanes, preferably in an amount of 0.01 to 5 parts by weight, in particular 0.01 to 2 parts by weight, based on the total monomers.
Neben den genannten Monomeren Ethylhexylacrylat, Butylacrylat, Vinylaromaten und den obengenannten Monomeren mit stabilisierenden Gruppen, sowie Siloxangruppen enthaltenden Monomeren können die erfindungsgemäßen Bindemittelpolymere auch weitere ethylenisch un- gesättigte Monomere in einer Menge bis zu 10 Gew.-Teile bezogen auf das Bindemittelpolymer einpolymerisiert enthalten. Es können also in der Monomermischung bis zu 10 Gew.-Teile die ser sonstigen Monomere enthalten sein. Bevorzugt enthält die Monomermischung bis zu 5 Gew.-Teile sonstige Monomere. In addition to the monomers mentioned ethylhexyl acrylate, butyl acrylate, vinyl aromatics and the abovementioned monomers with stabilizing groups and monomers containing siloxane groups, the binder polymers according to the invention can also contain further ethylenically unsaturated monomers in copolymerized form in an amount of up to 10 parts by weight, based on the binder polymer. So it can be contained in the monomer mixture up to 10 parts by weight of these other monomers. The monomer mixture preferably contains up to 5 parts by weight of other monomers.
Gemäß einer bevorzugten Ausführungsform besteht die Monomermischung aus Ethylhexylac- rylat, Butylacrylat, Vinylaromaten und einem oder mehreren Monomeren ausgewählt unter Sul- fonsäuren, Carbonsäuren, deren Alkalimetall- oder Ammoniumsalzen, Carbonsäureanhydriden, Amiden und Hydroxyalkylester und gegebenenfalls einem oder mehreren Siloxangruppen ent- haltenden Monomer. According to a preferred embodiment, the monomer mixture consists of ethylhexyl acrylate, butyl acrylate, vinyl aromatics and one or more monomers selected from sulfonic acids, carboxylic acids, their alkali metal or ammonium salts, carboxylic acid anhydrides, amides and hydroxyalkyl esters and optionally one or more siloxane-containing monomers.
Geeignete sonstige Monomere sind beispielsweise verzweigte und unverzweigte ethylenisch ungesättigte C3-Cio-Olefine, Ethylacrylat, n-Propylacrylat, n-Hexylacrylat, 2-Ethylhexylmethac- rylat, oder 2-Propylheptylacrylat, Cs-C-io-Alkylmethacrylate wie n-Hexylmethacrylat und 2-Ethyl- hexylmethacrylat, C5-Cio-Cycloalkyl(meth)acrylate, Ci-Cio-Dialkylmaleinate und/oder Ci-C-io-Di- alkylfumarate. Suitable other monomers are, for example, branched and unbranched ethylenically unsaturated C3-cio-olefins, ethyl acrylate, n-propyl acrylate, n-hexyl acrylate, 2-ethylhexylmethac- rylate, or 2-propylheptylacrylate, Cs-C-io-alkyl methacrylates such as n-hexyl methacrylate and 2-ethyl-hexyl methacrylate, C5-Cio-cycloalkyl (meth) acrylates, Ci-Cio-Dialkylmaleinate and / or Ci-C-io-Di - alkyl fumarates.
Geeignete sonstige Monomere sind weiterhin beispielsweise Vinylchlorid, Vinylidenchlorid, Ac- rylnitril, Methacrylnitril, sowie (Ci-C4)-Alkylester oder -Cycloalkylester der Methacrylsäure, bei- spielsweise Methylmethacrylat, Cyclohexylmethacrylat, Isobornylmethacrylat und tert.-Butylme- thacrylat, Suitable other monomers are furthermore, for example, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile and (C 1 -C 4) -alkyl esters or cycloalkyl esters of methacrylic acid, for example methyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and tert-butyl methacrylate,
Weiterhin als sonstige Monomere geeignete sind N-Vinylpyrolidon, N-(2-Methacryloyloxy- ethyl)ethylen-harnstoff, N-(2-Acryloyloxyethyl)-ethylenharnstoff, 2-Acetoacetoxyethylacrylat, 2- Acetoacetoxy-ethylmethacrylat, Diacetonacrylamid. Also suitable as other monomers are N-vinylpyrolidone, N- (2-methacryloyloxyethyl) ethylene urea, N- (2-acryloyloxyethyl) ethylene urea, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, diacetone acrylamide.
Geeignete sonstige Monomere sind weiterhin Monomere, die den jeweiligen Dispersionsfarben eine höhere Festigkeit verleihen. Diese Monomere weisen normalerweise wenigstens eine Epo- xygruppe oder wenigstens zwei nicht konjugierte ethylenisch ungesättigte Doppelbindungen auf. Beispiele hierfür sind zwei Vinylreste aufweisende Monomere, zwei Vinylidenreste aufwei- sende Monomere sowie zwei Alkenylreste aufweisende Monomere. Besonders vorteilhaft sind dabei die Di-Ester zweiwertiger Alkohole mit a,b-monoethylenisch ungesättigten Monocarbon- säuren unter denen die Acryl- und Methacrylsäure bevorzugt sind. Beispiele für derartige zwei nicht konjugierte ethylenisch ungesättigte Doppelbindungen aufweisende Monomere sind Alky- lenglykoldiacrylate und -dimethacrylate, wie Ethylenglykoldiacrylat, 1 ,2-Propylenglykoldiacrylat,Suitable other monomers are also monomers which give the respective emulsion paints higher strength. These monomers normally have at least one epoxy group or at least two non-conjugated ethylenically unsaturated double bonds. Examples of these are two monomers having vinyl residues, two monomers having vinylidene residues and two monomers having alkenyl residues. The di-esters of dihydric alcohols with a, b-monoethylenically unsaturated monocarboxylic acids are particularly advantageous, among which acrylic and methacrylic acid are preferred. Examples of such monomers having two non-conjugated ethylenically unsaturated double bonds are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate,
1 ,3-Propylenglykoldiacrylat, 1 ,3-Butylenglykoldiacrylat, 1 ,4-Butylenglykoldiacrylate, 1 ,6-Hexan- glykoldiacrylat und Ethylenglykoldimethacrylat, 1 ,2-Propylenglykoldimethacrylat, 1 ,3-Propylen- glykoldimethacrylat, 1 ,3-Butylenglykoldimethacrylat, 1 ,4-Butylenglykoldimethacrylat, 1 ,6-Hexan- diglycoldimethacrylat sowie Vinylmethacrylat, Vinylacrylat, Allylmethacrylat, Allyl-acrylat, Diallyl- maleat, Diallylfumarat, Cyclopentadienylacrylat, Triallylcyanurat oder Triallylisocy-anurat. 1, 3-propylene glycol diacrylate, 1, 3-butylene glycol diacrylate, 1, 4-butylene glycol diacrylate, 1, 6-hexane glycol diacrylate and ethylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol dimethacrylate, 1, 3 4-butylene glycol dimethacrylate, 1, 6-hexane diglycol dimethacrylate and vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, cyclopentadienyl acrylate, triallyl cyanurate or triallyl isocyanurate.
Alle als sonstige Monomere genannte Monomere können einzeln oder in Mischungen verwen- det werden. All monomers mentioned as other monomers can be used individually or in mixtures.
Die erfindungsgemäß eingesetzten Bindemittelpolymere weisen in der Regel Mindestfilmbilde- temperaturen im Bereich von -5 bis 30°C auf. Bevorzugt werden Bindemittelpolymere mit einer Mindestfilmbildetemperatur <10°C, bevorzugt <8°C, und besonders bevorzugt <5°C auf. The binder polymers used according to the invention generally have minimum film-forming temperatures in the range from -5 to 30 ° C. Binder polymers with a minimum film-forming temperature of <10 ° C., preferably <8 ° C. and particularly preferably <5 ° C. are preferred.
Die über Lichtstreuung ermittelte mittlere Teilchengröße der in den Polymerdispersionen enthal- tenen Bindemittelpolymerteilchen liegt vorzugsweise im Bereich von 50 bis 300 nm, besonders bevorzugt im Bereich von 50 bis 200 nm. The mean particle size of the binder polymer particles contained in the polymer dispersions, as determined by light scattering, is preferably in the range from 50 to 300 nm, particularly preferably in the range from 50 to 200 nm.
Die erfindungsgemäße eingesetzte wässrige Polymerdispersion wird durch radikalische Emulsi- onspolymerisation der obengenannten Monomere in Gegenwart von 0,01 bis 1 Gew.-Teilen, vorzugsweise 0,01 bis 0,5 Gew.-Teilen und insbesondere 0,01 bis 0,4 Gew.-Teilen, jeweils be- zogen auf die Menge der Gesamtmonomere wenigstens eines radikalischen Polymerisationsini- tiators durchgeführt. The aqueous polymer dispersion used according to the invention is obtained by radical emulsion polymerization of the abovementioned monomers in the presence of 0.01 to 1 part by weight, preferably 0.01 to 0.5 part by weight and in particular 0.01 to 0.4 part by weight. Parts, each based on the amount of total monomers carried out at least one radical polymerization initiator.
Als radikalische Polymerisationsinitiatoren kommen alle diejenigen in Betracht, die in der Lage sind, eine radikalische wässrige Emulsionspolymerisation auszulösen. Es kann sich dabei so- wohl um Peroxide, Hydroperoxide, z.B. Alkylimetallperoxodisulfate als auch um Azoverbindun- gen handeln. Auch werden kombinierte Systeme verwendet, die aus wenigstens einem organi- schen Reduktionsmittel und wenigstens einem Peroxid und/oder Hydroperoxid zusammenge- setzt sind, z.B. tert.-Butylhydroperoxid mit dem Natriumsalz der Hydroxymethansulfonsäure, Wasserstoffperoxid mit Ascorbinsäure oder Natriumperoxodisulfat mit Natriumdisulfit. Bevor- zugte kombinierte Systeme enthalten darüber hinaus eine geringe Menge einer im Polymerisati- onsmedium löslichen Metallverbindung, deren metallische Komponente in mehreren Wertig- keitsstufen auftreten kann, z.B. Ascorbinsäure/Eisen(ll)sulfat/Wasserstoffperoxid, wobei an- stelle von Ascorbinsäure auch häufig das Natriumsalz der Hydroxymethansulfinsäure, Natri umsulfit, Natriumhydrogensulfit oder Natriumbisulfit und anstelle von Wasserstoffperoxid tert.- Butyl-hydroperoxid oder Alkaliperoxodisulfate und/oder Ammoniumperoxodisulfat verwendet werden. Anstelle eines wasserlöslichen Eisen(ll)-Salzes wird häufig eine Kombination aus was- serlöslichen Eisen- und Vanadium-Salzen benutzt. Bevorzugte Initiatoren sind die Ammonium- oder Alkalimetallsalze von Peroxosulfaten oder Peroxodisulfaten, insbesondere Natrium- oder Kaliumperoxodisulfat. Free radical polymerization initiators are all those which are capable of initiating a free radical aqueous emulsion polymerization. Peroxides, hydroperoxides, e.g. Alkylimetallperoxodisulfate act as azo compounds. Combined systems are also used, which are composed of at least one organic reducing agent and at least one peroxide and / or hydroperoxide, e.g. tert-butyl hydroperoxide with the sodium salt of hydroxymethanesulfonic acid, hydrogen peroxide with ascorbic acid or sodium peroxodisulfate with sodium disulfite. Preferred combined systems also contain a small amount of a metal compound soluble in the polymerization medium, the metallic component of which can occur in several valence levels, e.g. Ascorbic acid / iron (II) sulfate / hydrogen peroxide, the sodium salt of hydroxymethanesulfinic acid, sodium sulfite, sodium hydrogen sulfite or sodium bisulfite and, instead of hydrogen peroxide, tert-butyl hydroperoxide or alkali peroxodisulfates and / or ammonium peroxodisulfate being used instead of ascorbic acid. Instead of a water-soluble iron (II) salt, a combination of water-soluble iron and vanadium salts is often used. Preferred initiators are the ammonium or alkali metal salts of peroxosulfates or peroxodisulfates, especially sodium or potassium peroxodisulfate.
Für die Herstellung der erfindungsgemäß einzusetzenden Polymerdispersion wird gegebenen- falls neben den für eine Emulsionspolymerisation üblichen oberflächenaktiven Substanzen we nigstens ein nichtionischer Emulgator in Mengen von vorzugsweise 0,5 bis 10 Gew.-%, insbe- sondere 1 bis 8 Gew.-% und besonders bevorzugt 2 bis 4 Gew.-%, jeweils bezogen auf die Ge- samtmonomermenge verwendet. Brauchbare nichtionische Emulgatoren sind aromatische oder aliphatische nichtionische Emulgatoren, beispielsweise ethoxylierte Mono-, Di- und Trial- kylphenole (EO-Grad: 3 bis 50, Alkylrest: C4-C9) , Ethoxylate langkettiger Alkohole (EO-Grad: 3 bis 50, Alkylrest: C8-C36) sowie Polyethylenoxid/Polypropylenoxid-Blockcopolymere. Bevorzugt werden Ethoxylate langkettiger Alkanole (Alkylrest C10-C22, mittlerer Ethoxylierungsgrad 10 bis 50) und darunter besonders bevorzugt solche mit einem linearen Ci2-Ci8-Alkylrest und einem mittleren Ethoxylierungsgrad 10 bis 50 als alleinige, nichtionische Emulgatoren verwendet. For the preparation of the polymer dispersion to be used according to the invention, at least one nonionic emulsifier in amounts of preferably 0.5 to 10% by weight, in particular 1 to 8% by weight and especially, is optionally used in addition to the surface-active substances customary for emulsion polymerization preferably 2 to 4% by weight, based in each case on the total amount of monomers used. Usable nonionic emulsifiers are aromatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO grade: 3 to 50, alkyl radical: C4-C9), ethoxylates of long-chain alcohols (EO degree: 3 to 50, alkyl radical) : C8-C36) as well as polyethylene oxide / polypropylene oxide block copolymers. Ethoxylates of long-chain alkanols (alkyl radical C10-C22, average degree of ethoxylation 10 to 50) and, particularly preferably, those with a linear Ci2-Ci8-alkyl radical and average degree of ethoxylation 10 to 50 are used as sole, nonionic emulsifiers.
Weitere gebräuchliche Emulgatoren sind vorzugsweise anionischer Natur. Hierzu zählen Alkali- und Ammoniumsalze von Alkylsulfaten (Alkylrest: C8-C12) , von Schwefelsäurehalbestern ethoxy- lierter Alkanole (EO-Grad: 2 bis 50, Alkylrest: C12 bis Cie) und ethoxylierter Alkylphenole (EO- Grad: 3 bis 50, Alkylrest: C4-C9) , von Alkylsulfonsäuren (Alkylrest: C12-C18) und von Alkylarylsul- fonsäuren (Alkylrest: Cg bis Cis) . Other common emulsifiers are preferably anionic in nature. These include alkali and ammonium salts of alkyl sulfates (alkyl radical: C8-C12), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 2 to 50, alkyl radical: C12 to Cie) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical : C4-C9), of alkylsulfonic acids (alkyl radical: C12-C18) and of alkylarylsulfonic acids (alkyl radical: Cg to Cis).
Bevorzugte anionische grenzflächenaktive Substanzen sind auch Verbindungen der folgenden allgemeinen Formel worin R1 und R2 Wasserstoff oder C4-C24-Alkyl bedeuten und nicht gleichzeitig Wasserstoff sind, und X und Y Alkalimetallionen und/oder Ammoniumionen sein können. In der Formel I bedeuten R1 und R2 bevorzugt lineare oder verzweigte Alkylreste mit 6 bis 18 C-Atomen oder Wasser- stoff, und insbesondere mit 6, 12 und 16 C-Atomen, wobei R1 und R2 nicht beide gleichzeitig Wasserstoff sind. X und Y sind bevorzugt Natrium, Kalium oder Ammonium, wobei Natrium be- sonders bevorzugt ist. Besonders vorteilhaft sind Verbindungen I, in denen X und Y Natrium, R1 ein verzweigter Alkylrest mit 12 C-Atomen und R2 Wasserstoff oder gleich R1 ist. Häufig werden technische Gemische verwendet, die einen Anteil von 50 bis 90 Gew.-% des monoalkylierten Produktes aufweisen, beispielsweise Dowfax® 2A1 (Warenzeichen der Dow Chemical Com- pany). Die Verbindungen sind allgemein bekannt, z.B. aus der US-A 4,269,749, und im Handel erhältlich. Preferred anionic surfactants are also compounds of the following general formula wherein R 1 and R 2 are hydrogen or C 4 -C24 alkyl and are not simultaneously hydrogen, and X and Y can be alkali metal ions and / or ammonium ions. In formula I, R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 C atoms or hydrogen, and in particular having 6, 12 and 16 C atoms, where R 1 and R 2 are not both hydrogen at the same time , X and Y are preferably sodium, potassium or ammonium, sodium being particularly preferred. Compounds I in which X and Y are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is hydrogen or R 1 are particularly advantageous. Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ® 2A1 (trademark of Dow Chemical Com pany). The compounds are generally known, for example from US Pat. No. 4,269,749, and are commercially available.
Weitere geeignete Emulgatoren finden sich beispielsweise in Houben-Weyl, Methoden der or- ganischen Chemie, Band 14/1 , Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961 , S. 192 bis 208. Further suitable emulsifiers can be found, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pp. 192 to 208.
Geeignete Emulgatoren sind kommerziell erhältlich, beispielsweise unter den Handelsbezeich- nungen Dowfax®2 A1 , Emulan® NP 50, Dextrol® OC 50, Emulgator 825, Emulgator 825 S, Emu- lan® OG, Texapon® NSO, Nekanil® 904 S, Lumiten® l-RA, Lumiten® l-SC, Lumiten® E 3065, Dis- ponil® FES 77, Lutensol® AT 18, Steinapol® VSL, Emulphor® NPS 25. Suitable emulsifiers are commercially available, for example under the tradenames of Dowfax ® 2 A1, Emulan ® NP 50, Dextrol ® OC 50, 825 emulsifier, emulsifier 825 S, Emulan ® OG, Texapon ® NSO, Nekanil ® 904 S, Lumiten ® l-RA, Lumiten ® l-SC, Lumiten ® E 3065, Disponil ® FES 77, Lutensol ® AT 18, Steinapol ® VSL, Emulphor ® NPS 25.
Darüber hinaus können geeignete Schutzkolloide, wie beispielsweise Polyvinylalkohole, Cellulo- sederivate oder Vinylpyrolidon enthaltende Copolymerisate eingesetzt werden. Eine ausführli- che Beschreibung weiterer geeigneter Schutzkolloide findet sich in Houben-Weyl, Methoden der Organischen Chemie, Bd. 14/1 , Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961 , S. 41 1 -420. Die Gesamtmenge an grenzflächenaktiven Substanzen (fest) macht üblicherweise bis zu 30 Gew.-%, vorzugsweise 0,3 bis 10 Gew.-% und besonders bevorzugt 0,5 bis 5 Suitable protective colloids, such as, for example, polyvinyl alcohols, cellulose derivatives or copolymers containing vinyl pyrolidone, can also be used. A detailed description of further suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 41 1 -420. The total amount of surface-active substances (solid) usually makes up to 30% by weight, preferably 0.3 to 10% by weight and particularly preferably 0.5 to 5
Gew.-%, bezogen auf die zu polymerisierenden Monomere aus. % By weight, based on the monomers to be polymerized.
Das Molekulargewicht der Bindemittelpolymere kann durch Zugabe geringer Mengen, in der Regel bis zu 2 Gew.-%, bezogen auf die zu polymerisierenden Monomere, einer oder mehrerer, das Molekulargewicht regelnder Substanzen, z.B. organische Thioverbindungen oder Allylalko- hole, eingestellt werden. Bevorzugt werden jedoch solche Bindemittelpolymere, die in Abwe- senheit solcher Verbindungen hergestellt wurden. Die Emulsionspolymerisation kann sowohl kontinuierlich als auch nach der Batch-Fahrweise, vorzugsweise nach einem halbkontinuierlichen Verfahren erfolgen. Dabei können die zu poly- merisierenden Monomere kontinuierlich, einschließlich Stufen- oder Gradientenfahrweise, dem Polymerisationsansatz zugefügt werden. Bevorzugt ist ein Zulaufverfahren mit kurzen Zulaufzei- ten, d.h. die Monomere werden, vorzugsweise als wässrige Emulsion, dem Reaktionsansatz in- nerhalb von 1 bis 4 Stunden, vorzugsweise innerhalb von 1 ,5 bis 3 Stunden zudosiert. The molecular weight of the binder polymers can be adjusted by adding small amounts, generally up to 2% by weight, based on the monomers to be polymerized, of one or more substances which regulate the molecular weight, for example organic thio compounds or allyl alcohols. However, preference is given to those binder polymers which have been prepared in the absence of such compounds. The emulsion polymerization can be carried out either continuously or according to the batch procedure, preferably according to a semi-continuous process. The monomers to be polymerized can be added continuously, including step or gradient procedures, to the polymerization batch. A feed process with short feed times is preferred, ie the monomers, preferably as an aqueous emulsion, are metered into the reaction mixture within 1 to 4 hours, preferably within 1.5 to 3 hours.
Neben der saatfreien Herstellungsweise kann zur Einstellung der Polymerteilchengröße die Emulsionspolymerisation nach dem Saatlatex-Verfahren oder in Gegenwart eines in situ herge- stellten Saatlatex erfolgen. Verfahren hierzu sind bekannt und können dem Stand der Technik entnommen werden (siehe EP-B 40 419 sowie’Encyclopedia of Polymer Science and Techno- logy’, Vol. 5, John Wiley & Sons Inc., New York, 1966, S. 847). In addition to the seed-free production method, the emulsion polymerization can be carried out by the seed latex process or in the presence of a seed latex produced in situ to adjust the polymer particle size. Methods for this are known and can be found in the prior art (see EP-B 40 419 and 'Encyclopedia of Polymer Science and Technology', vol. 5, John Wiley & Sons Inc., New York, 1966, p. 847 ).
So empfiehlt der Stand der Technik, beim Zulaufverfahren eine definierte feinteilige Saat-Poly- merisatdispersion im Polymerisationsgefäß vorzulegen und dann die Monomere in Gegenwart der Saat zu polymerisieren. Hierbei wirken die Saat-Polymerisatteilchen als’Polymerisations- keime’ und entkoppeln die Polymerteilchenbildung und das Polymerteilchenwachstum. Wäh- rend der Emulsionspolymerisation kann weitere Saatdispersion zugegeben werden. Hierdurch werden breite Größenverteilungen der Polymertteilchen erreicht, die insbesondere bei Polymer- dispersionen mit hohem Feststoffgehalt oftmals erwünscht sind (vgl. DE-A 42 13 965). Anstelle der Zugabe eines definierten Saatlatex kann dieser auch in situ erzeugt werden. Hierzu wird beispielsweise ein Teil der Monomere und des Initiators zusammen mit Emulgator vorgelegt und auf Reaktionstemperatur erwärmt, wobei ein relativ feinteiliger Latex entsteht. Anschlie- ßend wird im gleichen Polymerisationsgefäß die eigentliche Polymerisation nach dem Zulauf- verfahren durchgeführt (siehe auch DE-A 42 13 965). The prior art thus recommends that a defined, finely divided seed polymer dispersion be placed in the polymerization vessel in the feed process and then polymerize the monomers in the presence of the seeds. Here, the seed polymer particles act as 'polymerization nuclei' and decouple the polymer particle formation and the polymer particle growth. Further seed dispersion can be added during the emulsion polymerization. As a result, wide size distributions of the polymer particles are achieved, which are often desirable in particular in the case of polymer dispersions with a high solids content (cf. DE-A 42 13 965). Instead of adding a defined seed latex, this can also be generated in situ. For this purpose, for example, part of the monomers and the initiator are initially introduced together with the emulsifier and heated to the reaction temperature, a relatively finely divided latex being formed. The actual polymerization is then carried out in the same polymerization vessel using the feed process (see also DE-A 42 13 965).
Die Art und Weise, wie der Initiator der Emulsionspolymerisation zudosiert ist, ist nicht kritisch. Der Initiator kann sowohl vollständig im Polymerisationsgefäß vorgelegt oder aber, nach Maß- gabe seines Verbrauchs, im Verlauf der Emulsionspolymerisation kontinuierlich oder stufen- weise zugesetzt werden. Die Vorgehensweise hängt sowohl von der chemischen Natur des Ini tiators als auch von der Polymerisationstemperatur ab und kann vom Fachmann je nach Bedarf gewählt werden. Bevorzugt wird eine kontinuierliche oder stufenweise Zudosierung zum Reakti- onsansatz. The manner in which the initiator of the emulsion polymerization is metered in is not critical. The initiator can either be completely introduced into the polymerization vessel or, depending on its consumption, can be added continuously or in stages during the course of the emulsion polymerization. The procedure depends both on the chemical nature of the initiator and on the polymerization temperature and can be chosen by the person skilled in the art as required. A continuous or stepwise addition to the reaction mixture is preferred.
Polymerisationsdruck und Polymerisationstemperatur sind gleichfalls von untergeordneter Be- deutung. Im Allgemeinen arbeitet man bei Temperaturen zwischen Raumtemperatur und 120°C, vorzugsweise bei Temperaturen von 50 bis 95°C und besonders bevorzugt zwischen 70 und 90°C. The polymerization pressure and the polymerization temperature are also of minor importance. In general, temperatures between room temperature and 120 ° C, preferably at temperatures of 50 to 95 ° C and particularly preferably between 70 and 90 ° C.
Im Anschluss an die eigentliche Polymerisationsreaktion ist es in der Regel erforderlich, die wässrigen Polymerdispersionen weitgehend frei von Geruchsträgern, wie Restmonomeren und anderen organischen flüchtigen Bestandteilen zu gestalten. Dies kann in an sich bekannter Weise physikalisch durch destillative Entfernung (insbesondere über Wasserdampfdestillation) oder durch Abstreifen mit einem inerten Gas erreicht werden. Following the actual polymerization reaction, it is generally necessary to make the aqueous polymer dispersions largely free of odorants, such as residual monomers and other organic volatile constituents. This can be done physically in a manner known per se by removal by distillation (in particular by steam distillation) or by stripping with an inert gas.
Die Absenkung der Restmonomere kann weiterhin chemisch durch radikalische Nachpolymeri- sation, insbesondere unter Einwirkung von Redoxinitiatorsystemen, wie sie z.B. in der The lowering of the residual monomers can also be carried out chemically by radical postpolymerization, in particular under the action of redox initiator systems, such as those e.g. in the
DE-A 44 35 423, DE-A 44 19 518 sowie in der DE-A 44 35 422 aufgeführt sind, erfolgen. Als Oxidationsmittel zur redoxinitiierten Nachpolymerisation eignen sich insbesondere Wasserstoff- peroxid, tert.-Butylhydroperoxid, Cumolhydroperoxid oder Alkaliperoxidsulfate. Geeignete Re- duktionsmittel sind Natriumdisulfit, Natriumhydrogensulfit, Natriumdithionit, Natriumhydroxyme- thansulfinat, Formamidinsulfinsäure, Acetonbisulfit (= Natriumhydrogensulfit-Additionsproduckt an Aceton), Ascorbinsäure bzw. reduzierend wirkende Zuckerverbindungen, oder wasserlösli- che Mercaptane, wie Mercaptoethanol. Die Nachpolymerisation mit dem Redoxinitiatorsystem wird im Temperaturbereich von 10 bis 100°C, vorzugsweise bei 20 bis 90°C durchgeführt. Die Redoxpartner können der Dispersion unabhängig voneinander vollständig, portionsweise bzw. kontinuierlich über einen Zeitraum von 10 Minuten bis 4 Stunden zugegeben werden. Zur Ver- besserung der Nachpolymerisationswirkung der Redoxinitiatorsysteme können der Dispersion auch lösliche Salze von Metallen wechselnder Wertigkeit, wie Eisen-, Kupfer oder Vanadium- salze, zugesetzt werden. Häufig werden auch Komplexbildner zugegeben, die die Metallsalze unter den Reaktionsbedingungen in Lösung halten. DE-A 44 35 423, DE-A 44 19 518 and DE-A 44 35 422 are listed. Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide or alkali peroxide sulfates are particularly suitable as oxidizing agents for redox-initiated postpolymerization. Suitable reducing agents are sodium disulfite, sodium hydrogen sulfite, sodium dithionite, sodium hydroxymethanesulfinate, formamidine sulfinic acid, acetone bisulfite (= sodium hydrogen sulfite addition product on acetone), ascorbic acid or reducing sugar compounds, or water-soluble mercaptans, such as mercaptoethanol. The post-polymerization with the redox initiator system is carried out in the temperature range from 10 to 100 ° C., preferably at 20 to 90 ° C. The redox partners can be added to the dispersion completely, in portions or continuously over a period of 10 minutes to 4 hours, independently of one another. To improve the post-polymerization effect of the redox initiator systems, soluble salts of metals of varying valency, such as iron, copper or vanadium salts, can also be added to the dispersion. Complexing agents are also frequently added, which keep the metal salts in solution under the reaction conditions.
Üblicherweise werden die Polymerdispersion abschliessend mit einer Base neutralisiert, wie Al- kali- oder Erdalkalimetallhydroxyden, Erdalkalimetalloxyden oder flüchtige oder nichtflüchtige Aminen. Zu den nichtflüchtigen Aminen zählen insbesondere ethoxylierte Diamine oder Polya- mine, wie sie z.B. unter dem Namen Jeffamine® (Texaco Chemical Co.) kommerziell erhältlich sind. Nach diesem Verfahren hergestellt Polymerdispersion sind allgemein bekannt. The polymer dispersion is usually finally neutralized with a base, such as alkali metal or alkaline earth metal hydroxides, alkaline earth metal oxides or volatile or nonvolatile amines. Among the non-volatile amines include mine especially ethoxylated diamines or polyadenylation, as are commercially available, for example under the name Jeffamine ® (Texaco Chemical Co.). Polymer dispersions produced by this process are generally known.
Solche Polymerdispersionen können nun zusammen mit Alkalialkylsilikonat und/oder wasser- lösliches Silikat auf einen pH-Wert im Bereich von 10 bis 12 bevorzugt 11 bis 12 eingestellt wer- den. Diese Einstellung des pH-Wertes kann gemäß einer erfindungsgemäßen Ausführungsform beim Formulieren der erfindungsgemäßen Dispersionsfarbe erfolgen. Such polymer dispersions can now be adjusted together with alkali alkyl siliconate and / or water-soluble silicate to a pH value in the range from 10 to 12, preferably 11 to 12. According to an embodiment of the invention, this adjustment of the pH can be carried out when formulating the emulsion paint of the invention.
Die vorliegende Erfindung betrifft daher auch die Verwendung einer wässrigen Polymerdispersi- onen mit einem Feststoffgehalt im Bereich von 40 bis 60 Gew.-% erhältlich durch radikalische wässrige Emulsionspolymerisation einer Monomermischung enthaltend Ethylhexylacrylat, Buty- lacrylat und einen oder mehrere Vinylaromaten als organisches Bindemittel, in Kombination mit einem Alkalialkylsilikonat und/oder wasserlösliches Silikat in einem Beschichtungsmittel, bevor- zugt einer Dispersionsfarbe, mit einem pH-Wert im Bereich von 10 bis 12. The present invention therefore also relates to the use of an aqueous polymer dispersion having a solids content in the range from 40 to 60% by weight, obtainable by radical aqueous emulsion polymerization of a monomer mixture comprising ethylhexyl acrylate, butyl acrylate and one or more vinyl aromatics as organic binders, in combination with an alkali alkyl siliconate and / or water-soluble silicate in a coating agent, preferably an emulsion paint, with a pH in the range from 10 to 12.
Es ist jedoch auch möglich bereits die Polymerdispersion auf einen pH-Wert im Bereich von 10 bis 12, bevorzugt 1 1 bis 12 durch die Zugabe von Alkalialkylsilikonat und/oder wasserlösliche Silikate und gegebenenfalls anorganischer Base einzustellen. Geeignete anorganische Basen sind die obengenannten Alkali- oder Erdalkalimetallhydroxyde und Erdalkalimetalloxyden. Die Reihenfolge der Zugabe ist dabei beliebig. Die vorliegende Erfindung betrifft daher auch wässrige Polymerdispersionen, die erhältlich sind durch radikalische wässrige Emulsionspolymerisation einer Monomermischung enthaltend Ethylhexylacrylat, Butylacrylat und einen oder mehrere Vinylaromaten, bevorzugt Styrol, und anschließende Einstellung des pH-Werts auf einen Wert im Bereich von 10 bis 12 mit mindes- tens 0,5 Gew.-% Alkalialkylsilikonat und/oder wasserlösliche Silikate bezogen auf die wässrige Poylmerdispersion und gegebenenfalls mit einer anorganischen Base. However, it is also possible to adjust the polymer dispersion to a pH in the range from 10 to 12, preferably 1 to 12, by adding alkali alkyl siliconate and / or water-soluble silicates and optionally inorganic base. Suitable inorganic bases are the above-mentioned alkali or alkaline earth metal hydroxides and alkaline earth metal oxides. The order of addition is arbitrary. The present invention therefore also relates to aqueous polymer dispersions which are obtainable by free radical aqueous emulsion polymerization of a monomer mixture comprising ethylhexyl acrylate, butyl acrylate and one or more vinyl aromatics, preferably styrene, and subsequent adjustment of the pH to a value in the range from 10 to 12 with at least at least 0.5% by weight of alkali alkyl siliconate and / or water-soluble silicates based on the aqueous polymer dispersion and, if appropriate, with an inorganic base.
Bevorzugt werden wässrige Polymerdispersionen erhältlich durch radikalische wässrige Emulsi- onspolymerisation einer Monomermischung enthaltend 10 bis 30 Gew.-Teile, bezogen auf die Gesamtmonomere, Ethylhexylacrylat, 25 bis 50 Gew.-Teile, bezogen auf die Gesamtmono- mere, Butylacrylat und 30 bis 50 Gew.-Teile, bezogen auf die Gesamtmonomere, einen oder mehrere Vinylaromaten, bevorzugt Styrol und optional bis zu 10 Gew.-% weitere ethylenisch ungesättigte Monomere, wobei die Summe aller Monomere 100 Gew.-%Teile ergibt, polymeri- siert, und anschließende Einstellung des pH-Wert auf einen Wert im Bereich 10 bis 12 mit min- destens 0,5 vorzugsweise mit 0,5 bis 10 Gew.-% Alkalialkylsilikonat und/oder wasserlösliche Si- likate bezogen auf die wässrige Polymerisdispersion und gegebenenfalls mit einer anorgani- schen Base. Aqueous polymer dispersions are preferably obtainable by free-radical aqueous emulsion polymerization of a monomer mixture comprising 10 to 30 parts by weight, based on the total monomers, ethylhexyl acrylate, 25 to 50 parts by weight based on the total monomers, butyl acrylate and 30 to 50 parts by weight . Parts, based on the total monomers, one or more vinyl aromatics, preferably styrene and optionally up to 10% by weight of further ethylenically unsaturated monomers, the sum of all monomers giving 100% by weight, polymerized, and subsequent adjustment the pH to a value in the range from 10 to 12 with at least 0.5, preferably with 0.5 to 10,% by weight of alkali alkyl siliconate and / or water-soluble silicates, based on the aqueous polymer dispersion and, if appropriate, with an inorganic one Base.
Besonders bevorzugt werden die obengenannten bevorzugten Polymerdispersionen, die durch radikalische wässrige Emulsionspolymerisation erhalten werden und anschließend des pH-Wert auf einen Wert im Bereich 10 bis 12 mit mindestens 0,5 vorzugsweise mit 0,5 bis 10 Gew.-% Alkalialkylsilikonat und/oder wasserlösliche Silikate bezogen auf die wässrige Polymerisdisper- sion und gegebenenfalls mit einer anorganischen Base eingestellt werden. Particularly preferred are the preferred polymer dispersions mentioned above, which are obtained by free-radical aqueous emulsion polymerization and then the pH to a value in the range from 10 to 12 with at least 0.5, preferably with 0.5 to 10% by weight of alkali metal alkyl silicone and / or water-soluble Silicates based on the aqueous polymer dispersion and, if appropriate, with an inorganic base.
Die vorliegende Erfindung betrifft daher auch ein Verfahren zu Herstellung einer wässrigen Po- lymerdispersion, bei dem man eine Monomermischung enthaltend Ethylhexylacrylat, Butylac- rylat und einen oder mehrere Vinylaromaten, bevorzugt Styrol, radikalisch polymerisiert und an- schließend den pH-Wert der hiernach erhaltenen Dispersion mit Alkalialkylsilikonat und/oder ei- nem wasserlöslichen Silikat und gegebenenfalls einer anorganischen Base auf einen Wert im Bereich 10 bis 12 einstellt. The present invention therefore also relates to a process for the preparation of an aqueous polymer dispersion, in which a monomer mixture comprising ethylhexyl acrylate, butyl acrylate and one or more vinylaromatics, preferably styrene, is radically polymerized and then the pH of the dispersion obtained thereafter with an alkali alkyl siliconate and / or a water-soluble silicate and optionally an inorganic base to a value in the range 10 to 12.
Alkalimetallalkylsilikonate gemäß der Erfindung sind insbesondere Verbindungen mit der For- mel MOSi(R)(OH)z, wobei M ein Alkalimetall und R ein Alkylrest ist. Alkalimetallalkylsilikonate können beispielsweise durch Umsetzen von Alkylsilantriol mit einem Alkalimetallhydroxid erhal- ten werden. Die Herstellung von Lösungen von Akalimetallalkylsilikonaten, insbesondere wäss- rigen Lösungen, ist beispielsweise in der DE 1 031 910 beschrieben. Alkali metal alkyl siliconates according to the invention are in particular compounds with the formula MOSi (R) (OH) z, where M is an alkali metal and R is an alkyl radical. Alkali metal alkyl siliconates can be obtained, for example, by reacting alkylsilanetriol with an alkali metal hydroxide. The preparation of solutions of alkali metal alkyl silicates, in particular aqueous solutions, is described for example in DE 1 031 910.
In den Verbindungen MOSi(R)(OH)z, die für das erfindungsgemäße Alkalimetallalkylsilikonat in Frage kommen, kann das Alkalimetall M insbesondere ausgewählt sein aus der Gruppe beste- hen aus Lithium, Natrium, Kalium und Mischungen davon. Der Alkylrest R ist vorzugsweise aus- gewählt aus der Gruppe bestehend aus Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso- Butyl-, tert-Butyl, nPentyl-, iso-Pentyl-, tert-Pentyl-, Neopentyl-, Phenyl-, Aryl-, und Cyclohexyk Bevorzugt ist der Alkylrest Methyl- Weiter bevorzugt ist das Alkalimetallalkylsilikonat der erfin- dungsgemäßen Dispersionsfarbe ausgewählt aus der Gruppe bestehend aus Litiummethylsili- konat, Natriummethylsilikonat und Kaliummethylsilikonat. Am bevorzugtesten ist das Alkalime- tallalkylsilikonat Kaliummethylsilikonat. Diese Alkalimetallalkylsilikonate, insbesondere Kalium- methylsilikonat ergeben homogene Oberflächen und sind gut handhabbar. In the compounds MOSi (R) (OH) z which are suitable for the alkali metal alkyl siliconate according to the invention, the alkali metal M can in particular be selected from the group consisting of lithium, sodium, potassium and mixtures thereof. The alkyl radical R is preferably selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl , tert-pentyl, neopentyl, phenyl, aryl, and cyclohexyc The alkyl radical is preferably methyl. The alkali metal alkyl silicone of the emulsion paint according to the invention is more preferably selected from the group consisting of lithium methyl siliconate, sodium methyl siliconate and potassium methyl siliconate. Most preferably, the alkali metal alkyl siliconate is potassium methyl siliconate. These alkali metal alkyl silicates, in particular potassium methyl siliconate, result in homogeneous surfaces and are easy to handle.
Das Alkalimetallalkylsilikonat ist in der erfindungsgemäßen Dispersionsfarbe in einer Menge von 0,1 bis 5 Gew.-% enthalten, bezogen auf das Gesamtgewicht der Dispersionsfarbe. Bevor- zugt enthält die erfindungsgemäße Dispersionsfarbe 0,1 bis 2 Gew.-%, insbesondere 0,3 bis 2 Gew.-% oder 0,5 bis 1 ,5 Gew.-%, Alkalimetallalkylsilikonat, jeweils bezogen auf das Gesamtge- wicht der Dispersionsfarbe. Dispersionsfarben mit diesen Gehalten zeigen eine gute Verarbeit- barkeit und eine gute Lagerstabilität. The alkali metal alkyl siliconate is contained in the emulsion paint according to the invention in an amount of 0.1 to 5 wt .-%, based on the total weight of the emulsion paint. The emulsion paint according to the invention preferably contains 0.1 to 2% by weight, in particular 0.3 to 2% by weight or 0.5 to 1.5% by weight, of alkali metal alkyl siliconate, in each case based on the total weight of the emulsion paint. Dispersion paints with these contents show good processability and good storage stability.
Das wasserlösliche Alkalisilikat ist in der erfindungsgemäßen Dispersionsfarbe in einer Menge von 0,1 bis 5 Gew.-% (fest) enthalten, bezogen auf das Gesamtgewicht der Dispersionsfarbe. Bezogen auf den Si02-Gehalt beträgt der Anteil an wasserlöslichem Alkalisilikate in der Disper- sionsfarbe bevorzugt 0,06 bis 3,3 Gew.-% gerechnet als Siliciumdioxid. The water-soluble alkali silicate is present in the emulsion paint according to the invention in an amount of 0.1 to 5% by weight (solid), based on the total weight of the emulsion paint. Based on the Si0 2 content, the proportion of water-soluble alkali silicates in the dispersion paint is preferably 0.06 to 3.3% by weight, calculated as silicon dioxide.
Erfindungsgemäß geeignete wasserlösliche Silikate sind wasserlösliche Alkalisilikat, auch als Wasserglas bezeichnet, wie Lithium- Natrium- oder bevorzugt Kaliumsilikat (Kaliumwasserglas). Besonders bevorzugt wir ein Kaliumwasserglas mit einem K20-Gehalt (ISO 1692) in Bereich von 5 bis 15 Gew.-%, bevorzugt 7 bis 12 Gew.-% und einem Si02-Gehalt (nach ISO 2124) im Bereich von 15 - 30 Gew.-% in der wässrigen Lösung eingesetzt. Water-soluble silicates suitable according to the invention are water-soluble alkali silicate, also referred to as water glass, such as lithium-sodium or preferably potassium silicate (potassium water glass). We particularly prefer a potassium water glass with a K 2 0 content (ISO 1692) in the range of 5 to 15% by weight, preferably 7 to 12% by weight and an Si0 2 content (according to ISO 2124) in the range of 15 - 30 wt .-% used in the aqueous solution.
Die erfindungsgemäßen wässrigen Polymerdispersionen eignen sich bevorzugt zur Formulie- rung von Dispersionsfarben, insbesondere von Innenfarben, mit einer Pigmentvolumenkon- zentration >50, bevorzugt 60 bis 90. The aqueous polymer dispersions according to the invention are preferably suitable for the formulation of emulsion paints, in particular interior paints, with a pigment volume concentration> 50, preferably 60 to 90.
Die Dispersionsfarben enthalten weiterhin erfindungsgemäß 20 bis 70 Gew.-% anorganischer Füllstoffe. Geeignete Füllstoffe sind z. B. Alumosilicate, wie Feldspäte, Silicate, wie Kaolin, Tal- kum, Glimmer, Magnesit, Erdalkalicarbonate, wie Calciumcarbonat, beispielsweise in Form von Calcit oder Kreide, Magnesiumcarbonat, Dolomit, Erdalkalisulfate, wie Calciumsulfat, Siliciumdi- oxid etc. In Anstrichmitteln werden naturgemäß feinteilige Füllstoffe bevorzugt. Die Füllstoffe können als Einzelkomponenten eingesetzt werden. In der Praxis haben sich jedoch Füllstoffmi schungen besonders bewährt, z. B. Calciumcarbonat/Kaolin, Calciumcarbonat/Talkum. According to the invention, the emulsion paints also contain 20 to 70% by weight of inorganic fillers. Suitable fillers are e.g. B. aluminosilicates, such as feldspar, silicates, such as kaolin, talc, mica, magnesite, alkaline earth carbonates, such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates, such as calcium sulfate, silicon dioxide, etc. In paints naturally fine fillers preferred. The fillers can be used as individual components. In practice, however, Füllstoffmi mixtures have proven particularly useful, e.g. B. calcium carbonate / kaolin, calcium carbonate / talc.
Feinteilige Füllstoffe können auch zur Erhöhung der Deckkraft und/oder zur Einsparung von Weißpigmenten eingesetzt werden. Zur Einstellung der Deckkraft des Farbtons und der Farb- tiefe werden vorzugsweise Abmischungen aus Farbpigmenten und Füllstoffen eingesetzt. Finely divided fillers can also be used to increase opacity and / or to save white pigments. Mixtures of color pigments and fillers are preferably used to adjust the opacity of the color and depth of color.
Die Dispersionsfarben können weiterhin bis zu 30 Gew.-%, wenigstens eines Pigments enthal- ten. Geeignete Pigmente sind beispielsweise anorganische Weißpigmente wie Titandioxid, vor- zugsweise in der Rutilform, Bariumsulfat, Zinkoxid, Zinksulfid, basisches Bleicarbonat, Antimon- trioxid, Lithopone (Zinksulfid + Bariumsulfat) oder farbige Pigmente, beispielsweise Eisenoxide, Ruß, Graphit, Zinkgelb, Zinkgrün, Ultramarin, Manganschwarz, Antimonschwarz, Manganviolett, Pariser Blau oder Schweinfurter Grün. Neben den anorganischen Pigmenten können die erfin- dungsgemäßen Dispersionsfarben auch organische Farbpigmente, z. B. Sepia, Gummigutt, Kasseler Braun, Toluidinrot, Pararot, Hansagelb, Indigo, Azofarbstoffe, anthrachinoide und indi- goide Farbstoffe sowie Dioxazin, Chinacridon-, Phthalocyanin-, Isoindolinon- und Metallkompl- expigmente enthalten. Geeignet sind auch synthetische Weißpigmente mit Lufteinschlüssen zur Erhöhung der Lichtstreuung, wie die Rhopaque®-Dispersionen. The emulsion paints can also contain up to 30% by weight of at least one pigment. Suitable pigments are, for example, inorganic white pigments such as titanium dioxide. preferably in the rutile form, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopone (zinc sulfide + barium sulfate) or colored pigments, for example iron oxides, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, Paris blue or Schweinfurt green. In addition to the inorganic pigments, the emulsion paints according to the invention can also contain organic color pigments, e.g. B. sepia, gummy gut, Kasseler Braun, toluidine red, Pararot, Hansa yellow, indigo, azo dyes, anthraquinone and indigo dyes as well as dioxazine, quinacridone, phthalocyanine, isoindolinone and metal compliments contain. Synthetic white pigments with air pockets to increase light scattering are also suitable, such as the Rhopaque® dispersions.
Die Dispersionsfarben enthalten weiterhin 0,1 bis 10 gew.-% wietere Hilfsstoffe enthalten, wie sie in Dispersionsfarben auf Basis wässriger Polymerdispersionen üblich sind. Zu den üblichen Hilfsmitteln zählen, neben den bei der Polymerisation eingesetzten Emulgatoren, auch Netz- o- der Dispergiermittel, wie Natrium-, Kalium- oder Ammoniumpolyphosphate, Alkalimetall- und Ammoniumsalze von Acrylsäure- oder Maleinsäureanhydridcopolymeren, Polyphosphonate, wie 1-Hydroxyethan-1 ,1-diphosphonsaures Natrium sowie Naphthalinsulfonsäuresalze, insbe- sondere deren Natriumsalze. The emulsion paints also contain 0.1 to 10% by weight of other auxiliaries, as are customary in emulsion paints based on aqueous polymer dispersions. In addition to the emulsifiers used in the polymerization, the customary auxiliaries also include wetting or dispersing agents, such as sodium, potassium or ammonium polyphosphates, alkali metal and ammonium salts of acrylic or maleic anhydride copolymers, polyphosphonates, such as 1-hydroxyethane-1, 1-diphosphonic acid sodium and naphthalenesulfonic acid salts, in particular their sodium salts.
Weitere geeignete Hilfsmittel sind Verlaufsmittel, Entschäumer, Biozide und Verdicker. Geeig- nete Verdicker sind z. B. Assoziativverdicker, wie Polyurethanverdicker. Die Menge des Verdi- ckers beträgt vorzugsweise weniger als 1 Gew.-%, besonders bevorzugt weniger als Other suitable auxiliaries are leveling agents, defoamers, biocides and thickeners. Suitable thickeners are e.g. B. associative thickeners, such as polyurethane thickeners. The amount of the thickener is preferably less than 1% by weight, particularly preferably less than
0,6 Gew.-%, bezogen auf den Feststoffgehalt der Dispersionsfarbe. 0.6% by weight, based on the solids content of the emulsion paint.
Die PVK beschreibt das Verhältnis des Volumens an Pigmenten (VP) und Füllstoffen (VF) zum Gesamtvolumen, bestehend aus den Volumina an Bindemittel (VB), Pigmenten und Füllstoffen eines getrockneten Beschichtungsfilms in Prozent: PVK = (VP + VF) x 100 / (VP + VF + VB) (vgl. Ullmann's Enzyklopädie der technischen Chemie, 4. Auflage, Band 15, S. 667). The PVK describes the ratio of the volume of pigments (VP) and fillers (VF) to the total volume, consisting of the volumes of binder (VB), pigments and fillers of a dried coating film in percent: PVK = (VP + VF) x 100 / ( VP + VF + VB) (see Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 15, p. 667).
Besonders bevorzugt werden wässrige Dispersionfarben enthaltend a) 5 bis 30 Gew.-%, bevorzugt 8 bis 15 Gew.-% der wässrigen Polymerdispersion mit einem Feststoffgehalt im Bereich von 40 bis 60 Gew.-%, Aqueous emulsion paints containing a) 5 to 30% by weight, preferably 8 to 15% by weight of the aqueous polymer dispersion with a solids content in the range from 40 to 60% by weight are particularly preferred,
b) 0,1 bis 3,5 Gew.-%, bevorzugt 0,2 bis 2 Gew.-% Alkalialkylsilikonat und/oder was- serlösliches Silikat, bevorzugt 0,3 bis 1 ,5 Gew.-% Kaliumalkylsilikonat b) 0.1 to 3.5% by weight, preferably 0.2 to 2% by weight of alkali alkyl siliconate and / or water-soluble silicate, preferably 0.3 to 1.5% by weight of potassium alkyl siliconate
c) 20 bis 70 Gew.-%, bevorzugt 30 bis 60 Gew.-% anorganischer Füllstoffe c) 20 to 70 wt .-%, preferably 30 to 60 wt .-% of inorganic fillers
d) 0 bis 30 Gew.-%, bevorzugt 0 bis 20 Gew.-% wenigstens eines anorganischen Pig- ments d) 0 to 30% by weight, preferably 0 to 20% by weight, of at least one inorganic pigment
e) 0,1 bis 10 Gew.-% übliche Hilfsmittel, sowie e) 0.1 to 10% by weight of conventional auxiliaries, and
f) Wasser f) water
jeweils bezogen auf die Gesamtmenge der Dispersionsfarbe wobei der pH-Wert der Dispersi- onsfarbe einen Wert im Bereich von 10 bis 12, bevorzugt 1 1 bis 12 aufweist. Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung einer wässrigen Poly- merdispersion, wie zuvor definiert, in Dispersionsfarben, bevorzugt für hochgefüllte Innenfar- ben. in each case based on the total amount of the emulsion paint, the pH of the emulsion paint having a value in the range from 10 to 12, preferably 11 to 12. Another object of the present invention is the use of an aqueous polymer dispersion, as previously defined, in emulsion paints, preferably for highly filled interior paints.
Die erfindungsgemäßen Dispersionsfarben mit einem pH-Wert >10 weisen eine gute pH-Stabili- tät auf, so dass sie nicht oder nur schwach anfällig für einen Befall durch Mikroorganismen sind. Diese sehr gute Stabilität ermöglicht es ohne oder mit deutlich geringeren Mengen an Konser- vierungsstoffen und/oder Bioziden zu formulieren. The emulsion paints according to the invention with a pH> 10 have good pH stability, so that they are not or only slightly susceptible to attack by microorganisms. This very good stability makes it possible to formulate without or with significantly smaller amounts of preservatives and / or biocides.
Gleiches gilt auch für die erfindungsgemäßen neuen Dispersionen, die mit Alkalialkylsilikonat und/oder wasserlösliches Silikat und gegebenenfalls einer alkalischen Base auf einen pH-Wert von 10 bis 12, vorzugsweise 11 bis 12 gestellt wurden. Auch sie weisen eine gute pH-Stabilität auf und neigen nicht zu einem Befall mit Mikroorganismen. The same also applies to the new dispersions according to the invention which have been adjusted to a pH of 10 to 12, preferably 11 to 12, with alkali alkyl siliconate and / or water-soluble silicate and optionally with an alkaline base. They also have good pH stability and are not prone to attack by microorganisms.
Weiterhin bilden die erfindungsmäßen Dispersionen bei hohem pH-Wert kein Koagulat. Koagu- late führen im Allgemeinen zu Filtrationsproblemen. Dispersionen mit Koagulat bzw. Koagu- latneigung sind üblicherweise auch in der Anwendung problematisch. Furthermore, the dispersions according to the invention do not form a coagulum at a high pH. Coagulates generally lead to filtration problems. Dispersions with coagulate or tendency to coagulate are usually also problematic in use.
Die im Folgenden angegebenen Beispiele sollen die Erfindung erläutern, ohne sie jedoch einzu- schränken. The examples given below are intended to explain the invention, but without restricting it.
Die Teilchengrösse (Z-Mittelwert) der Polymerteilchen wurde durch dynamische Lichtstreuung an einer 0,01 gew.-%igen Dispersion bei 23°C mittels eines Autosizer llc der Fa. Malvern Instru- ments, England, ermittelt. Angegeben wird der mittlere Durchmesser der Kumulantenauswer- tung (cumulant z-average) der gemessenen Autokorrelationsfunktion. The particle size (Z mean) of the polymer particles was determined by dynamic light scattering on a 0.01% strength by weight dispersion at 23 ° C. using an Autosizer IIc from Malvern Instruments, England. The average diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function is given.
Die Bestimmung des pH-Wertes erfolgte mit einem pH-Meter der Fa. Knick (Modell: Portamess 913 (X) ph). The pH value was determined using a Knick pH meter (model: Portamess 913 (X) ph).
Festgehalte der Polymerdispersionen wurden bestimmt, indem 0,5 bis 1 ,5 g der Polymerdisper- sion in einem Blechdeckel mit 4 cm Durchmesser verteilt wurde und anschließend mit Hilfe ei- nes Trockners (Mettler Toledo HR 83 Halogentrockner) bei 140°C bis zur Massenkonstanz ge- trocknet wurden. Das Verhältnis der Masse der Probe nach Trocknung zur Masse bei der Pro- bennahme ergibt den Feststoffgehalt des Polymers. Solid contents of the polymer dispersions were determined by distributing 0.5 to 1.5 g of the polymer dispersion in a metal lid with a 4 cm diameter and then using a dryer (Mettler Toledo HR 83 halogen dryer) at 140 ° C. to constant weight were dried. The ratio of the mass of the sample after drying to the mass during sampling gives the solids content of the polymer.
Die Bestimmung der Viskosität erfolgte nach zwei verschieden Methoden: The viscosity was determined using two different methods:
ICI: wird mit einem I.C.I Cone & Plate Viscosimeter Fa. Epprecht Instruments & Controls AG ge- messen und in der Einheit Poises [P] angegeben ICI: is measured with an I.C.I Cone & Plate Viscosimeter from Epprecht Instruments & Controls AG and specified in the unit Poises [P]
KU: wird mit Hilfe eines Brookfield Viscosimeter (Fa. Brookfield) gemessen bei 200rpm und in der Einheit Krebs Units [KU] angegeben Untersuchung der Polymerdispersion auf Stabilität gegen Koagulatbildung: KU: is measured using a Brookfield viscometer (from Brookfield) measured at 200rpm and in cancer units [KU] Examination of the polymer dispersion for stability against coagulum formation:
Eine gelagerte Dispersion wurde dünn auf eine Glasplatte appliziert (mit Hilfe eines Glasstabes) und die Defekte visuell bewertet (Stippen/Grieß). Je weniger Stippen-Bildung bzw. Grieß-Bil dung über die Lagerungsdauer desto geringer die Koagulatneigung der Dispersion und desto stabiler die kolloidale Stabilität der Dispersion. A stored dispersion was applied thinly to a glass plate (using a glass rod) and the defects were assessed visually (specks / semolina). The less speck formation or semolina formation over the storage period, the lower the tendency of the dispersion to coagulate and the more stable the colloidal stability of the dispersion.
Allgemeine Vorschrift zur Herstellung der Polymerdispersion: General instructions for the preparation of the polymer dispersion:
Es wurden Polymerdispersionen mittels semi-kontinuierlicher Emulsionspolymerisation herge- stellt. Dabei wurden die Teilchengrößen mittels einer Polystyrolsaat in der Reaktorvorlage kon- trolliert und auf 100-300 nm eingestellt. Die Mengenverhältnisse der verwendeten Monomere sind in Tabelle 1 zusammengestellt. Die Wasserverteilung wurde so gewählt, dass der theoreti- sche Feststoffgehalt der auspolymerisierten Dispersion bei den in Tabelle 1 angegebenen Wer- ten lag. Polymer dispersions were produced by means of semi-continuous emulsion polymerization. The particle sizes were checked using a polystyrene seed in the reactor template and adjusted to 100-300 nm. The quantitative ratios of the monomers used are summarized in Table 1. The water distribution was chosen so that the theoretical solids content of the polymerized dispersion was at the values given in Table 1.
Beispiele B1 und B2 und Vergleichsbeispiele V1 , V2 und V3 Examples B1 and B2 and comparative examples V1, V2 and V3
Gemäß der allgemeinen Vorschrift zu Herstellung der Polymerdispersion wurden mit den in Ta- belle 1 angegebenen Monomeren und in den angegebenen Mengen die erfindungsgemäßen Dis- persionen B1 und B2 bzw. nichterfindungsgemäßen Vergleichsdispersionen V1 , V2 und V3 her- gestellt. In accordance with the general instructions for the preparation of the polymer dispersion, the dispersions B1 and B2 according to the invention or comparative dispersions V1, V2 and V3 not according to the invention were prepared using the monomers specified in Table 1 and in the amounts stated.
Tabelle 1 : Monomerzusammensetzung der Dispersionen Table 1: Monomer composition of the dispersions
pphm: parts per hundered monomers Das Reaktionsprodukt wird anschließend bei Reaktions- oder bei Raumtemperatur mit Hilfe einer Base versetzt und dabei der pH-Wert auf >11 eingestellt. Die genauen Bedingungen der Einstel- lung des pH-Wertes sind den einzelnen Beispielen zu entnehmen. pphm: parts per hundred monomers The reaction product is then mixed with a base at reaction temperature or at room temperature and the pH is adjusted to> 11. The exact conditions for setting the pH value can be found in the individual examples.
Herstellung der Dispersion D1V1 , D2B1 , D3B2, D4V2 und D5V3 durch Nachbehandlung Die Nachbehandlung erfolgte gemäß den in Tabelle 2 zu entnehmenden Angaben. Zunächst wurden V1 , B1 und B2 mittels Natronlauge neutral (pH 7) gestellt. Dann wurden 400 g der so eingestellten Dispersion mit 10 g SILRES® BS 16 versetzt. Falls notwendig wurde anschließend mittels 20 gew.-%iger Kalilauge auf einen pH>1 1 eingestellt (siehe pH-Wert direkt, Tabelle 2). Preparation of the dispersion D1V1, D2B1, D3B2, D4V2 and D5V3 by aftertreatment The aftertreatment was carried out in accordance with the information given in Table 2. First, V1, B1 and B2 were made neutral (pH 7) using sodium hydroxide solution. Then 400 g of the dispersion set in this way were mixed with 10 g of SILRES® BS 16. If necessary, the pH was then adjusted to> 1 1 using 20% strength by weight potassium hydroxide solution (see pH value directly, Table 2).
Tabelle 2: Herstellung der nachbehandelten Dispersionen: Table 2: Preparation of the post-treated dispersions:
Als Kaliummethylsiliconat wurde SILRES® BS 16 eingesetzt. SILRES® BS 16 was used as the potassium methyl siliconate.
Silres BS16 (Firma Wacker, Feststoffgehalt 55 Gew.-%) Silres BS16 (Wacker company, solids content 55% by weight)
Die Dispersionen wurden unter verschiedenen Bedingungen gelagert. Nach verschiedenen La- gerzeiten wurde die Dispersion auf ihre Eigenschaften hin untersucht. Die Ergebnisse sind in Tabelle 3 zusammengefasst. The dispersions were stored under various conditions. After various storage times, the properties of the dispersion were examined. The results are summarized in Table 3.
Tabelle 3: pH-Werte nach Lagerung Table 3: pH values after storage
Die Messergebnisse zeigen, dass sich bei der erfindungsgemäß hergestellten Dispersion D2B1 der pH-Wert auch über eine längere Lagerung hält und sich nicht abschwächt. Bei Dispersio- nen, bei denen der pH-Wert unter einem Wert von 1 1 fällt, ist im Allgemeinen ein verstärkter Befall mit Mikroorganismen zu erwarten. Der Abfall des pH-Wertes lässt sich als Trend bei der Lagerung der Probe D1V1 bereits erkennen. Die erfindungsgemäßen Dispersionen D2B1 wei- sen somit eine bessere Lagerstabilität auf. Herstellung der Dispersion D6B1 und D7B2 durch Nachbehandlung (erfindungsgemäß) The measurement results show that the dispersion D2B1 produced according to the invention maintains the pH even over prolonged storage and does not weaken. In the case of dispersions in which the pH falls below a value of 1 1, an increased infestation with microorganisms is generally to be expected. The drop in the pH value can already be recognized as a trend in the storage of sample D1V1. The dispersions D2B1 according to the invention thus have better storage stability. Preparation of dispersion D6B1 and D7B2 by aftertreatment (according to the invention)
Die Nachbehandlung erfolgte gemäß den in Tabelle 2 zu entnehmenden Angaben. Hierzu wurden die Reaktionsprodukte B1 und B2 zunächst mittels Natronlauge neutral (pH 7) gestellt und an- schließend mit Trasol® KH-K (Kaliwasserglas, der Firma BASF) in einem Massenverhältnis 80 zu 20 (Polymerdispersion/T rasol KW-K) unter Rühren versetzt und homogenisiert. Es ergaben sich die in Tabelle 4 angegeben pH-Werte The aftertreatment was carried out in accordance with the information given in Table 2. For this purpose, the reaction products B1 and B2 were first made neutral with sodium hydroxide solution (pH 7) and then with Trasol ® KH-K (potassium water glass, from BASF) in a mass ratio of 80 to 20 (polymer dispersion / T rasol KW-K) with stirring offset and homogenized. The pH values given in Table 4 resulted
Tabelle 4: pH-Wert der nachbehandelten Dispersionen: Table 4: pH of the post-treated dispersions:
Trasol® KH-K (Kaliwasserglas, Feststoffgehalt 30-40%, K20-Gehalt (ISO 1692): 10,5 - 11 ,2 %; Si02-Gehalt (nach ISO 2124): 23,4 - 24,4) Trasol ® KH-K (potash water glass, solids content 30-40%, K 2 0 content (ISO 1692): 10.5 - 11.2%; Si0 2 content (according to ISO 2124): 23.4 - 24.4 )
Die Dispersionen wurden unter verschiedenen Bedingungen gelagert. Nach verschiedenen La- gerzeiten wurde die Dispersion auf ihre Eigenschaften hin untersucht. Die Ergebnisse sind in Tabelle 5 zusammengefasst. The dispersions were stored under various conditions. After various storage times, the properties of the dispersion were examined. The results are summarized in Table 5.
Tabelle 5: pH-Werte nach Lagerung Table 5: pH values after storage
Jeweils eine Probe der gelagerten Dispersion wurde mit einem Glasstab dünn auf eine Glasplatte appliziert und auf visuellen Defekte hin bewertet. In each case a sample of the stored dispersion was applied thinly to a glass plate using a glass rod and evaluated for visual defects.
Tabelle 6: Koagulatbildung nach Lagerung der Dispersionen D6B1 und D7B2 Table 6: Coagulum formation after storage of dispersions D6B1 and D7B2
Bewertung Ok Ok Rating Ok Ok
Aus den beschriebenen Beispielen wird deutlich, dass Dispersionen hergestellt nach dem bean- spruchten Verfahren sehr stabil sind gegenüber einem hohen pH-Wert. Dies erkennt man daran, dass die physikalischen Eigenschaften wie pH-Wert, Viskosität oder Stabilität (Koagulatbildung) sehr konstanter sind. It is clear from the examples described that dispersions produced by the process claimed are very stable to a high pH. This can be seen from the fact that the physical properties such as pH, viscosity or stability (coagulum formation) are very constant.
Es wurden weitere Untersuchungen vorgenommen. B1 und V3 wurden mit Natronlauge auf neut- ral (pH 7) gestellt und anschließend mit Trasol® KW-N (Kaliumwasserglas mit einem Feststoff- gehalt von 28% im Massenverhältnis 80 zu 20 (Polymerdispersion/T rasol KW-N) unter Rühren versetzt und homogenisiert. Man erhält die Dispersionen D8B1 und D9V3 mit einem Ausgangs- pH-Wert von 10,9. Beide Dispersionen haben niedrige Viskosität und sind fließfähig. Es wurden wiederum Stabilitätsuntersuchungen durchgeführt. Nach einem Tag Lagerung bei 50°C dickte die Dispersion D9V3 stark ein, weshalb keine weiteren Untersuchungen möglich waren, während D8B1 auch nach 14 Tagen bei 50°C Lagerung noch den gleichen pH-Wert von 10,9 aufweist und niedrige Viskosität (keine sichtbare Veränderung zum Ausgangszustand). Further investigations have been carried out. B1 and V3 were adjusted to neutral (pH 7) with sodium hydroxide solution and then Trasol® KW-N (potassium water glass with a solids content of 28% in a mass ratio of 80 to 20 (polymer dispersion / T rasol KW-N) was added with stirring Dispersions D8B1 and D9V3 with an initial pH of 10.9 are obtained. Both dispersions have low viscosity and are flowable. Again, stability tests were carried out. After one day of storage at 50 ° C., the dispersion D9V3 thickened considerably , which is why no further studies were possible, while D8B1 still has the same pH of 10.9 after 14 days at 50 ° C and low viscosity (no visible change to the initial state).
Disperisonsfarbe F1 (erfindungsgemäß) Disperison color F1 (according to the invention)
Es wurde eine Dispersionsfarbe mit folgender Zusammensetzungen hergestellt: A dispersion paint was produced with the following compositions:
Die obige Formulierung hat einen Feststoffgehalt von 48,9 Gew.-% und eine PVK von 71 ,7. Die Farbe hat nach Herstellung einen pH-Wert von 10 und wurde mit 20% gew.-%iger Kalilauge auf einen pH-Wert von 1 1 ,3 eingestellt. Alternativ kann die mit Kaliummethylsiliconat und Kalilauge auf pH>11 eingestellte Dispersion D2B1 als Bindemittel in der Formulierung als Farbe eingesetzt werden und zeigt einen stabilen pH-Wert nach Lagerung. The above formulation has a solids content of 48.9% by weight and a PVC of 71.7. After production, the color had a pH of 10 and was adjusted to a pH of 11.3 with 20% strength by weight potassium hydroxide solution. Alternatively, the dispersion D2B1, which is adjusted to pH> 11 with potassium methyl siliconate and potassium hydroxide solution, can be used as a binder in the formulation as a color and shows a stable pH after storage.
Tabelle 7: Stabilitätsuntersuchungen an der Farbformulierung F1 : Table 7: Stability tests on the color formulation F1:
RT: Raumtemperatur, 25°C Die Dispersionsfarbe zeigt sehr gute Stabilität im Hinblick auf Viskosität und pH-Wert. RT: room temperature, 25 ° C The emulsion paint shows very good stability with regard to viscosity and pH.
Claims
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PCT/EP2019/066242 WO2020002102A1 (en) | 2018-06-28 | 2019-06-19 | Aqueous dispersions and emulsion paints comprising ethylhexyl acrylate-butyl acrylate-styrene copolymers |
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US20240279130A1 (en) * | 2021-05-27 | 2024-08-22 | Arkema Inc. | Storage stable pigmented coating composition |
WO2023038642A1 (en) * | 2021-09-13 | 2023-03-16 | Celanese International Corporation | Wood stains and penetration primers comprising low voc level aqueous dispersions |
CN115124924A (en) * | 2021-12-16 | 2022-09-30 | 环涂士涂料有限公司 | Antivirus emulsion paint composition without bactericide addition, preparation method and application |
WO2023118439A1 (en) | 2021-12-23 | 2023-06-29 | Basf Se | Use of polymer dispersions in waterborne coating formulations and polymer dispersions therefor |
WO2024056515A1 (en) | 2022-09-12 | 2024-03-21 | Basf Se | Method for producing aqueous polymer dispersions from organic waste materials |
US20250026874A1 (en) | 2022-11-02 | 2025-01-23 | Wacker Chemie Ag | Multi-stage copolymers as binder for coating agents |
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AU761916B2 (en) * | 1998-07-24 | 2003-06-12 | Rohm And Haas Company | Polymer dispersions |
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BR112016029350B1 (en) * | 2014-06-18 | 2021-08-03 | Basf Se | AQUEOUS POLYMER DISPERSION, USE OF AN AQUEOUS POLYMER DISPERSION, COATING MATERIAL IN THE FORM OF AN AQUEOUS COMPOSITION, AND, PAINT MATERIAL |
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US11608441B2 (en) * | 2017-11-29 | 2023-03-21 | Celanese International Corporation | Biocide- and ammonia-free polymer dispersions |
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